GB2567957A - Method of monitoring a hydrocarbon reservoir - Google Patents
Method of monitoring a hydrocarbon reservoir Download PDFInfo
- Publication number
- GB2567957A GB2567957A GB1814955.9A GB201814955A GB2567957A GB 2567957 A GB2567957 A GB 2567957A GB 201814955 A GB201814955 A GB 201814955A GB 2567957 A GB2567957 A GB 2567957A
- Authority
- GB
- United Kingdom
- Prior art keywords
- tracer
- fluid
- groups
- reservoir
- derivatives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 25
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- 238000012544 monitoring process Methods 0.000 title claims abstract description 10
- 239000000700 radioactive tracer Substances 0.000 claims abstract description 84
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2823—Oils, i.e. hydrocarbon liquids raw oil, drilling fluid or polyphasic mixtures
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B47/00—Survey of boreholes or wells
- E21B47/10—Locating fluid leaks, intrusions or movements
- E21B47/11—Locating fluid leaks, intrusions or movements using tracers; using radioactivity
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B47/00—Survey of boreholes or wells
- E21B47/10—Locating fluid leaks, intrusions or movements
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/2882—Markers
Abstract
A method of monitoring a hydrocarbon reservoir is disclosed. The method comprises releasing a tracer 1 into the reservoir, producing a fluid from the reservoir and detecting the tracer in the fluid. The tracer comprises a core material 2 having a density greater than 1.5 g/cm3 encapsulated in an encapsulating material 3. The encapsulating material may be a polymer and the settling velocity of the tracer in water may be less than 1 mm/s. The core material may be an upconverting phosphor material.
Description
Method of Monitoring a Hydrocarbon Reservoir
Field of Invention
The present invention concerns a method of monitoring a hydrocarbon reservoir.
Background
It is known to monitor hydrocarbon reservoirs, for example oil wells, using tracers to monitor the production of hydrocarbons and water. Examples of such monitoring include inter-well tracer tests and inflow tracer tests. Chemical tracers are widely used. Such chemical tracers are normally compounds soluble in the production fluids. The chemicals are typically either soluble in the produced water or the produced hydrocarbons. Chemical tracers are typically sent to a laboratory for analysis and therefore may not be suitable for the provision of real-time, on-line information. Such information would be desirable to allow quick decisions to be taken. Fluorescent tracers are an example of optical tracers, which may be more suited to real-time detection using spectrometry methods, but they can be hampered by the natural fluorescence of crude oil.
Fluorescent tracers can also be chemicals that are soluble in the production fluids, but there are a limited number of such compounds that are suitable for reservoir tracing applications.
The present invention seeks to ameliorate some or all of the above problems. The present invention seeks to provide an improved method of monitoring a hydrocarbon reservoir .
Summary of the Invention
According to a first aspect of the invention there is provided a method of monitoring a hydrocarbon reservoir comprising: releasing a tracer into the reservoir, producing a fluid from the reservoir and detecting the tracer in the fluid, wherein the tracer comprises a core material having a density greater than 1.5 g/cm3 encapsulated in an encapsulating material. Preferably the density is greater than 2.0 g/cm3 and more preferably the density is greater than 2.5 g/cm3.
By encapsulating the core material having a density greater than 1.5 g/cm3, the settling velocity of the tracer can be modified. The settling velocity may be a key parameter in determining how faithfully the tracer follows the fluid that it is tracing. Reducing the settling velocity may improve the tracing of the fluid. The tracers of the invention are preferably in the form of tracer particles. It is advantageous, particularly when using online detection methods, to be able to use dense materials in tracers. However, such dense materials have the problem that their settling velocity is high and they thus settle out of the fluid over timescales that are too short to allow them to reliably function as tracers. The encapsulating material may modify the surface properties of the tracer. For example, the encapsulating material may have a hydrophilic surface to improve dispersibility in water or an oleophilic or lyophilic surface to improve dispersal by a solvent or oil. The encapsulating material may act as physical spacer to separate the otherwise aggregating core material. The encapsulating material, for example polymers, at the outer surface of the tracer may provide steric stabilisation to the tracer. Also, the encapsulating material may have a surface charge so as to reduce agglomeration of the tracer. That may be advantageous as agglomeration of the tracer may lead to larger tracer particles, which may therefore settle more rapidly. The kinetic stability of the tracer suspending in the fluid may be improved. It is also one aspect of the invention, as a result of changing the surface properties of the tracers, that the core material can be encapsulated so that the tracers are selectively dispersible in the form of single particles in either oil or water. The encapsulating material may modify the overall density of the tracer. The kinetic stability of the tracer against settling in the fluid can be further enhanced by the change of apparent density. The encapsulating material may be chemically crosslinked or fused together by physical forces. The encapsulating material is preferably at least partially insoluble in the targeted fluids. It may be that the encapsulating material is less dense than the core material and swells on exposure to the reservoir fluid. For example, the encapsulating material may by a polyacrylate. The swelling of the encapsulating material may result in a tracer having a density close (for example, within + /60%, preferably +/- 50%, more preferably +/- 30% and most preferably +/- 10%) to the density of the reservoir fluid.
Preferably the encapsulating material comprises a polymer material. Polymer materials may be readily available and suitable for use as encapsulating materials. They may also have advantageous surface properties or densities to improve the flow-tracing properties of the tracer.
Preferably the encapsulating material is selected from the group consisting of: melamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, melamine-phenol-formaldehyde resin, furan-formaldehyde resin, epoxy resin, ethylene-vinyl acetate copolymer, polypropylene, polyethylene, polypolypropylenepolyethylene copolymer, polyacrylic acid, polymethacrylic acid, poly (ethylene-alt-maleic anhydride) and derivatives, derivatives, derivatives, poly (styrene-alt-maleic anhydride) and poly (isobutylene-alt-maleic anhydride) and poly(methyl vinyl ether-alt-maleic anhydride) and derivatives, polyacrylics or polyacrylates, polyesters, polyurethane, polyamides, polyethers, polyimides, polyether ether ketones, polyolefins, polystyrene and functionalized polystyrene, polyvinylalcohol, polyvinylpyrrolidone, polymaleic anhydride, hydrolysed polymaleic anhydride, gelatine or gelatine derivatives, polyethyleneamine, cellulose and cellulose derivatives, starch and starch derivatives, chitosan, polysaccharides and chemically modified polysaccharides, polyamino acid, peptides, proteins, polysiloxanes, homo and copolymers thereof, crosslinked polymers thereof and mixtures thereof.
Preferably the tracer is in suspension in the fluid. It will be appreciated that an advantage of the invention is that it allows solid, non-soluble tracers to be used for tracing flows in reservoirs. The advantage of such tracers is that they may be easier to detect, with methods such as optical and spectroscopic methods and electrochemical methods, and particularly with online methods, than chemical tracers that dissolve in the fluids. The invention advantageously provides solid tracers that remain in suspension in the fluid for sufficient time for them to be carried with the flow of fluid out of the reservoir. For example, the tracer may remain suspended in the fluid for at least 1 hour, preferably at least 12 hours and more preferably at least 1 day.
Preferably the settling velocity of the tracer in the fluid is reduced compared to the settling velocity of the tracer without the encapsulating material. In that way tracers that would not normally be suitable for reservoir use because they settle out of the fluid too quickly can be used in reservoirs by using them as the core material in the invention. The encapsulating material preferably modifies the density and/or surface properties of the tracer so as to reduce the settling velocity compared to the tracer without the encapsulating material (that is, compared to the un-encapsulated core material).
Preferably the settling velocity of the tracer is not more than one tenth, more preferably one twentieth and yet more preferably one hundredth, of the settling velocity of the un-encapsulated core material.
It may be that the fluid is an aqueous fluid produced by the reservoir. It is often useful to trace the flow of aqueous fluids, such as formation water, from a hydrocarbon reservoir, for example to determine the zone(s) of the reservoir in which water has broken through. When the fluid is an aqueous fluid the encapsulating material may be selected so as to interact with the aqueous fluid to better suspend the tracer in the aqueous fluid. For example, the encapsulating material may have a hydrophilic surface. It is desirable to trace aqueous fluids produced by the reservoir, for example so as to determine an inflow profile of where in the reservoir the aqueous fluids originate. For example, different tracers may be positioned in different zones of the reservoir and the amounts of the tracers detected in the produced aqueous fluids used to determine the inflow profile of the aqueous fluids from each zone.
When the fluid is an aqueous reservoir fluid, the settling velocity of the tracer in water is preferably not more than 1 mm/s. More preferably the settling velocity of the tracer in water is not more than 0.1 mm/s .
It may be that the fluid is a hydrocarbon fluid produced by the reservoir. It is desirable to trace hydrocarbon fluids produced by the reservoir, for example so as to determine an inflow profile of where in the reservoir the fluids originate. For example, different tracers may be positioned in different zones of the reservoir and the amounts of the tracers detected in the produced hydrocarbon fluids used to determine the inflow profile of the hydrocarbon fluids from each zone. When the fluid is a hydrocarbon fluid produced by the reservoir, the settling velocity of the tracer in Dowtherm Q is preferably not more than 1 mm/s and more preferably not more than 0.1 mm/s. Dowtherm Q may be a suitable model fluid for characterising the settling velocity of the tracer so as to determine the tracer's ability to faithfully follow the flow of hydrocarbon fluids produced by the reservoir.
The tracer can be tailored to be preferentially dispersible and suspending in aqueous fluid, or preferentially dispersible and suspending in hydrocarbon based oil fluid, or dispersible and suspending in both agueous fluid and hydrocarbon based oil fluid. The tailoring may be made by adjusting the chemical composition of the chemical groups present at the outer surface of the tracer. The tailoring is also made by controlling the structure and morphology of the outer surface of the tracer. We have found that by tailoring the ratio of the different chemical groups attached to the polymer chain present at the outer surface, the selectivity of the tracers to disperse and suspend in different fluids can be effectively controlled.
A first family of chemical groups are classified as predominantly hydrophobicity/oleophilicity contributing moieties. This family of chemical groups includes alkyl groups (such as methyl, ethyl propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, heptyl, hexyl, octyl, nonyl, undecyl, dodecyl), vinyl groups, benzyl groups, substituted benzyl groups, benzyl alkyl groups, chlorinated or brominated alkyl benzyl groups, chlorinated or brominated benzyl groups, ethylenic linkages, propylene linkages, triazine linkages, ethylene linkages, styrenic linkages, siloxane and substituted siloxane groups.
A second family of chemical groups are classified as predominantly hydrophilicity/oleophobicity contributing moieties. This family of chemical groups includes hydroxyl, carboxylate, amide, amine, glucose unit, sulphonate, alkyl sulphate, aryl sulphate, alkylated amine, anhydride, carbonyl, acetyl, isocyanate, phosphate, sulfate, nitrile, nitro, thiol, aldehyde, quaternised amine, N-alkylamide, N-methylol, silanol, pyrrolidonyl, pyridinyl, pyrimidinyl, ester linkage, urethane linkage, ester linkage and amide linkage.
Preferably the tracers are tailored to be preferentially dispersible and suspending in hydrocarbon based oil fluid by bearing one or more predominantly hydrophobic/oleophilic chemical groups at the outer surface of the tracer. The hydrophobic groups preferably account for greater than 85%, more preferably greater than 90% and most preferably greater than 95% of the chemical groups present at the outer surface of the tracer. The chemical groups are chemically bonded to one or more polymers which are part of the encapsulating materials .
Preferably the tracers are tailored to be preferentially dispersible and suspending in aqueous fluid by bearing one or more predominantly hydrophilic/oleophobic chemical groups at the outer surface of the tracer. The hydrophilic groups preferably account for greater than 20%, more preferably greater than 30%, and yet more preferably greater than 40% of the chemical groups present at the outer surface of the tracer. The chemical groups are chemical bonded to one or more polymers which are part of the encapsulating materials.
Preferably the tracers are tailored to be dispersible and suspending in both aqueous fluids and hydrocarbon based oil fluids. This is achieved by reaching a balance of hydrophobic/oleophilic chemical groups and hydrophilic/ oleophobic chemical groups at the outer surface of the tracer .
The core material can be an inorganic or organic pigment. Examples of inorganic pigments are known to the skilled person and include aluminium pigments, copper pigments, and others. Examples of organic pigments are known to the skilled person and include anthraquinones, quinacridone/quinons, Azo pigment, stilbene pigments, diketopyrrolopyrrol pigment and isoindolines. The pigment can be, for example, fluorescent or phosphorescent.
Preferably the core material has a particle size (D50) of from 5 nm to 2000 nm and most preferably from 10 nm to 1000 nm.
Preferably the core material is a phosphor material. It may be that the core material is a down conversion phosphor. Preferably the core material is an upconverting phosphor material. The use of phosphor materials, and particularly upconverting phosphor materials, may be particularly advantageous in systems where the detection is carried out on-line. The upconverting phosphors may be particularly suited to on-line detection, for example using a detector with an excitation light source and a detector for detecting the emitted light. The phosphors may produce a strong signal that can be reliably detected in the short time-scales available for on-line detection. The upconverting nature of the phosphors means that the emitted light is at a shorter wavelength than the excitation light and can therefore by readily distinguished from any other fluorescence that would occur at a longer wavelength.
Preferably the tracer is in the form of particles having a core consisting of the upconverting phosphor material and surrounded by a layer of the encapsulating material. Many prior art methods use chemical tracers that dissolve in the fluids. However, such tracers may be more difficult to detect, particularly on-line. Using a tracer particle may facilitate detection and provide opportunities for using detection and tracer separation or concentration techniques that are not available for dissolved chemical tracers. By encapsulating the phosphor material in a layer of the encapsulating material, the overall properties of the tracer, such as density and surface properties, may be controlled so as to cause the tracer to more faithfully follow the flow of a particular fluid type. For example, the surface properties may be controlled so as to encourage suspension of the tracer in hydrocarbon fluids.
Preferably the upconverting phosphor is a lanthanide, or optionally other transition metal, doped particle, preferably selected from the group consisting of: NaYF4, NaGdF4, LiYF4, YF3, CaF2, Gd2O3, LaF3, Y2O3, ZrO2, Y2O2S and La2O2S doped with lanthanide ions, such as Yb3+ or Er3+.
Preferably the detecting is carried out on-line and comprises exciting the produced fluid with a light source and detecting emitted light from the upconverting phosphor. The detection is preferably carried out using a detector comprising the light source, the light source being positioned so as to transmit light into a conduit, such as a pipeline, carrying the produced fluid, the detector further comprising a light detector configured to detect light emitted from the produced fluid and a processor configured to determine an amount of the tracer, for example a weight/weight concentration of the particles in the fluid, based on an intensity of light detected by the light detector. Preferably the light detector is a spectrometer configured to detect a spectrum of the light emitted and the processor is configured to determine an amount of the tracer based on an intensity of light in a region of interest of the spectrum. For example, it may be that the intensity of light in the region of interest is proportional to the amount of the tracer. It will be appreciated that while the detector may comprise a light detector that measures a received light intensity, for example through filters focussed on a region of interest in the light spectrum, it may be advantageous to use a spectrometer to record a spectrum of the light emitted as the processor can then detect the presence of one or more tracers emitting in different parts of the spectrum from a single recorded spectrum. That may permit the simultaneous detection of multiple tracers, which may be particularly advantageous in an on-line detector. Preferably the light source is a visible or infra-red light source.
Upconverting phosphors may be particularly advantageous as tracers and therefore, in an aspect of the invention there is provided a method of monitoring a hydrocarbon reservoir comprising: releasing a tracer into the reservoir, producing a fluid from the reservoir and detecting the tracer in the fluid, wherein the tracer comprises a core material comprising an upconverting phosphor, the core material being encapsulated in an encapsulating material. It will be appreciated that any features described above or below in relation to the first aspect of the invention may apply equally to this aspect of the invention. For example, the core material may consist of the upconverting phosphor. As another example, the upconverting phosphor may have a density of greater than 1.5 g/cm* 3.
It will be appreciated that features described in relation to one aspect of the invention may be equally applicable to other aspects of the invention. It will also be appreciated that optional features may not apply, and may be excluded from, certain aspects of the invention.
Description of the Drawings
The invention will now be described, by way of example, with reference to the following drawings, of which:
Fig 1 is a schematic representation of a tracer for use in a method according to the invention; and
Fig 2 is a schematic representation of a method according to the invention.
Detailed Description
In figure 1 a tracer 1 comprises a core material 2 having a density greater than 1.5 g/cm3. The core material 2 may for example be an upconverting phosphor such as
NaYF4:Yb:Er and may have a particle size (D50) in the range 5 nm to 2000 nm, for example about 400 nm. The core material 2 is encapsulated by an encapsulating material
3, which may for example comprise a polymer such as poly (ethylene-co-maleic acid) and cured melamine formaldehyde resin. The encapsulating material 3 may be added, for example, by mixing the core material 2 in a solution of the encapsulating material 3 to form a colloid which is then cured, filtered and dried to form the tracer 1.
In figure 2, a method of monitoring a hydrocarbon reservoir 10 comprises releasing a tracer 14 into the reservoir 10, producing fluid from the reservoir 10 and detecting the tracer 14 in the fluid so as to monitor the reservoir 10. The tracer 14 may for example be a tracer as described in relation to figure 1. The tracer 14 is introduced into the reservoir 10 in a release system 11. The release system 11 may for example be a polymer release system whereby the tracer 14 is embedded in a polymer material that degrades to allow steady release of the tracer 14. The tracer 14 is released from the release system 11 and carried by the production flow 12 of the reservoir fluids to the surface where it is detected. The reservoir 10 includes a surface facility 15 and the detection may be carried out at the surface facility 15, either by detecting the tracer 14 in real-time using an online detector, or by sampling the produced fluids and sending the samples to a laboratory for analysis to detect the tracer 14. Preferably the analysis is carried out online in real time. For example, the tracer may comprise an up-converting phosphor and the detection may involve exciting the up-converting phosphor with an excitation light source and detecting the light emitted by the up-converting phosphor in response to that excitation. That detection may, for example, be carried out using a spectrometer. Up-converting phosphors may be particularly useful for such online detection as the emission is at a shorter wavelength to the excitation and there is therefore no interference with the measurement from the natural fluorescence of the reservoir fluids, which occurs at longer wavelengths to the excitation.
Comparative Example 1 -- Settling of commercial upconversion pigments in water
A test of settling of a commercially available upconversion phosphor pigment (NaYF4:Yb: Er) was performed. The up-conversion phosphor pigment was used as received for the tests. The average size of the pigment particles was 2.8 micron (D50, measured by laser diffraction using a Malvern Mastersizer 3000 instrument).
0.2 gram of the pigment was mixed with 10.0 gram of deionized water in a 20 mL glass vial at room temperature and shake to obtain an opaque, milk-white coloured suspension. Upon stopping shaking, the pigments started to sink, and in less than 3 seconds settled to the bottom of the vial and left quite clear liquor on the top.
Comparative Example 2 -- Settling of milled commercial up-conversion pigments in water
The commercial up-conversion phosphor pigment (NaYF4:Yb: Er) used in comparative example 1 was beadmilled to reduce the particle size and then used for the tests. The average size of the original pigment particles was 2.8 micron (D50, measured by laser diffraction using Malvern Mastersizer 3000 instrument). lOOg of the commercial pigment was mixed with 300 grams water and milled with a Netzsch LabStar milling machine using Zr beads (ZetaBeads) for 40 minutes. The average size of the milled pigment particles was 0.4 micron (D50, measured by laser diffraction using a Malvern Mastersizer 3000 instrument). Transmission electron microscope observation showed that the primary milled pigment particle size was ~20 nm and they tended to aggregated into clusters of ~ 4 0 0 nm.
0.2 gram of the milled pigment was mixed with 10.0 gram of deionized water in a 20 mL glass vial at room temperature and shake to obtain an opaque, milk-white coloured suspension. Upon stopping shaking, the milled pigment started to sink, and within 30 seconds settled to the bottom of the vial and left quite clear liquor on the top .
Example 1 -- microencapsulation of milled commercial upconversion pigments in accordance with the invention
The milled commercial up-conversion phosphor pigment (NaYF4:Yb: Er) was encapsulated with a polymer layer in accordance with the invention.
The commercial up-conversion phosphors pigment (NaYF4:Yb: Er) was bead-milled to reduce the particle size and then used for the tests. The average size of the original pigment particles was 2.8 micron (D50, measured by laser diffraction using Malvern Mastersizer 3000 instrument). 100 grams of the commercial pigment was mixed with 300 grams of water and milled with a Netzsch LabStar milling machine using Zr beads (ZetaBeads) for 40 minutes. The average size of the milled pigment particles was 0.4 micron (D50, measured by laser diffraction using a Malvern Mastersizer 3000 instrument). Transmission electron microscope observation showed that the primary milled pigment particle size was ~20 nm and they tended to aggregated into cluster of ~400 nm.
0.453 grams poly (ethylene-alt-maleic anhydride) was fully neutralised in 10 gram water with aqueous NaOH. 10 gram of the above milled phosphor pigment was mixed with 120 gram of water, the neutralised polymer solution and 1.7 grams Beetle resin (BIP) and homogenised using a Silverson L4R laboratory homogenizer at pH 4.0 for 1 hour at room temperature. The formed colloid was cured in a glass reactor at 33 °C for 2 hours. A total of 2.5 gram of Beetle resin was added during the process. The mixture was continuously cured at 55-65 °C for 2 hours and 80 °C for 2 hours. The mixture was then cooled to room temperature and filtered. The filtrate was dried at room temperature in air for 3 days and finally dried in a vacuum oven at room temperature for 8 hours. Free flowing powder was obtained.
Example 2 -- Slow Settling of microencapsulated upconversion pigments in water in accordance with the invention
0.2 gram of the microencapsulated pigment obtained from Example 1 was mixed with 10.0 gram of deionized water in a 20 mL glass vial at room temperature and shake to obtain an opaque, milk-white coloured suspension. After shaking was stopped, the pigments settled, but at a low speed. It took 10 minutes for most of the pigments to settle to the bottom of the vial. The microencapsulation according to the invention had thus increased the settling time, or reduced the settling velocity, by a factor of 20 compared to the non-encapsulated product of the prior art. It will be appreciated that such an increase can have a significant benefit, for example to cause a tracer material to more faithfully follow a flow that it is intended to trace.
It will be appreciated that the embodiments set out above are examples of the invention and that the skilled person would appreciate that variations were possible within the scope of the invention.
Claims (21)
1. A method of monitoring a hydrocarbon reservoir comprising: releasing a tracer into the reservoir, producing a fluid from the reservoir and detecting the tracer in the fluid, wherein the tracer comprises a core material having a density greater than 1.5 g/cm3 encapsulated in an encapsulating material.
2. A method according to claim 1, wherein the encapsulating material is a polymer material.
3. A method according to claim 2, wherein the encapsulating material is selected from the group consisting of: melamine-formaldehyde resin, ureaformaldehyde resin, phenol-formaldehyde resin, melamine-phenol-formaldehyde resin, furanformaldehyde resin, epoxy resin, ethylene-vinyl acetate copolymer, polypropylene, polyethylene, polypolypropylene-polyethylene copolymer, polyacrylic acid, polymethacrylic acid, poly (ethylene-alt-maleic anhydride) and derivatives, poly (styrene-alt-maleic anhydride) and derivatives, poly (isobutylene-alt-maleic anhydride) and derivatives, poly(methyl vinyl ether-alt-maleic anhydride) and derivatives, polyacrylics or polyacrylates, polyesters, polyurethane, polyamides, polyethers, polyimides, polyether ether ketones, polyolefins, polystyrene and functionalized polystyrene, polyvinylalcohol, polyvinylpyrrolidone, polymaleic anhydride, hydrolysed polymaleic anhydride, gelatine or gelatine derivatives, polyethyleneamine, cellulose and cellulose derivatives, starch and starch derivatives, chitosan, polysaccharides and chemically modified polysaccharides, polyamino acid, peptides, proteins, polysiloxanes, homo and copolymers thereof, crosslinked polymers thereof and mixtures thereof.
4. A method according to any preceding claim, wherein the outer surface of the tracer comprises one or more predominantly hydrophobic/oleophilic groups.
5. A method according to claim 4, wherein the groups are selected from: alkyl groups, vinyl groups, benzyl groups, substituted benzyl groups, benzyl alkyl groups, chlorinated or brominated alkyl benzyl groups, chlorinated or brominated benzyl groups, ethylenic linkages, propylene linkages, triazine linkages, ethylene linkages, styrenic linkages, siloxane and substituted siloxane groups.
6. A method according to any preceding claim, wherein the outer surface of the tracer comprises one or more predominantly hydrophilic/oleophobic groups.
7. A method according to claim 6, wherein the groups are selected from: hydroxyl, carboxylate, amide, amine, glucose unit, sulphonate, alkyl sulphate, aryl sulphate, alkylated amine, anhydride, carbonyl, acetyl, isocyanate, phosphate, sulfate, nitrile, nitro, thiol, aldehyde, guaternised amine, Nalkylamide, N-methylol, pyridinyl, pyrimidinyl, silanol, pyrrolidonyl, ester linkage, urethane linkage, ester linkage and amide linkage.
A method according to any preceding claim, wherein the tracer is in suspension in the fluid.
9. A method according to claim 8, wherein the settling velocity of the tracer in the fluid is reduced compared to the settling velocity of the tracer without the encapsulating material.
10. A method according to any preceding claim, wherein the fluid is an aqueous fluid produced by the reservoir .
11. A method according to claim 10, wherein the settling velocity of the tracer in water is not more than 1 mm/s .
12. A method according to any of claims 1 to 9, wherein the fluid is a hydrocarbon fluid produced by the reservoir .
13. A method according to claim 12, wherein the settling velocity of the tracer in Dowtherm Q is not more than 1 mm/s.
14. A method according to any preceding claim wherein the core material has a D50 in the range from 5 nm to 2000 nm.
15. A method according to any preceding claim, wherein the core material is an upconverting phosphor material.
16. A method according to claim 15, wherein the tracer is in the form of particles having a core consisting of the upconverting phosphor material and surrounded by a layer of the encapsulating material.
17. A method according to claim 15 or claim 16, wherein the upconverting phosphor is selected from the group consisting of: NaYF4, NaGdF4, LiYF4, YF3, CaF2, Gd2O3, LaF3, Y2O3, ZrO2, Y2O2S and La2O2S doped with lanthanide ions.
18. A method according to any of claims 15 to 17, wherein the detecting is carried out on-line and comprises exciting the produced fluid with a light source and detecting emitted light from the upconverting phosphor.
19. A method according to claim 18, wherein the detection is carried out using a detector comprising the light source, the light source being positioned so as to transmit light into a conduit carrying the produced fluid, the detector further comprising a spectrometer configured to record a spectrum of light emitted from the produced fluid and a processor configured to determine an amount of the tracer based on an intensity of light detected by the spectrometer in a region of interest of the spectrum.
20. A method according to claim 19, wherein the intensity of light in the region of interest is proportional to the amount of the tracer.
21. A method according to any of claims 18 to 20, wherein the light source is a visible or infra-red light source.
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| GBGB1715107.7A GB201715107D0 (en) | 2017-09-19 | 2017-09-19 | Method of monitoring a hydrocarbon reservoir |
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| GB1814955.9A Expired - Fee Related GB2567957B (en) | 2017-09-19 | 2018-09-14 | Method of monitoring a hydrocarbon reservoir |
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| US20220412210A1 (en) * | 2021-06-24 | 2022-12-29 | Halliburton Energy Services, Inc. | Monitoring wellbore fluids using metal ions from tracers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010140032A2 (en) * | 2009-06-03 | 2010-12-09 | Schlumberger Technology B.V. | Use of encapsulated tracers |
| US20130017610A1 (en) * | 2011-07-12 | 2013-01-17 | Jeffery Roberts | Encapsulated tracers and chemicals for reservoir interrogation and manipulation |
| US20150322776A1 (en) * | 2013-08-01 | 2015-11-12 | Tyler W. Blair | Oil and Gas Well Fracture Liquid Tracing Using DNA |
| US20160075937A1 (en) * | 2014-09-17 | 2016-03-17 | Sandia Corporation | Proppant compositions and methods of use |
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| US5929437A (en) * | 1995-08-18 | 1999-07-27 | Protechnics International, Inc. | Encapsulated radioactive tracer |
| WO2014207000A1 (en) * | 2013-06-24 | 2014-12-31 | Institutt For Energiteknikk | Mineral-encapsulated tracers |
| GB201507480D0 (en) * | 2015-04-30 | 2015-06-17 | Johnson Matthey Plc | Oil field chemical delivery fluids, methods for their use in the targeted delivery of oil field chemicals to subterranean hydrocarbon reservoirs and methods |
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- 2017-09-19 GB GBGB1715107.7A patent/GB201715107D0/en not_active Ceased
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- 2018-09-14 WO PCT/GB2018/052613 patent/WO2019058098A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010140032A2 (en) * | 2009-06-03 | 2010-12-09 | Schlumberger Technology B.V. | Use of encapsulated tracers |
| US20130017610A1 (en) * | 2011-07-12 | 2013-01-17 | Jeffery Roberts | Encapsulated tracers and chemicals for reservoir interrogation and manipulation |
| US20150322776A1 (en) * | 2013-08-01 | 2015-11-12 | Tyler W. Blair | Oil and Gas Well Fracture Liquid Tracing Using DNA |
| US20160075937A1 (en) * | 2014-09-17 | 2016-03-17 | Sandia Corporation | Proppant compositions and methods of use |
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| WO2019058098A1 (en) | 2019-03-28 |
| GB201814955D0 (en) | 2018-10-31 |
| GB201715107D0 (en) | 2017-11-01 |
| GB2567957B (en) | 2020-02-12 |
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