Sulfide and process chemical treatment of production fluids using metal oxide particles

Abstract

Methods and apparatus for treatment of hydrocarbon streams containing hydrogen sulfide are described herein. The hydrocarbon stream is contacted with metal oxide particles loaded with a hydrogen sulfide scavenger and a production aid. The hydrocarbon sulfide scavenger removes hydrogen sulfide from the hydrocarbon stream and the production aid moves from the metal oxide particles into the hydrocarbon stream to facilitate subsequent processing.

Description

SULFIDE AND PROCESS CHEMICAL TREATMENT OF PRODUCTION FLUIDS USING METAL OXIDE PARTICLESCROSS REFERENCE PARAGRAPH

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 387,824, entitled ‘SULFIDE AND PROCESS CHEMICAL TREATMENT OF PRODUCTION FLUIDS USING METAL OXIDE PARTICLES," filed December 16, 2022, the disclosure of which is hereby incorporated herein by reference.FIELD

[0002] This patent application describes methods of treating fluids produced from an oil well. Specifically, methods of treating such fluids to add process chemicals and remove sulfide species are described herein.BACKGROUND

[0003] Hydrocarbon produced from oil wells commonly contains sulfide species such as hydrogen sulfide (H2S) that must be removed from the produced fluids. It is also common to add process chemicals to such fluids to aid surface processing of the produced fluids. Efficient and effective ways to perform such treatments are always sought.SUMMARY

[0004] Embodiments described herein provide a method of treating a hydrocarbon stream, the method including passing the hydrocarbon stream through a bed of metal oxide particles loaded with a hydrogen sulfide scavenger and a hydrocarbon production aid.

[0005] Other embodiments described herein provide a method that includes mixing a hydrocarbon stream containing hydrogen sulfide with a treatment material comprising a carrier fluid and metal oxide particles loaded with a hydrogen sulfide scavenger and a hydrocarbon production aid; and removing hydrogen sulfide from the hydrocarbon stream using the hydrogen sulfide scavenger.

[0006] Other embodiments described herein provide a method that includes obtaining a treatment material comprising a carrier fluid and metal oxide particles loaded with ahydrogen sulfide scavenger and a hydrocarbon production aid; pumping the treatment material into a subterranean formation to contact a hydrocarbon material containing hydrogen sulfide within the subterranean formation; and reacting the hydrogen sulfide scavenger with the hydrogen sulfide within the subterranean formation.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Fig. 1 is a schematic flow diagram summarizing a method according to one embodiment.

[0008] Fig. 2 is a schematic flow diagram summarizing a method according to another embodiment.

[0009] Fig. 3 is a schematic flow diagram summarizing a method according to another embodiment.DETAILED DESCRIPTION

[0010] Materials conventionally used to provide hydrogen sulfide scavenger treatment for produced hydrocarbon streams are used to deliver production chemicals such as scale inhibitors, corrosion inhibitors, bactericides, and water clarifiers. Fig. 1 is a schematic process diagram of a method 100 of making a hydrocarbon treatment material. At 102, a metal oxide containing raw material is sized and sorted to provide a plurality of metal oxide particles having a desired particle size distribution. The metal oxide particles will be used to provide hydrogen sulfide scavenging and delivery of production chemicals to a produced hydrocarbon stream. Particle sizing can be used to select rate of scavenging and chemical delivery, with smaller particles having a higher rate and larger particles having a lower rate.

[0011] The particles are generally produced by grinding or otherwise contacting together metal oxide materials or metal oxide containing materials to provide contact force between metal oxide structures that breaks down the structures into smaller structures. A mill, blender, mixer, crusher, or other solids equipment that can reduce the size of solid particles can be used. Processing is performed for a time selected to yield a particle size distribution expected to provide a substantial fraction of particles having the desired size.Sorting is performed using mesh screens. Over-size particles are recycled to the sizing, and under-size particles are discarded or routed to other uses. In some cases, particle sizes ranging from 10 pm to 100 pm are produced and / or selected. Processing time depends on the solid raw materials to be used for producing the metal oxide particles. Larger particles and harder materials take longer to reduce to a target size or size range. In some cases, a solid raw material is subjected to size reduction for a duration of about 30 to 60 minutes.

[0012] The metal oxide particles can be homogeneous or a mixture of materials. Additionally, each metal oxide particle can be homogeneous or a mixture of materials. In some cases, each metal oxide particle is a particle coated with a metal oxide material. Thus, in some cases, each metal oxide particle can have a core made of a support material and coated with a metal oxide material. In some cases, the core is a clay material. The metal oxide coating material can be homogeneous or a mixture of metal oxide materials.

[0013] At 104, the metal oxide particles are exposed to a loading mixture containing at least a hydrogen sulfide scavenger and a production aid. The hydrogen sulfide scavenger is a liquid material miscible with water, such as triazine or another material that reacts with hydrogen sulfide. The production aid is a scale inhibitor, a corrosion inhibitor, a water clarifier, or another production aid. Scale inhibitors that can be used include phosphonic acid salts; co-polymers or ter-polymers of maleic, acrylic, aspartic, vinyl phosphonic acids, sulfonic acids, and AMPS. Corrosion inhibitors that can be used include primary and secondary amines, imidazoline, imines, and quaternary amines. Combinations of such scale inhibitors and corrosion inhibitors can be used. The hydrogen sulfide scavenger and the production aid are added to water to form an aqueous dispersion or solution that serves as the loading mixture. The metal oxide particles absorb and / or adsorb the hydrogen sulfide scavenger and the production aid, and more than one hydrocarbon scavenger and more than one production aid can be loaded onto the metal oxide particles.

[0014] The metal oxide particles can be exposed to the loading mixture by supporting the metal oxide particles in a bed and flowing the loading mixture through the bed. Alternately, the metal oxide particles can be exposed to the loading mixture by injecting the metal oxide particles into a flowing stream of the loading mixture to form a flowingdispersion and filtering the loaded metal oxide particles from the dispersion to recover the loaded metal oxide particles. A combination of such methods can also be used. Particle density during the exposure can be controlled and selected to provide a desired exposure intensity, which can affect loading of the particles. For example, in one case of performing loading of metal oxide particles in a bed format, particle density of about 50% can be obtained by structuring a bulk volume of metal oxide particles within a bed volume about twice the size of the bulk volume. The bed volume can be controlled using liquid- permeable particle restraints, such as mesh screens and / or baskets.

[0015] The metal oxide particles may be exposed to the loading mixture during sizing or after sizing. Exposing the metal oxide particles after sizing subjects the metal oxide particles to uniform loading so all the metal oxide particles receive a similar loading. Exposing the metal oxide particles during sizing can promote uniform sizing by lubricating the particles somewhat during the sizing process, but particles can receive different loading profiles because different surfaces of the particles become exposed to the loading mixture at different times and therefore have different loading exposure times. Thus, when the metal oxide particles are exposed to the loading mixture during sizing, the particles receive a more varied loading profile. Depending on the embodiment, the more uniform loading profile or the more varied loading profile may be desired. For example, the more uniform loading profile will generally exhibit a relatively flat unloading characteristic. In other words, as a hydrocarbon mixture is passed through metal oxide particles having a uniform loading profile, the metal oxide particles generally release production aid and scavenge hydrogen sulfide at similar rates, resulting in an unloading profile that quickly rises to a plateau and quickly falls upon depletion. The varied loading profile can exhibit a less plateaued unloading profile arising from the more mottled loading of the particles resulting from the non-uniform exposure to loading mixture during sizing.

[0016] The loading mixture can be concentrated or dilute depending on requirements of a given process. A concentrated loading mixture will add more scavengers and production aids to the particles, up to the sorption limit of the particles. Smaller particles will generally load with more chemicals generally due to the larger surface area available for mass transport. Larger particles, however, can be useful where a slower release of production aid and slower hydrogen sulfide scavenging is desired. In one example, asolution of 30% by weight of triazine and 30% by weight of poly-phosphono carboxylic acid (PPCA) in water can be used as a loading mixture.

[0017] The amount of production aid and hydrogen sulfide scavenger used in the loading mixture can be determined by expected concentration of hydrogen sulfide in the hydrocarbon to be produced. Where a production stream is expected to contain more hydrogen sulfide, a ratio of hydrogen sulfide scavenger to production aid in the loading mixture can be increased, and vice versa. Amount of production aid and hydrogen sulfide scavenger can also be determined by sorption capacity of the metal oxide materials for the scavengers and production aids. Where the sorption capacity of individual metal oxides for individual scavenger or production aid chemicals is known, a straightforward linear calculation can provide a composition target for the loading mixture.

[0018] Duration of exposing the metal oxide particles to the loading mixture affects loading of the particles with hydrogen sulfide scavenger and production aid. Concentration of the loading mixture also affects loading. Exposure profile, whether of all particles at once under the same conditions or during size reduction, also affects loading and loading profile of the particles. Exposure duration can be selected based on loading mixture concentration and desired loading profile of the particles. In one example, particles that have been previously sized are exposed to an aqueous loading mixture having about 30% by weight of triazine and 30% by weight of PPCA for a duration of about 1 hour.

[0019] In this case, the metal oxide particles are exposed to hydrogen sulfide scavenger and production aid at the same time, but in other cases, the metal oxide particles can be exposed to scavenger and production aid in any combination of sequentially and at the same time, and multiple such exposures can be performed to complete the loading of the metal oxide particles. For example, in one case, the metal oxide particles can be exposed first to hydrogen sulfide scavenger and then to production aid. In another case, the metal oxide particles can be exposed first to production aid and then to hydrogen sulfide scavenger. These processes are performed by exposing the metal oxide particles to a first loading mixture comprising a hydrogen sulfide scavenger and a second loading mixture comprising a production aid at different times, in any order. Exposure of the metal oxide particles to the first and second loading mixtures can be repeated, if desired, andcan be supplemented with exposure to loading mixture having both hydrogen sulfide scavenger and production aid.

[0020] At 106, the loaded metal oxide materials are optionally separated from the loading mixture, if excess loading mixture remains. The metal oxide materials may be dried, or may be used in a moist state. Flowing a hydrocarbon stream containing hydrogen sulfide and intended for further processing through the loaded metal oxide material treats the hydrocarbon steam by reacting hydrogen sulfide with the hydrogen sulfide scavenger (one or more) added to the metal oxide particles and adds production aids to the hydrocarbon stream by removing the production aids from the metal oxide particles.

[0021] It should be noted that sorption of materials into the metal oxide particles can be affected by temperature. Performing the loading process at higher temperature can load the metal oxide particles with hydrogen sulfide scavenger and production aid at a faster rate. In some cases, the loading mixture may be heated to near a boiling point of the loading mixture to maximize the rate of loading. In other cases, the loading mixture may be heated slightly or not at all depending on the needs of particular processes.

[0022] It should also be noted that a loaded metal oxide material may be formed by loading two or more separate lots of metal oxide particles with hydrogen sulfide scavenger and production aid and then mixing the lots together to form the loaded metal oxide material. In such cases, a first quantity of metal oxide particles is exposed to a first loading mixture and a second quantity of metal oxide particles is exposed to a second loading mixture. The first quantity of metal oxide particles and the second quantity of metal oxide particles may be the same, or may differ in composition, particle size distribution, and / or quantity. Likewise, the first loading mixture and the second loading mixture may be the same or may differ in composition and / or quantity. The first quantity of metal oxide particles and the second quantity of metal oxide particles may be exposed at the same conditions or at conditions that may differ in temperature, pressure, and / or exposure time.

[0023] As noted above, the two lots of metal oxide particles loaded with hydrogen sulfide scavenger and production aid may be mixed together to form a loaded metal oxide material. Alternately, the two loaded metal oxide materials may be used separately totreat a hydrocarbon stream using a sequential treatment by contacting the first loaded metal oxide material and then contacting the second loaded metal oxide material. Where the two lots of loaded metal oxide material are used as a mixture, the mixture will have a non-uniform and / or non-normal distribution of any of particle type, particle size, and loading of the various chemicals. In some cases, the two lots of loaded metal oxide particles can be disposed in a structured manner such that contacting of the two lots of loaded metal oxide particles occurs in a desired way. For example, the two lots of loaded metal oxide particles may be structured into two or more layers such that a hydrocarbon stream contacts the two lots in a patterned way.

[0024] It should also be noted that a first lot of metal oxide particles can be loaded with hydrogen sulfide scavenger, a second lot of metal oxide particles can be loaded with production aid, and the two lots mixed together to form a loaded metal oxide particle mixture having a first plurality of metal oxide particles loaded with a hydrogen sulfide scavenger and a second plurality of metal oxide particles loaded with a production aid. Alternately, the first lot of loaded metal oxide particles and the second lot of loaded metal oxide particles can be used separately and sequentially. The two lots of loaded metal oxide particles perform different treatments when used on a hydrocarbon stream containing hydrogen sulfide. The first lot removes hydrogen sulfide from the hydrocarbon stream and the second lot releases production aid into the hydrocarbon stream. These two treatments can be performed together in one exposure or separately and sequentially in any order.

[0025] It should also be noted that multiple different lots of loaded metal oxide particles can be loaded with any number and combination of hydrogen sulfide scavengers and production aids. Such lots of loaded metal oxide particles can be mixed together in any convenient way to form a loaded metal oxide particle mixture configured to perform a combined treatment on a hydrocarbon stream, or such lots can be used separately and sequentially to perform the treatments on the hydrocarbon stream at different times. Each lot of metal oxide particles can be the same as every other lot of metal oxide particles, or some or all of the lots of metal oxide particles may differ in composition and / or particle size distribution.

[0026] Fig. 2 is a flow diagram summarizing a method 200 according to another embodiment. The method 200 is a method of treating a hydrocarbon stream containing hydrogen sulfide. At 202, a metal oxide particle material loaded with a hydrogen sulfide scavenger and a production aid is disposed in a vessel. The vessel may be a tank, drum, or pipe, and may include a support structure for the metal oxide particle material, such as a screen. The vessel is configured to allow a fluid to flow through the vessel and contact the loaded metal oxide particle material substantially without removing the metal oxide particles from the vessel. The metal oxide particle material may be prepared by any of the methods described above in connection with Fig. 1 .

[0027] At 204, a hydrocarbon stream produced from a subterranean reservoir is flowed through the vessel to contact the loaded metal oxide particles. The loaded metal oxide particles may be supported in a bed structure such that the hydrocarbon stream flows through the loaded metal oxide particles, or the loaded metal oxide particles may be disposed into the flowing hydrocarbon stream and allowed to flow with the hydrocarbon stream. A combination of such methods can also be used.

[0028] At 206, the hydrocarbon stream is separated from the metal oxide particles to yield a treated stream having reduced hydrogen sulfide content and a concentration of production aid to facilitate subsequent processing. If the loaded metal oxide particles are restrained in a bed structure, the hydrocarbon stream flows out of the vessel to separate from the metal oxide particles. If the loaded metal oxide particles are injected into the flowing hydrocarbon stream, the metal oxide particles can be separated from the flowing hydrocarbon stream by filtration or other solids removal process.

[0029] The loaded metal oxide particles release hydrogen sulfide scavenger and production aid as the hydrocarbon stream is contacted with the metal oxide particles. Thus, during the contacting, the metal oxide particles are unloaded and eventually become inactive. At such time, the metal oxide particles can be re-loaded with hydrogen sulfide scavenger and / or production aid by a reloading process. The reloading process generally comprises removing materials encountered during processing of the hydrocarbon stream, and then contacting the cleaned metal oxide particles with a loading mixture. Materials that may need removing from the metal oxide particles include hydrocarbons, hydrocarbon impurities, organic chemicals, salts, and the like. In oneexample, the metal oxide particles are dried at high temperature in a non-reactive atmosphere to remove volatile species, subjected to a combustion environment to remove any remaining trace organic materials, and then washed in clean water. Any of such steps can be repeated. The resulting cleaned metal oxide particles can be used directly by reloading with hydrogen sulfide scavenger and / or production aid. Alternately, the cleaned metal oxide particles can be mixed with freshly made metal oxide particles.

[0030] It is anticipated that repeated cycling of metal oxide particles may reduce the loading capacity of the particles over time. If desired, the metal oxide particles can be discarded when loading capacity approaches or falls below a threshold. Loading of the metal oxide particles can be detected by detecting composition of the loading mixture after contact with the metal oxide particles in the loading process or by direct analysis of the loaded metal oxide particles. For example, a sample of the loaded metal oxide particles can be extracted into a medium and analyzed by any convenient method to determine quantity of hydrogen sulfide scavenger and / or production aid loaded onto the metal oxide particles. Alternately, the metal oxide particles can be regenerated by exposure to an energetic process to separate impurities and reform the metal oxide particles. Such energetic processes may include exposure to appropriate acids to remove impurities and / or dissolve the metal oxide particles, exposure to a strongly reducing atmosphere to form metals from the metal oxide particles, separating the metals and re-oxidizing the metals, and / or melting the metal oxide particles to decompose, volatilize, oxidize, or otherwise convert impurities to removable form. After reforming metal oxide particles, the reformed metal oxide can be subjected to sizing again, as described above in connection with the method 100.

[0031] The loaded metal oxide particles can be used in a hydrocarbon operation in other ways. For example, the loaded metal oxide particles could be injected into oilfield production systems as part of scale, corrosion or paraffin inhibitor squeeze treatments, injected into the rathole area to act primarily as chemical releasers but with added hydrogen sulfide removal or added to frac or gravel packs alongside proppant depending on the production system conditions to be treated. Squeeze treatments could be conducted prior to water production in newly drilled oil wells, known as pre-emptive squeezing, with the solid matrix being mostly disposed into the formation withoutcontacting water or hydrocarbon, and then releasing chemicals once water is produced, then reacting with hydrogen sulfide later in field life when hydrocarbon is produced.

[0032] The loaded metal oxide particles can also be deployed into a subterranean formation to react with hydrogen sulfide in hydrocarbon materials in-situ within the formation. Fig. 3 is a flow diagram summarizing a method 300 according to another embodiment. At 302, a treatment material is obtained that contains metal oxide particles of the kind described herein that are loaded with at least a hydrogen sulfide scavenger and a production aid of the kinds described herein. The treatment material also contains a carrier fluid that can be used to deploy the metal oxide particles into a subterranean formation. The carrier fluid can be any fluid suitable for introduction into a subterranean formation and suitable for interaction with a hydrocarbon material. The carrier fluid can be miscible with hydrocarbon or dispersable with hydrocarbon. For example, an organic material that can be introduced downhole can be used as a carrier fluid. In other cases, an emulsion of water, or an aqueous phase, in a hydrocarbon compatible material can be used. In other cases, the carrier fluid can be an aqueous material that contains a component, such as EGMBE to improve compatibility with hydrocarbon.

[0033] The metal oxide particles are dispersed within the carrier fluid such that when the treatment material is introduced to the subterranean formation, the metal oxide particles become dispersed, at least partially, within the hydrocarbon. A dispersant or dispersion aid can be used to improve dispersion of the metal oxide particles, for example by improving chemical compatibility between the particles and the carrier fluid and / or by adjusting fluid properties of the carrier fluid to prevent or slow separation or settling of the metal oxide particles. The dispersant or dispersion aid can be a surfactant, a viscosifier, or both, and multiple substances can be used. Some can be dispersants and some dispersion aids, all can be dispersants, or all can be dispersion aids. Some can be surfactants and some viscosifiers, all can be surfactants, or all can be viscosifiers. In some cases, one or more substances that are both surfactant and viscosifier can be used. Polyamines are examples of surfactants that can be used. Polysaccharides are examples of viscosifiers that can be used.

[0034] The metal oxide particles are loaded with hydrogen sulfide scavenger and production aid prior to dispersion in the carrier fluid. When the metal oxide particles areintroduced to the carrier fluid, the treatment material can be mixed in a vessel, or pumping can be used to mix the treatment material such that the metal oxide particles become dispersed, at least partially, within the carrier fluid.

[0035] At 304, the treatment material is pumped into a subterranean formation to contact a hydrocarbon material containing hydrogen sulfide within the subterranean formation. The treatment material may be placed within the formation such that the treatment material comes into contact with the hydrocarbon in the formation upon placement. Alternately, the treatment material can be deployed to a location such that the metal oxide particles are placed in flow pathways to contact the hydrocarbon flowing within the formation to a well for production. Thus, in one embodiment, the metal oxide particles are placed within openings in the subterranean formation that are near the well to be used to produce hydrocarbon from the formation, such that hydrocarbon flowing from the formation toward the well interacts with the metal oxide particles shortly before passing through the well wall into the well. The metal oxide particles can be deployed to form something of a layer of particles just beyond the well wall that have hydrogen sulfide scavenger materials such that the hydrocarbon flows through the layer of particles before reaching the well.

[0036] At 306, the hydrogen sulfide scavenger is reacted with hydrogen sulfide in the hydrocarbon within the subterranean formation. As noted above, the metal oxide particles can be dispersed within hydrocarbon in the formation or the metal oxide particles can be placed into openings in the formation such that the particles do not flow with the hydrocarbon but react with hydrogen sulfide in the hydrocarbon as the hydrocarbon flows past the particles toward the well.

[0037] The subterranean formation can be treated, using known methods, to increase the availability of openings for placing metal oxide particles. For example, the formation can be subjected to a fracturing or squeeze operation to create or increase openings. In some cases, the metal oxide particles described herein can be dispersed within a fracturing fluid such that, upon fracturing of the formation, the metal oxide particle immediately enter the newly created openings, potentially along with any propping materials. In some cases, in fact, the metal oxide particles can be sized to perform, or assist, propping openings in the formation.

[0038] Where the metal oxide particles are deployed into a subterranean formation, the metal oxide particles can be recovered from hydrocarbon produced from the formation, to the extent any of the particles flow to the surface with produced hydrocarbon. The particles can be filtered, for example. Where other solids might be produced with the metal oxide particles, size-selective filtration, for example using different sized mesh or differential hydrocyclone treatment, can be used to separate, at least partially, the metal oxide particles from other solids.

[0039] The production aid or aids are released into the hydrocarbon, either in-situ within the subterranean formation, or at the surface upon treatment, to address production issues downhole or at the surface. The production aids used depend on chemical compatibility with hydrocarbon and water of the formation, and many known production aids can be used and loaded onto the metal oxide particles to address such issues.

[0040] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

CLAIMSWe claim:

1. A method of treating a hydrocarbon stream, the method comprising: contacting the hydrocarbon stream with metal oxide particles loaded with a hydrogen sulfide scavenger and a hydrocarbon production aid.

2. A method, comprising: mixing a hydrocarbon stream containing hydrogen sulfide with a treatment material comprising a carrier fluid and metal oxide particles loaded with a hydrogen sulfide scavenger and a hydrocarbon production aid; and removing hydrogen sulfide from the hydrocarbon stream using the hydrogen sulfide scavenger.

3. A method, comprising: obtaining a treatment material comprising a carrier fluid and metal oxide particles loaded with a hydrogen sulfide scavenger and a hydrocarbon production aid; pumping the treatment material into a subterranean formation to contact a hydrocarbon material containing hydrogen sulfide within the subterranean formation; and reacting the hydrogen sulfide scavenger with the hydrogen sulfide within the subterranean formation.

4. The method of any of claims 1 to 3, wherein the metal oxide particles are sized based on a target release rate of the hydrocarbon production aid.

5. The method of claims 1 to 4, wherein the metal oxide particles are clay particles coated with a metal oxide material.

6. The method of any of claims 1 to 5, wherein the hydrocarbon production aid comprises a material selected from the group consisting of a scale inhibitor, a corrosion inhibitor, a bactericide, and a water clarifier.

7. The method of any of claims 1 to 6, wherein the metal oxide particles are loaded with a plurality of hydrogen sulfide scavengers.

8. The method of any of claims 1 to 7, wherein each metal oxide particle is loaded with the hydrogen sulfide scavenger and the hydrocarbon production aid.

9. The method of any of claims 1 to 8, wherein the metal oxide particles are supported in a vessel to form a bed, and the hydrocarbon stream is flowed through the bed.

10. The method of any of claims 2 to 9, wherein the carrier fluid is miscible with hydrocarbon.11 . The method of any of claims 1 to 10, further comprising dispersing the metal oxide particles into the hydrocarbon stream.

12. The method of any of claims 2 to 10, wherein the treatment material further comprises a dispersant.

13. The method of claim 3, wherein the metal oxide particles are placed within openings in the subterranean formation.

14. The method of claim 3, wherein the process aids inhibit corrosion, mineral scale, or both within process equipment at the surface or in a well used to pump the treatment material into the subterranean formation.

15. The method of claim 3, further comprising treating the formation to increase openings in the formation for deploying the metal oxide particles.

16. The method of claim 3, further comprising releasing the hydrocarbon production aid into the hydrocarbon material within the subterranean formation.

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