MULTIPLE-LOADED NON-CERAMIC DRY CARRIER PRODUCT AND METHOD

Abstract

A multiple-loaded non-ceramic dry carrier product and method for the loading of reagent liquids, solids dissolved in liquids as solutions, suspensions, and solids heated to reduce viscosity, onto perlite, pumice, scoria, or exfoliated vermiculite or activated charcoal particles, which are used as carriers, and then dried in multiple iterations to achieve a powdered, free-flowing material for use in hydraulic fracturing processes and other uses such as environmental remediation and animal control, providing improvements in cost, carrier stability, and chemical retention properties.

Claims

1. A multiple-loaded non-ceramic dry carrier product comprising: (i) a non-ceramic carrier material having porous small and granular particles; (ii) at least one reagent; wherein said reagent is loaded onto said non-ceramic carrier material and then dried to form a reagent-loaded dry carrier, in repeating iterations until said non-ceramic carrier material is substantially completely loaded with the reagent.

2. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said non-ceramic carrier material is chosen from a group consisting of perlite, pumice, and scoria.

3. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said non-ceramic carrier material is chosen from a group consisting of exfoliated vermiculite and activated charcoal.

4. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein each said reagent is a substance chosen from a group consisting of liquids, solutions of solids dissolved in liquids, suspensions, and solids heated to reduce viscosity.

5. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said reagent further comprises a surfactant chemical.

6. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said reagent further comprises a microbial enzymatic system.

7. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said reagent further comprises a substance for animal control.

8. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said reagent further comprises a fragrance.

9. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein said non-ceramic carrier material has porous small and granular particles with aspect ratios in the range of approximately 0.5:1.0 to 0.95:1.0.

10. The multiple-loaded non-ceramic dry carrier product of claim 1, further comprising more than one said reagent.

11. The multiple-loaded non-ceramic dry carrier product of claim 1, wherein each said reagent further comprises a substance chosen from a group consisting of corrosion inhibitors, scale inhibitors, surfactants, biocides, fungicides, microbial, and enzymatic systems.

12. A multiple-loaded non-ceramic dry carrier method comprising: (i) providing a multiple-loaded non-ceramic dry carrier product comprising: (a) a non-ceramic carrier material having porous small and granular particles; and (b) at least one reagent; (ii) loading said reagent onto said non-ceramic carrier material; (iii) drying said reagent loaded onto said non-ceramic carrier material to form a reagent-loaded dry carrier; (iv) repeating iterations of said loading and drying steps until said non-ceramic carrier material is substantially completely loaded with the reagent; and (v) using said reagent-loaded dry carrier.

13. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagent is a cleaning chemical and said using said reagent-loaded dry carrier is cleaning hydrocarbon-contaminated formations.

14. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of surfactants, microbial and enzymatic systems and said using said reagent-loaded dry carrier is oil and stain remediation of concrete and gravel.

15. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagent is an animal control substance, where said non-ceramic carrier material provides time-release and preservative properties to said reagent, and impedes movement of said reagent through soil.

16. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of an animal control substance active on a first type of animal, and an animal control substance repellant to a second type of animal, discouraging said second type of animal from interacting with said reagent-loaded dry carrier.

17. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of a first substance and a second substance acting upon said first substance as a preservative.

18. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of a first substance and a second substance acting upon said first substance as a time-release agent.

19. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of a first substance and a second substance acting upon said first substance as a buffer.

20. The multiple-loaded non-ceramic dry carrier method of claim 12, wherein said reagents are a mixture of a first substance and a second substance acting upon said first substance as an activator.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Reference will now be made to the drawings, wherein like parts are designated by like numerals, and wherein:

[0033] FIG. 1 is a schematic representation of the process of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0034] This invention provides a multiple-loaded non-ceramic dry carrier product and method for the loading of reagent liquids, solids dissolved in liquids as solutions, suspensions, and solids heated to reduce viscosity, onto perlite, pumice, scoria, or exfoliated vermiculite or activated charcoal particles, which are used as carriers, and then dried in multiple iterations to achieve a powdered, free-flowing material for use in hydraulic fracturing processes and other uses such as environmental remediation and animal control, providing improvements in cost, carrier stability, and chemical retention properties.

[0035] Referring to FIG. 1, a schematic representation of the process of loading the multiple-loaded non-ceramic dry carrier. The specific carrier materials used are non-ceramic materials. The non-ceramic materials having high crush strength, which are therefore more suited for most downhole hydraulic fracturing operations, are expanded perlite, pumice, and scoria, which are related volcanic glass ejecta, all with low density, with expanded perlite having the lowest density and scoria having the highest. Exfoliated vermiculite and activated carbon are non-ceramic materials, which do not have high crush strength and are less appropriate for downhole hydraulic fracturing use and are more appropriate for uses such as environmental remediation and animal control.

[0036] Ceramics are made by calcining clay minerals or pure alumina to create porous carriers for catalysts, filtration media, etc., and may be modified. The chemical composition of manufactured ceramic materials may be modified by chemically altering the structure by exchange of ions on active sites within the structure. The non-ceramic materials expanded perlite, pumice, scoria, exfoliated vermiculite, and activated carbon cannot be modified in this way as they have been chemically formed naturally already and do not undergo further chemical reaction as there are no active sites. Thus, they are chemically stable, as opposed to manufactured ceramics.

[0037] The non-ceramic carrier materials expanded perlite, pumice, scoria, exfoliated vermiculite, and activated carbon are capable of a higher percentage loading of reagent than other materials presently used as carriers, such as diatomaceous earth. As treated above, diatomaceous earth and other crystalline silicates can damage the health of persons using those materials and can damage the health of humans or animals exposed to such materials in the environment. The non-ceramic carrier materials of the multiple-loaded non-ceramic dry carrier product and method do not present those health risks.

[0038] The non-ceramic materials expanded perlite, pumice, scoria, exfoliated vermiculite, and activated carbon, as used in this multiple-loaded non-ceramic dry carrier invention, form porous small and granular particles, often substantially spherical, as opposed to larger and more elaborate structures such as tubular or cylindrical structures as are formed by, for example, graphene. The porous small and granular particles are much less likely to affect the fluid conductance or electrical properties of a formation, and are therefore much less likely to interfere with telemetry equipment. The porous small and granular particles have aspect ratios in the range of approximately 0.5:1.0 to 0.95:1.0.

[0039] For oilfield downhole use, the particle size of the carriers is in the range of 8 to 100 microns with an optimal size of 10 to 20 mesh. However, the optimal size and range may be tailored according to the specific use. For carriers used with surfactants, microbes, animal attractants, etc. the particle size may be of the 8 to 100 micron range but may be up to ½″ granules in size. Depending on the exact needs for a specific operation, the specific properties of one of the carrier materials might present an advantage over the others. For example, expanded perlite is less dense than water and will generally be at least somewhat buoyant in most fluids even after loading, while scoria is more dense than water and will be much less buoyant in heavy fluids and not at all buoyant in water. The difference in buoyancy might be a significant factor in some operations, where, for example, it might be beneficial to carry a surfactant or dispersant to concentrate at a higher or a lower level in a pool of oil-contaminated water.

[0040] The reagent or reagents used are liquids, solids dissolved in liquids as solutions, suspensions, and solids heated to reduce viscosity. The reagents are meant to be injected or otherwise applied in order to cause, prevent, advance, retard, or control some aspect of the operation being performed. Many examples of various reagents and various operations are given below. The reagent or reagents are loaded onto the carrier material using one or more of the methods treated above, and are dried, again using one or more of the above methods. The result is a reagent-loaded dry carrier, which after the initial loading and drying is not yet loaded to full capacity. Use of dry loaded carrier is crucial in processes where a substance or substrate is to be: (a) expanded by a pressurized propellant and held in an expanded state by a proppant of granular solid material, including, without limitation, hydraulic fracturing for hydrocarbons, manufacturing, oil well treatment and production chemicals, or (b) non-pressurized for biological treatment and remediation systems, animal attractants or repellents, certain fragrances, cleaning chemicals, combinations of the above, and any material, manufacturing process, or remediation process benefiting from these materials. If the drying method causes agglomeration of the particles or any change of effective particle size and shape, the dried particles are comminuted and returned to their small and granular size and shape.

[0041] Even after a first iteration of loading with reagent and drying, the carrier material will have void space not loaded with reagent. Such void space is inefficient and requires a greater amount of partially loaded carrier to be applied in order to apply a given amount of reagent. For downhole operations, this might mean more trips and more operation costs. A possible reason for this remaining void space is migration of reagent, during drying, from pores at the surface of particles to pores toward the center. The initial uptake of reagent at the surface of the particles might block further uptake until the reagent migrates toward the center. The multiple-loaded non-ceramic dry carrier of the invention provides for multiple iterations of loading and drying to achieve a substantially complete loading of reagent on the carrier. The non-ceramic carrier materials provided by the invention are able to tolerate multiple iterations of loading and drying because the materials are chemically stable and non-reactive, in contrast with ceramic materials. It is possible that for a specific operational use, for a specific reagent or combination of reagents, for a specific carrier, and for specific mixing and drying methods, a single iteration of loading and drying could be sufficient to produce a reagent-loaded dry carrier which either fully loaded or fully-enough loaded for the operational use. In such a case, the needed additional iterations of loading and drying will be zero. Such a case is contemplated by this invention, with the necessary additional iterations being zero.

[0042] In one embodiment of the multiple-loaded non-ceramic dry carrier invention, downhole chemicals are loaded onto carriers such as scoria, perlite, and pumice, and are introduced to the formation via being mixed with propellants and proppants or other means. In downstream gas and oil well production, chemicals are loaded onto such carriers such as scoria, perlite, pumice, and so forth, and introduced into the stream by means of a bed placed inline. The carrier substrates can impart time release properties, avoid undesirable side reactions prior to use, improve shelf life, and increase distribution of the treatment system. Perlite, pumice and vermiculite in particular have a low density, and can float on water. Adding a liquid and drying can adjust the material density so that the treated materials are heavier than water and will sink when applied to a water environment. Scoria, in contrast, possesses a high density, naturally which makes it preferable for use in applications where the material needs to be heavier than water initially. Meanwhile, scoria and pumice each possess hard structures that can allow for higher-crush applications.

[0043] In another embodiment of the multiple-loaded non-ceramic dry carrier invention, cleaning chemicals, such as surfactants, can be loaded onto carriers, such as scoria, perlite, pumice, and vermiculite, for delivery on hydrocarbon contaminated substrates. An advantage of using these materials instead of clay is that when they absorb water, they do not turn into a sludge, retaining their physical structure. This makes clean up easier and more environmentally friendly.

[0044] In another embodiment of the multiple-loaded non-ceramic dry carrier invention, cleaning chemicals, such as surfactants, can be loaded onto carriers, such as scoria, perlite, pumice, and vermiculite, and where the surfactant loading can be increased by repeated addition and drying of the carrier for delivery on hydrocarbon contaminated substrates.

[0045] In another embodiment of the multiple-loaded non-ceramic dry carrier invention, microbial and/or enzymatic systems are mixed with a surfactant and loaded onto carriers, such as scoria, perlite, pumice, and vermiculite. The surfactants provide an initial food source for the microbes and to solubilize oils, fats, etc., for microbes and enzymes to act on. The surfactant-microbe-enzyme combination has been shown to work synergistically on oil spills, as opposed to individual treatments of each component. The densities of scoria and pumice can allow the system to sink to the bottom of the water, or can be adjusted by amendments to gradually sink or float. The particle size of the carrier can be selected to lock into the soil substrate or facilitate application via rotary spreader. Proper carrier substrate formulation can allow oil and stain remediation of concrete or gravel, such as found at fueling stations, fuel transfer and oil change facilities, railway beds and yards, convenience stores, and so forth.

[0046] In another embodiment of the multiple-loaded non-ceramic dry carrier invention, liquid animal attractants (such as pheromones and/or flavors or fragrances) or repellents are loaded onto carriers such as scoria, perlite, pumice, vermiculite, and activated charcoal, which possess a large internal carrying capacity. The internally absorbent carriers can act to extend the shelf life of normally temperature, oxygen and light sensitive agents, as well as allow time-release action.

[0047] Examples of uses of the multiple-loaded non-ceramic dry carrier are:

[0048] A 57.1 wt. % downhole scale inhibitor is produced by loading 13.3 grams of inhibitor on 10 grams of perlite.

[0049] A 33.3 wt. % carrier downhole scale inhibitor is produced by loading 10 pounds of inhibitor on 20 pounds of pumice.

[0050] A 33.3 wt. % carrier downhole corrosion inhibitor is produced by loading 10 pounds of inhibitor on 20 pounds of pumice.

[0051] A 50 wt. % carrier downhole corrosion inhibitor is produced by loading 5 grams of inhibitor on 5 grams of perlite.

[0052] A 54.3 wt. % carrier downhole scale inhibitor is produced by loading 38 ounces of inhibitor on 32 ounces of perlite.

[0053] A 60 wt. % carrier downhole corrosion inhibitor is produced by loading 24 ounces of inhibitor on 16 ounces of perlite.

[0054] A 61.4 wt. % slurry of tire pyrolysis oil is produced on perlite powder with up to ½-inch particles. Tire pyrolysis oil can be used to remove paraffinic compounds in down-hole applications.

[0055] An 18.7 wt. % slurry of tire pyrolysis oil is produced on scoria granules up to ⅛ inches in diameter. Tire pyrolysis oil can be used to remove paraffinic compounds in down-hole applications.

[0056] A 20.4 wt. % slurry of tire pyrolysis oil is produced on pumice with granule sizes ranging from ⅛ to ½ inches in diameter. Tire pyrolysis oil can be used to remove paraffinic compounds in down hole applications.

[0057] A 61 wt. % carrier of 10% surfactant solution is produced by loading 17 grams of a 10% surfactant solution onto 11 grams of activated charcoal. The surfactant used is made by mixing 11 grams of Wisk concentrate in 93 grams of water. The activated carbon used may be Aqua-Tech. This liquid infused dried carrier can be used as a cleaner and hydrocarbon remediation product. The liquid infused dried carrier allows the surfactant to stay in place and time release into or on the treated matrix such as soil, or other solid substrates.

[0058] A 10 vol. % of surfactant in water was loaded onto a low porosity perlite to show how loadings increase with multiple additions of the same liquid and after drying. An initial loading of 23.7 wt % was obtained after drying. A second infusion of surfactant produced a loading of 36.8 wt %. A third infusion of surfactant produced a loading of 51.5 wt %.

[0059] A 52 wt. % bacterial carrier is produced by loading 12 grams of the bacteria solution onto 11 grams of activated charcoal. The bacterial solution used may be AquaVitro Remediation Bacteria, designed to remediate organic waste such as food, sludge, and detritus. The activated carbon used may be Aqua-Tech. The liquid infused dried carrier formulation of the bacteria allows its waste remediation properties to stay in place and time release into the treated matrix such as soil, or other solid substrates.

[0060] A 52 wt. % bacterial carrier is produced by loading 14 grams of the bacteria solution onto 13 grams of activated charcoal. The bacterial solution used may be AquaVitro Seed Bacteria, which contains anaerobic and aerobic facultative and nitrifying and denitrifying bacteria. The activated carbon used may be Aqua-Tech. The liquid infused dried carrier formulation of the bacteria allows its waste remediation properties to stay in place and time release into the treated matrix such as soil, or other solid substrates.

[0061] A 57.5 wt. % carrier of microbes from First Generation Microbials, LLC is produced on perlite powder with up to ½-inch particles.

[0062] A 10.3 wt. % carrier of microbes from First Generation Microbials, LLC is produced on scoria granules up to ⅛ inches in diameter.

[0063] A 16.2 wt. % carrier of microbes from First Generation Microbials, LLC is produced on pumice with granule sizes ranging from ⅛ to ½ inches in diameter.

[0064] An 81.3 wt. % carrier of microbes from First Generation Microbials, LLC is produced on vermiculite with granule sizes ranging from 1/16 to ½ inches in diameter.

[0065] A 50 wt. % bacteria carrier is produced by loading 1 pound of bacteria on 1 pound of vermiculite.

[0066] An 81.3 wt. % bacteria carrier is produced by loading 87.2 grams of bacteria on 20 grams of vermiculite.

[0067] A 56 wt. % bacterial carrier is produced by loading 14 grams of the bacteria solution onto 11 grams of activated charcoal. The bacterial solution used may be AP StressZyme, which is designed to remove sludge from aquatic surfaces. The activated carbon used may be Aqua-Tech. The liquid infused dried carrier DLC formulation of the bacteria allows its waste remediation properties to stay in place and time release into the treated matrix such as soil, filter media, gravel, or other solid substrates.

[0068] A 52 wt. % bacterial carrier is produced by loading 13 grams of the bacteria solution onto 12 grams of activated charcoal. The bacterial solution used may be Bio-Spira, which contains nitrifiers designed to remove ammonia and nitrite from aquatic environments. The activated carbon used may be Aqua-Tech. The liquid infused dried carrier formulation of the bacteria allows its waste remediation properties to stay in place and time release into the treated matrix such as soil, filter media, gravel, or other solid substrates.

[0069] A 48 wt. % carrier of hog attractant is produced by loading 9.1 grams of a hog attractant onto 10 grams of activated charcoal. The activated carbon used may be API Activated Filter Carbon. The hog attractant used may be Black Gold hog attractant. The liquid infused dried carrier DLC formulation of the liquid hog attractant allows the active ingredient to lock into place and time release into the soil matrix.

[0070] A 38 wt. % carrier of thymol is produced by loading 6.2 grams of thymol onto 10 grams of activated charcoal. The activated carbon used may be API Activated Filter Carbon. The liquid infused dried carrier formulation of the thymol allows its germicidal properties to stay in place and time release into the treated matrix such as soil, or other substrates.

[0071] A 32 wt. % of peppermint oil is produced by loading 4.8 grams of the active ingredient onto 10 grams of activated charcoal. The activated carbon used may be API Activated Filter Carbon. The liquid infused dried carrier formulation of the peppermint oil allows its animal repellent properties to lock in place and time release in the soil matrix or other substrate where it is applied.

[0072] A 33 wt. % carrier of eucalyptol is produced by loading 5.0 grams of the active ingredient onto 10 grams of activated charcoal. The activated carbon used may be API Activated Filter Carbon. The liquid infused dried carrier formulation of the eucalyptol allows its animal repellent properties to lock in place and time release in the soil matrix or other substrate where it is applied.

[0073] A 58% active ingredient carrier of hog attractant is produced by loading equal portions of Black Gold hog pheromone, Pigout brand liquid hog attractant, and water onto perlite. The mixing was performed in a clear plastic sealable container to emulate a drum mixer process and to minimize escaping “fines.” The resulting product is a fluffy powder with no clumping. Other attractants may be used instead of or to complement the above formulation.

[0074] Ten (10) wt. % of peanut butter powder is added to compliment the hog attractant listed above. This formulation improvement was created after increased feral hog activity was observed around peanut fields. The peanut butter powder does not load into the carrier matrix, rather it mechanically mixes in interparticle space between the carrier particles.

[0075] The hog attractant listed above is treated with a denaturant or fragrance to discourage consumption by humans and certain animals. Feral hogs and rats are attracted to all liquids in the formulations. Human consumption is by accidental ingestion, primarily. By varying the concentration and type of the denaturant it is possible to tailor formulations which deter consumption by humans and are attractive to hogs, rats, squirrels, or other animals. For example, a loading of 10 ppmw of Denatonium Benzoate in the formulations will repel rats and squirrels, but not feral hogs. A minimal loading of 10 ppbw is bitter to humans and deters consumption, whereas that loading is not detected by animals. Fragrances, such as peppermint oil, may be used in the formulations as the scents deter many animals from even approaching the formulations when applied. The denaturants and fragrances are applied to the carrier along with the primary components by the same methods outlined above or may be added later.

[0076] The formulation of the hog attractant with peanut butter powder is treated with a denaturant or fragrance to discourage consumption by humans and certain animals. Feral hogs and rats are attracted to all liquids in the formulations, while deer are attracted mainly to the peanuts. Human consumption is by accidental ingestion, primarily. By varying the concentration and type of the denaturant it is possible to tailor formulations which deter consumption by humans and are attractive to hogs, but not deer, rats, squirrels, or other animals. For example, a loading of 10 ppmw of Denatonium Benzoate in the formulations will repel rats and squirrels, but not feral hogs. Formulations containing 0.2 wt % of Denatonium Benzoate will repel deer. A minimal loading of 10 ppbw is bitter to humans and deters consumption, whereas that loading is not detected by animals. Fragrances, such as peppermint oil, may be used in the formulations as the scents deter many animals from even approaching the formulations when applied. The denaturants and fragrances are applied to the carrier along with the primary components by the same methods outlined above or may be added later.

[0077] Many other changes and modifications can be made in the system and method of the present invention without departing from the spirit thereof. We therefore pray that our rights to the present invention be limited only by the scope of the appended claims.