Methods of hydraulically fracturing and recovering hydrocarbons
09828542 · 2017-11-28
Assignee
Inventors
- Timothy Moeller (Magnolia, TX)
- Walter Sherwood (Glenville, NY)
- Mark Land (Houston, TX)
- John Ely (Montgomery, TX)
- Thomas Dyk (Cody, WY)
- Andrew Hopkins (Houston, TX)
Cpc classification
C09K2208/00
CHEMISTRY; METALLURGY
C08G77/20
CHEMISTRY; METALLURGY
C04B2235/3418
CHEMISTRY; METALLURGY
C08L83/00
CHEMISTRY; METALLURGY
C04B35/5603
CHEMISTRY; METALLURGY
C04B35/571
CHEMISTRY; METALLURGY
C04B2235/3217
CHEMISTRY; METALLURGY
C08L83/00
CHEMISTRY; METALLURGY
C04B2235/5445
CHEMISTRY; METALLURGY
C04B2235/3463
CHEMISTRY; METALLURGY
C04B2235/5436
CHEMISTRY; METALLURGY
Y02P40/60
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C04B2235/5427
CHEMISTRY; METALLURGY
E21B43/01
FIXED CONSTRUCTIONS
International classification
C09K8/588
CHEMISTRY; METALLURGY
C04B35/571
CHEMISTRY; METALLURGY
C04B33/135
CHEMISTRY; METALLURGY
Abstract
There is provided synthetic proppants, and in particular polysilocarb derived ceramic proppants. There is further provided hydraulic fracturing treatments utilizing these proppants, and methods of enhance hydrocarbon recovery.
Claims
1. A method of hydraulically fracturing a well, the method comprising: a. preparing at least about 100,000 gallons of a hydraulic fracturing fluid, the hydraulic fracturing fluid comprising a polysiloxane derived ceramic proppant made by the process of first curing a polysiloxane precursor batch to form a cured bead and pyrolizing the cured bead to form the polysiloxane derived ceramic proppant; b. pumping at least about 100,000 gallons of hydraulic fracturing fluid into a borehole in a formation, and out of the borehole into the formation; whereby fractures are created in the formation; and, c. leaving at least some of the proppant in the fractures.
2. The method of claim 1, wherein the fracturing fluid has at least about 2 lbs per gallon of proppant.
3. The method of claim 1, wherein the fracturing fluid has at least 3 lbs per gallon of proppant.
4. The method of claim 1, wherein the fracturing fluid has at least 4 lbs per gallon of proppant.
5. The method of claim 1, wherein the proppants have a particle size distribution of at least about 95% of the proppants being within about a 10 mesh range.
6. The method of claim 1, wherein the proppants have a specific gravity of less 1.9.
7. The method of claim 1, wherein the proppants have a bulk density of less about 1.3 g/cc.
8. The method of claim 1, wherein the formation is a shale formation.
9. The method of claim 8, wherein the shale formation is Eagleford shale.
10. The method of claim 8, wherein the shale formation is Barnett shale.
11. The method of claim 8, wherein the shale formation is Bakken shale.
12. The method of claim 8, wherein the shale formation is Utica shale.
13. A method of hydraulically fracturing a well, the method comprising: a. preparing at least about 100,000 gallons of a hydraulic fracturing fluid, the hydraulic fracturing fluid comprising a synthetic proppant; b. the proppant having an apparent specific gravity of less than about 2 and a crush test of less than about 1% fines generated at 10,000 psi.; c. pumping at least about 100,000 gallons of hydraulic fracturing fluid into a borehole in a formation, and out of the borehole into the formation; whereby fractures are created in the formation; and, d. leaving at least some of the proppant in the fractures.
14. The proppant of claim 13, wherein the proppant consists essentially of silicon, carbon and oxygen.
15. The method of claim 13, wherein the fracturing fluid has at least about 2 lbs per gallon of proppant.
16. The method of claim 13, wherein the fracturing fluid has at least 3 lbs per gallon of proppant.
17. The method of claim 13, wherein the fracturing fluid has at least 4 lbs per gallon of proppant.
18. The method of claim 14, wherein the fracturing fluid has at least about 2 lbs per gallon of proppant.
19. The method of claim 14, wherein the fracturing fluid has at least 3 lbs per gallon of proppant.
20. The method of claim 14, wherein the fracturing fluid has at least 4 lbs per gallon of proppant.
21. The proppant of claim 15, wherein the proppant consists essentially of silicon, carbon and oxygen.
22. The method of claim 14, wherein the fracturing fluid has at least about 2 lbs per gallon of proppant.
23. The method of claim 15, wherein the fracturing fluid has at least about 2 lbs per gallon of proppant.
24. The method f claim 13, wherein the formation is a shale formation.
25. The method of claim 24, wherein the shale formation is Eagleford shale.
26. The method of claim 24, wherein the shale formation is Barnett shale.
27. The method of claim 24, wherein the shale formation is Bakken shale.
28. The method of claim 24, wherein the shale formation is Utica shale.
29. The method of claim 13, wherein the fracturing fluid has at least about 10 lbs per gallon of proppant.
30. The method of claim 13, wherein the fracturing fluid has at least 10 lbs per gallon of proppant.
31. The method of claim 13, wherein the fracturing fluid has at least 10 lbs per gallon of proppant.
32. A method of hydraulically fracturing a well, the method comprising: a. preparing at least about 100,000 gallons of a hydraulic fracturing fluid, the hydraulic fracturing fluid comprising a synthetic proppant; b. the proppant having an apparent specific gravity of less than about 2.0 and a crush test of less than about 1% fines generated at 15,000 psi., c. pumping at least about 100,000 gallons of hydraulic fracturing fluid into a borehole in a formation, and out of the borehole into the formation; whereby fractures are created in the formation; and, d. leaving at least some of the proppant in the fractures.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
(73) In general, the present inventions relate to synthetic proppants; methods for making these proppants; fracing fluids utilizing the proppants; and hydraulic fracturing methods.
(74) In general, embodiments of the present inventions relate to polymeric derived ceramic proppants; methods for making these proppants; fracing fluids utilizing these proppants; and hydraulic fracturing methods. In particular, the present inventions relate to proppants and hydraulic fracturing activities that utilize polymeric derived siloxane based ceramics, e.g., polysilocarb derived materials.
(75) In general, embodiments of the present inventions further relate to treating wells, e.g., hydrocarbon producing wells, water wells and geothermal wells, to increase and enhance the production from these wells; and thus, for example, these embodiments relate to new hydraulic fracturing treatments and methods. Still more particularly, embodiments of methods are provided for increasing the fluid conductivity between a subterranean formation containing a desired natural resource, e.g., natural gas, crude oil, water, and geothermal heat source, and a well or borehole to transport the natural resource to the surface or a desired location or collection point for that natural resource. For example, embodiments of the present inventions further relate to treating wells, e.g., hydrocarbon producing wells, water wells and geothermal wells, to increase and enhance the production from these wells by synthetic proppant hydraulic fracturing treatments, including siloxane based polymeric derived ceramic proppant hydraulic fracturing, and including polysilocarb based polymer derived ceramic proppant hydraulic fracturing.
(76) As used herein, unless specified otherwise, the terms “%”, “percent”, “weight %” and “mass %” and similar such terms are used interchangeably and refer to the weight of a first component as a percentage of the weight of the total, e.g., batch, mixture or proppant. As used herein, unless specified otherwise “volume %” and “% volume” and similar such terms refer to the volume of a first component as a percentage of the volume of the total, e.g., batch, mixture or proppant. As used herein, unless specified otherwise, mesh size and mesh can be corresponded to the relative diameters as set forth in Table 1. As used herein, unless specified otherwise: if particles are described as having a mesh size of “A” it means that the particles will pass through that mess, but will be stopped by a smaller mesh size; if particles are described as having a mesh size of +(plus) mesh “A” it means that the particles will sit upon (e.g., be stopped by) the mesh “A” screen or sieve; and, if particles are described as being − (minus) mesh “A” it means that the particles will pass through (e.g., not be stopped by) the mesh “A” screen or sieve. When particle sizes, for a sample of proppants (a few 100 proppants, to thousands of proppants, to millions of proppants, to tons of proppants) are described as “A”/“B”, “A” denotes the largest size of the distribution of sizes, and “B” denotes the smallest size of the distribution of sizes. Thus, a sample of proppants being characterized as mesh 20/40 would have proppants that will pass through a 20 mesh sieve, but will not pass through (i.e., are caught by, sit a top) a 40 mesh sieve.
(77) TABLE-US-00001 TABLE 1 U.S. Mesh Microns Millimeters (i.e., mesh) Inches (μm) (mm) 3 0.2650 6730 6.730 4 0.1870 4760 4.760 5 0.1570 4000 4.000 6 0.1320 3360 3.360 7 0.1110 2830 2.830 8 0.0937 2380 2.380 10 0.0787 2000 2.000 12 0.0661 1680 1.680 14 0.0555 1410 1.410 16 0.0469 1190 1.190 18 0.0394 1000 1.000 20 0.0331 841 0.841 25 0.0280 707 0.707 30 0.0232 595 0.595 35 0.0197 500 0.500 40 0.0165 400 0.400 45 0.0138 354 0.354 50 0.0117 297 0.297 60 0.0098 250 0.250 70 0.0083 210 0.210 80 0.0070 177 0.177 100 0.0059 149 0.149 120 0.0049 125 0.125 140 0.0041 105 0.105 170 0.0035 88 0.088 200 0.0029 74 0.074 230 0.0024 63 0.063 270 0.0021 53 0.053 325 0.0017 44 0.044 400 0.0015 37 0.037
(78) Generally, the synthetic proppants and, any preforms, may be any predetermined volumetric shape. The preform proppants may be the same shape or a different shape from the final synthetic proppants. Thus, the preforms, the proppants and both, may be shaped into balls, spheres, squares, prolate spheroids, ellipsoids, spheroids, eggs, cones, rods, boxes, multifaceted structures, and polyhedrons (e.g., dodecahedron, icosidodecahedron, rhombic triacontahedron, and prism), as well as, other structures or shapes. The synthetic proppants may be made into the shape of any proppant that has been used, has been suggested, is being used, or may be developed in the future for use in hydraulic fracing, or in other similar types of operations. There shapes may also be random, such obtained from breaking up a block of material.
(79) Spherical type structures are examples of a presently preferred shape for proppants. Sphere and spherical shall mean, and include unless expressly stated otherwise, any structure that has at least about 90% of its total volume within a “perfect sphere,” i.e., all points along the surface of the structure have radii of equal distance. A spherical type structure shall mean, and include all spheres, and any other structure having at least about 70% of its total volume within a perfect sphere.
(80) Although this specification focuses on proppants, and in particular proppants for hydraulic fracturing, it is to be understood that the small volumetric shapes (preferably predetermined volumetric shapes) of the present materials, e.g., beads, etc., may have many other uses, in addition to hydraulic fracturing, and that the scope of protection to be afford such materials is not limited to proppants, and hydraulic fracturing. These shapes can be many different sizes (for proppant, as well as other uses), including any of the sizes on Table 1, and can be larger and smaller.
(81) The batch formulations and processes of making synthetic proppants provides the ability to make proppants that are, among other shapes, spheres, perfect spheres, essentially perfect spheres (any other structure having at least about 98% of its total volume within a perfect sphere), and substantially perfect spheres (any other structure having at least about 95% of its total volume within a perfect sphere).
(82) Turning to
(83) Embodiments of the synthetic proppant preferably have an apparent density that is close to, i.e., within 90% of the actual density of the material making up the proppant; more preferably the apparent density of the proppant is essentially the same as the actual density, i.e., within 95% of the actual density, and still more preferably the apparent density of the proppant is the same as the actual density, i.e., within 98% of the actual density. Thus, it is understood that apparent density takes into consideration (would include in the calculation) the voids in a structure if any; while actual density would not. For example, a common sponge would have an apparent density that is significantly lower than its actual density. The absence of pores, or voids, from the structure of the volumetric shapes is preferred, both absent from the surface and from the interior.
(84) The volumetric shapes of the synthetic proppants may also be characterized by using a Krumbein and Sloss chart (
(85) Synthetic proppants, e.g., polysilocarb derived ceramic proppants (“PsDC proppant”), may, for example, also have some, or all of, the characteristics set forth in Table 2, which characteristics are based upon testing and methodologies that are well know in the art, and which are also set forth in ANSI/API Recommended Practice 19C, May 2008 (also ISO 13503-2:2006) as well as, API RP 56/58/60 (the entire disclosure of each of which is incorporated herein by reference). Generally, testing that may be used in categorizing proppants can be found in, and is known to those of skill in the art, in ANSI, API, and ISO, publications, reports, standards, etc., which collectively will be referred to herein as “API (ISO).” Other additional testing and categorizations may be used, which generally known to those of skill in the art, or that are set forth in this specification. Embodiments of the present inventions can exceed, out perform and both, one or more of the characteristics set forth in Table 2.
(86) TABLE-US-00002 TABLE 2 More Characteristic/Physical Example PsDC PsDC Preferred Preferred Property 31 Example 1 Example 2 proppant proppant Range Range Turbidity (NTU) 57 19 26 15 13 ≦250 ≦20 Krumbein Shape Factors Roundness >0.9 >0.9 >0.9 0.7 0.7 ≧0.8 ≧0.95 Sphericity >0.9 >0.9 >0.9 .07 0.8 ≧0.8 ≧0.95 Clusters (%) 0 0 0 1 0 ≦2 ≦1 Bulk Density (g/cc) 1.25 1.27 1.27 1.4 1.20 Bulk Density lbs/ft.sup.2 78.12 79.25 79.44 87.40 74.91 Specific Gravity 2.1 2.09 2.12 1.90 1.70 2.1-1.0 1.8-1.3 Particle size distribution Sieve 16 0.0 0.0 0.0 0.0 0.0 18 0.0 0.0 0.0 0.0 0.0 20 0.0 0.2 0.0 0.0 0.0 25 3.5 13.3 1.4 0.0 0.0 30 96.5 73.1 96.9 1 0.0 35 0.1 9.5 1.6 8 0.0 40 0.0 2.2 0.0 89 0.0 50 0.0 0.4 0.0 2 0.0 60 0.0 0.0 0.0 0.0 0.0 70 0.0 0.0 0.0 0.0 0.0 80 0.0 0.0 0.0 0.0 0.0 90 0.0 0.0 0.0 0.0 0.0 100 0.0 0.0 0.0 0.0 0.0 110 0.0 0.0 0.0 0.0 1 120 0.0 0.0 0.0 0.0 97 130 0.0 0.0 0.0 0.0 2 140 0.0 0.0 0.0 0.0 0.0 150 0.0 0.0 0.0 0.0 0.0 160 0.0 0.0 0.0 0.0 0.0 Pan 0.0 0.0 0.0 0.0 0.4 ≦1.0 ≦0.5 % in size 100 98.1 99.9 99 93 ≧95* ≧97** Mean Particle 0.659 0.653 0.655 0.400 0.149 1.680-0.053 0.841-0.074 Diameter mm Median Particle 0.657 0.645 0.652 0.395 0.140 1.680-0.053 0.841-0.074 Diameter (MPD) mm Solubility in 12/3 3.5 3.1 2.4 3.5 3.8 ≦7.0 ≦4 HCL/HF for 0.5 HR @ 150 F. (% weight loss) Solubility in 15% 0.2 1.8 0.3 0.4 ≦7.0 ≦4 HCL for 0.5 HR @ 150 F. (% weight loss) Settling Rate (ft/min) 51.26 49.24 51.74 15.00 10.00 ≦30 ≦12 ISO crush Analysis 9.6 7.5 7.5 ≦10 ≦8.0 (% Fines) 4 lbs/ft.sup.2 @ 4,000 psi ISO crush Analysis 13.2 9.7 9.1 6.7 ≦10 ≦8.0 (% Fines) 4 lbs/ft.sup.2 @ 5,000 psi ISO crush Analysis 11.3 9.9 8.4 ≦10 ≦8.0 (% Fines) 4 lbs/ft.sup.2 @ 6,000 psi ISO crush Analysis 8.6 10 8.9 ≦10 ≦8.0 (% Fines) 4 lbs/ft.sup.2 @ 7,000 psi ISO crush Analysis 10.4 12 9.9 ≦10 ≦8.0 (% Fines) 4 lbs/ft.sup.2 @ 8,000 psi Wettability (pH of Fair Fair Good Fair Wettable Fair or Water Extract) better pH of Water Extract Initial pH 7.99 8.56 8.4 8.2 x x mL NaOH to pH 9 0.70 0.55 0.6 0.75 0.6 ± 0.2 0.6 ± 0.05 mL NaOH to pH 10 3.00 2.30 3.10 2.10 2.5 ± 1.5 2.5 ± 0.5 mL NaOH to pH 11 6.20 6.10 6.25 6.0 6.0 ± 1 6.0 ± 0.5 * **for a particular targeted diameter sphere size within the targeted range
(87) The characteristics and physical properties identified in Table 2 are further explained as follows.
(88) Turbidity—A measure to determine the levels of dust, silt, suspended clay, or finely divided inorganic matter levels in fracturing proppants. High turbidity reflects improper proppant manufacturing and/or handling practices. The more often and more aggressively a proppant is handled, the higher the turbidity. Offloading pressures exceeding characteristics or guidelines can have a detrimental effect on the proppant performance. Produced dust can consume oxidative breakers, alter fracturing fluid pH, and/or interfere with crosslinker mechanisms. As a result, higher chemical loadings may be required to control fracturing fluid rheological properties and performance. If fluid rheology is altered, then designed or modeled fracture geometry and conductivity will be altered. A change in conductivity directly correlates to reservoir flow rate.
(89) Krumbein Shape Factors—Determines proppant roundness and sphericity. Grain roundness is a measure of the relative sharpness of grain corners, or of grain curvature. Particle sphericity is a measure of how closely a proppant particle approaches the shape of a sphere. Charts developed by Krumbein and Sloss in 1963 are the most widely used method of determining shape factors.
(90) Clusters—Proppant grains should consist of single, well-rounded particles. During the mining and manufacturing process of proppants, grains can attach to one another causing a cluster. It is recommended by ISO 13503-2 that clusters be limited to less than 1% to be considered suitable for fracturing proppants.
(91) Bulk Density—A dry test to gain an estimation of the weight of proppant that will fill a unit volume, and includes both proppant and porosity void volume. This is used to determine the weight of a proppant needed to fill a fracture or a storage tank.
(92) Specific Gravity—Also called Apparent Density, it includes internal porosity of a particle as part of its volume. It is measured with a low viscosity fluid that wets the particle surface.
(93) Sieve Analysis: Particle Size Distribution & Median Particle Diameter—Also called a sieve analysis, this test determines the particle size distribution of a proppant sample. Calibrated sieves are stacked according to ISO 13503-2 recommended practices and loaded with a pre-measured amount of proppant. The stack is placed in a Ro-Tap sieve shaker for 10 minutes and then the amount on each sieve is measured and a percent by weight is calculated on each sieve. A minimum of 90% of the tested proppant sample should fall between the designated sieve sizes. Not over 0.1% of the total tested sample should be larger than the first sieve size and not over 1.0% should fall on the pan. The in-size percent, mean particle diameter, and median particle diameter are calculated, which relates directly to propped fracture flow capacity and reservoir productivity.
(94) API/ISO Crush Test—The API test is useful for comparing proppant crush resistance and overall strength under varying stresses. A proppant is exposed to varying stress levels and the amount of fines is calculated and compared to manufacturer specifications. A PT Crush Profile—can show graphically how median particle diameter (MPD) can vary with changes in closure stress. Unlike the ISO crush test, the PT Crush Profile uses the entire proppant sample for crushing at each stress, the sample is then sieved to determine particle distribution, and MPD is then calculated. A change in MPD directly correlates to flow capacity and reservoir productivity.
(95) Acid Solubility—The solubility of a proppant in 12-3 hydrochloric-hydrofluoric acid (HCl—HF) is an indication of the amount of undesirable contaminates. Exposing a proppant (specifically gravel pack/frac pack materials) may result in dissolution of part of the proppant, deterioration in propping capabilities, and a reduction in fracture conductivity in the zone contacted by such acid. The loss of fracture conductivity near the wellbore may cause a dramatic reduction in well productivity.
(96) pH of Water Extract—This test reflects the potential chemical impact of a proppant on fracturing fluid pH. Processing or manufacturing of prior art proppants can leave residues, or ‘free phenol’ in the case of resin coated proppants, which can interfere with polymer hydration rates, crosslinking mechanisms, etc. These effects if detected can usually be remedied by increasing buffering capacity, but if undetected can alter fracturing fluid rheology, change fracture geometry, and impact propped fracture conductivity. A change in conductivity directly correlates to reservoir production rate.
(97) Preferably the synthetic proppant has, minimal, little, to no affect on the chemistry of the fracturing fluid, regardless of the different additives that can be in a fracturing fluid. In particular, it is highly preferable that the synthetic proppant does not effect or change the chemistry of the fracturing fluid. The synthetic proppant many, in embodiments, provide enhancements or benefits, either chemical, physical or both, to the fracturing fluid, e.g., reduced abrasion, increased lubricity, buffering and specialty properties, e.g., by having a specialty surface treatment, such as a biocide.
(98) In general PsDC proppants essential have little to no affect on the pH of the fracturing fluid. Thus, they can be used with most, in not all, fracturing fluids and will not adversely affect or impact pH, buffering, or pH control, or intentional or planned pH variations, of the wellbore fluids during the fracturing procedures. Further, the PsDC proppants may be coated with, or otherwise contain pH control or solution buffering materials, or sites, and in this manner help to control or maintain a predetermined pH for the fracturing fluids in the down hole environment during fracturing procedures or during production of hydrocarbons.
(99) Regardless of the failure mechanism, fluid flow, or hydraulic mechanisms taking place, the synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants exhibit surprising and exceptional performance features, including among other things improved strength to weight ratios, and improved conductivities over prior art proppants.
(100) For example, turning to
(101) Further, embodiments of synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants can exhibit conductivity data, at pressures about 5,000 psi over its API (ISO) crush test rating: that are at least about 70% of its conductivity data at its rated pressure; that are at least about 80% of its conductivity data at its rated pressure; that are at least about 90% of its conductivity data at its rated pressure; and greater. Embodiments of PsDC proppants can exhibit conductivity data, at pressures about 10,000 psi over its API (ISO) crush test rating: that are at least about 60% of its conductivity data at its rated pressure; that are at least about 70% of its conductivity data at its rated pressure; that are at least about 80% of its conductivity data at its rated pressure; and greater.
(102) The enhanced conductivity data alone or in combination with other enhanced features of embodiments of synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants, such as sphericity, roundness, uniform size distribution, and density provide for the potential for significant improvements in both long-term and short-term in reservoir recovery, e.g., for enhanced initial production, short term and long term production of hydrocarbons from a well.
(103) Thus, for example, performing a synthetic, e.g., PDC, e.g., PsDC hydraulic fracture treatment, and thus having these proppants in the hydrocarbon reservoir, may for example provide benefits such as increases in initial flow of the hydrocarbons, increases in the ability to maintain those increased initial flows for extend or longer periods of time over the life of the well, increase time when the well remains producing, increases in the ability to drain larger areas of a reservoir with or from a single well, and combinations and variations of these and other benefits that may be realized through the use of synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants in hydrocarbon, water and geothermal resources exploration and production.
(104) Thus, for example, turning to
(105) Turning to
(106) Thus, the PsDC hydraulic fracturing treatments provide the ability to increase the Initial Product (IP) from the well (e.g., the amount of production that the well produces during an initial time period typically, about 90 days, about 180 days, and generally less than 1 year), to increase the Decline Curve Reduction (DCR) for the well (e.g., generally over time the amount of production from a well declines over time, slowing this decline in production is viewed as an increase in the DCR), and both. Turning to
(107) In general, unless specifically stated otherwise, the percentage increases, improved performance, and other comparisons that are made in this specification to current and prior art proppants, fracturing technologies, and treatments, are based upon modeling, predictions, data and calculations known to those of skill in the art for providing the production and performance features for a well that is treated with such current or prior art technologies.
(108) The processes and the formulations used to make the synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants, provide the ability to make proppants having a very narrow particle size distribution. Thus, embodiments of these processes produce proppants that are within at least 90% of the targeted size, at least 95% of the targeted size, and at least 99% of the targeted size. For example, the process can produce spherical proppant, spherical type proppants, essentially perfect spherical proppant, and substantially perfect spherical proppant, each of which can have at least about 90% of their size within a 10 mesh range, at least about 95% of their size within a 10 mesh range, at least about 98% of their size within a 10 mesh range, and at least about 99% of their size within a 10 mesh range. Further, and for example, the process can produce spherical proppant, spherical type proppants, essentially perfect spherical proppant, and substantially perfect spherical proppant, each of which can have at least about 90% of their size within a 5 mesh range, at least about 95% of their size within a 5 mesh range, at least about 98% of their size within a 5 mesh range, and at least about 99% of their size within a 5 mesh range. Preferably, these levels of uniformity in the production of the synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants, is obtained without the need for filtering, sorting or screening the cured proppants, and without the need for filtering, sorting or screening the pyrolized proppants. In addition to having the ability to tightly control size distribution, embodiments of the present processes and formulations provide the ability to make a large number of highly uniform predetermined shapes, e.g., at least about 90%, at least about 95% and at least about 99% of the proppants have a predetermined sphericity and/or roundness. For example, at least about 98% of the proppants made from a batch can be essentially spherical.
(109) In
(110) A high-pressure line 805 that transfers high pressure fracturing fluid from the pump trucks 806 into the well. The wellhead 804 may also have further well control devices associated with it, such as a BOP. Fracturing fluid from holding units 812 is transferred through lines 813 to mixing truck 808, where proppant from storage containers 810, 811 is feed, (metered in a controlled fashion) by assembly 809 and mixed with the fracturing fluid. The fracturing fluid and proppant mixture is then transferred to the pump trucks 806, by line 803, where the pump trucks 806 pump the fracturing fluid into the well by way of high pressure line 805.
(111) In embodiments, the PsDCs are mixed with fracing fluids for down hole hydraulic fracturing operations to, for example, recover hydrocarbons, such as crude oil and natural gas. Typically, between about 0.1 and about 12 lbs/gal, between about 3 and about 10 lbs/gal, between about 0.1 and about 1 lbs/gal, between about 1.1 and about 2 lbs/gal, between about 2.1 and about 4 lbs/gal, and between about 3.1 and about 8 lbs/gal of PsDC are mixed into fracing fluid, greater and lesser amounts than about 12 lbs/gal and about 1 lbs/gal are also contemplated. Typically, at least about 10,000 gals, at least about 100,000 gals, at least about 1,000,000 gals and more of fracing fluid are used in a fracing operation. Thus, in general hundreds of thousands, if not millions of pounds of proppant, e.g., PsDC proppant, could be used in a single hydraulic fracturing operation.
(112) The highly uniform nature of embodiments of the present proppants provides for many new and previously unavailable advantageous ways to meter and add in a controlled manner, the proppant to fracturing fluid, for a fracturing treatment. The proppant can be added using volumetric measurements, or metering systems, instead of weight based metering system of the prior art. Volumetric systems using embodiments of the present proppants provides the same or greater level of control because, among other things, the proppants of the present invention are highly uniform and thus volume of these proppants equates linearly, and with high predictability, to the weight of the proppants. This ability to meter, in a controlled manner, by volume, the proppants of the present inventions provides the ability to add these proppants in a controlled manner to the well head, to the high pressure line, and generally, after the high pressure, high volume pumps. Such addition will greatly reduce the wear on the pumps and increase their lives.
(113) Because such large volumes of proppants are used in these operations, and because of the importance in understanding and knowing the characteristics of the proppant, both on a micro level (e.g., a single spherical type structure) and on the macro level (e.g., how the proppant pack behaves in the down hole environment) sampling methods have been developed and are well know in the art to obtain representative samples for testing and characterization of a larger volume of proppant, e.g., a lot, a load, a rail car, etc. These sampling methods are set forth in API RP 56, ISO 13503-2:2006, and in ANSI/API Recommended Practice 19C, First Edition, May 2008. Unless expressly stated otherwise, or contrary to the context, as used herein, when PsDC characteristics, properties, or both are used they will refer to a representative sample of the proppant.
(114) Generally, in the manufacture of PsDCs a polysilocarb batch is formed into a preform proppant. Depending upon the viscosity and other characteristics of the polysilocarb batch, and the intended shape of the proppant, the preform may be made by techniques such as extruding, molding, drawing, spinning, dripping, spraying, vibrating, polymer emulsion (emulsion polymerization, including micro-emulsion polymerization, capable of making a substantial range of sizes, e.g., from about 10 mesh to about 400 mesh, from about 20 mesh to about 200 mesh, from about 500 microns and less, from about 50 microns and less, from about 10 microns and less) and other techniques known to the arts to create small structures of a predetermined shape, and preferably in large volumes, preferably that are highly uniform and more preferably both. Further it is understood, that although it is presently preferred that the preform and the proppant be their approximate size and shape upon cure, or prior to pyrolysis, the polysilocarb batch can be cured into a puck like structure, e.g., roughly the size and shape of a hockey puck, a brick like structure or other larger volumetric shape. This larger shape can be cured, hard cured, and pyrolized, and broken down into smaller sizes (preferably after pyrolysis). This process of later breaking down, typically, although not necessarily, results in a proppant that is not of uniform or consistent shape, size and both.
(115) The curing process may take place upon initial forming, if the preform is unrestrained, to make certain that the predetermined shape is locked, e.g., fixed or set, so that later handing of the preform will not change the shape. The curing process may be continuous, e.g., initial cure to hard cure occurs in one time period and process, or may take place in several stages, e.g., an initial cure for a set time period and temperature, a cure of a set time period and temperature, and a hard cure for a set time period and temperature. These cure stages may take place back-to-back with no intervening time periods or they may be staggered in time, with intervening time periods where the preform is maintained at ambient temperature, or where the preform is subjected to some other process. For example, an initial cure may be performed, a cure may then be performed, in which case the preform has the appearance of having a hard skin with gelatinous center, at which point the preform could be subjected to a shaping operation to get it into is final form, at which point the hard cure would be performed.
(116) In general, and for example, for the purposes of making beads, or ball shaped proppants one or more of the process parameters and equipment set forth in table 3 can be used.
(117) TABLE-US-00003 TABLE 3 Nozzle Thermal Heat Exchanger Curing Process Production of proppant Temperature range 0 to Temperature beads thru the use of internal 1600 C. multi zone/range range 0 to 1600 and external orifices, controlled C. multi atomization mechanically, zone/range con- pressure, and gas to produce trolled (manually tight mesh distribution or automated - (within 1 to 5 mesh sizes of local or remote) target size) beads ranging from 2000 micron to 75 micron. Produced thru the use of a Air, Steam, Electrical, Phased curing temperature compensated Gas, Waste Heat, or process in part or (liquid, air, gas, radiant, or Solar source of heat whole mechanical) controllable one or more active orifices or filament, (vibration, heat, pressure, pulsation, 20 Hz to 20,000 Hz frequency) Orifices or filament Material of Air or inert gas material; made from metal, Construction—metallic, controlled composite, plastic, precious composite, fire brick, or atmosphere metal, jewel, or ceramic, ceramic Gravity or pressure Radiant, convection, Air, Steam, compensated orifices direct heat, Electrical, Gas, or filament Waste Heat, or Solar source of heat Continuous operation and Vertical to horizontal Heat transferring flow; or batch process orientations media of air, inert gas, radiant, con- vection, con- densing, vapor, or direct heat Viscosity range 1 to 1000 Up to and including Multi Chambered Adiabatic enabled or portioned Static and dynamic particle 1′ to 500′ Structure Continuous and processing Height batch Multi Chambered or Static and portioned dynamic particle processing Heat transferring media of air, inert gas, radiant, convective, condensing, vapor or direct heat Static and dynamic particle processing
(118) Turning to
(119) In general, preferred embodiments of the synthetic proppants of the present inventions are made from unique and novel silicon (Si) based materials that are easy to manufacture, handle and have surprising and unexpected properties and applications. These silicon based materials go against the general trends of the art of silicon chemistry and uses. Generally, the art of silicon chemistry, and in particular organosilicon chemistry, has moved toward greater and greater complexity in the functional groups that are appended to, and a part of, a silicon based polymeric backbone. Similarly, in general, the processes that are utilized to make these polymers have moved toward greater and greater complexity. Embodiments of the present new material systems for use as proppants move away from this trend, by preferably functionalizing a silicon based polymeric backbone with simpler structures, such as phenyl, phenylethyl and smaller groups, and do so with processes that are simplified, e.g., solvent free, reduced solvent, lower cost starting materials, fewer steps, and reduction of reaction intermediates.
(120) Further, and generally, the art views silicones as tacky, soft or liquid materials that are used with, on, or in conjunction with, other materials to enhance or provide a performance feature to those other materials. Silicon based materials generally are not viewed as stand alone products, primary products, or structural elements. The preferred silicon based materials for use as proppants, however, move away from this trend and understanding in the art. These silicon based materials provide materials that are exceptionally strong, and can function as stand alone products and composites, among other things.
(121) Generally, preferred embodiments of the synthetic proppants of the present inventions are directed to polymer derived ceramics (PDC), and more preferably toward “polysilocarb” materials, e.g., material containing silicon (Si), oxygen (O) and carbon (C), and materials that have been pyrolized from such materials. Polysilocarb materials may also contain other elements. Polysilocarb materials are made from one or more polysilocarb precursor formulation or precursor formulation. The polysilocarb precursor formulation contains one or more functionalized silicon polymers, or monomers, as well as, potentially other ingredients, such as for example, inhibitors, catalysts, pore formers, fillers, reinforcers, fibers, particles, colorants, pigments, dies, polymer derived ceramics (“PDC”), ceramics, metals, metal complexes, and combinations and variations of these and other materials and additives.
(122) The precursor batch may also contain non-silicon based cross linking agents, that are intended to, provide, the capability to cross-link during curing. For example, cross linking agents that can be used include DCPD—dicylcopentadiene, 1,4 butadiene, divnylbenzene, Isoprene, norbornadiene, propadiene, 4-vinylcyclohexene, 2-3 heptadiene 1, 3 butadiene and cyclooctadiene. Generally, any hydrocarbon that contains two (or more) unsaturated, C═C bonds that can react with a Si—H, Si—OH, or other Si bond in a precursor, can be used as a cross linking agent. Some organic materials containing oxygen, nitrogen, and sulphur may also function as cross linking moieties.
(123) The polysilocarb precursor formulation is then cured to form a solid or semi-sold material, e.g., a plastic. The polysilocarb precursor formulation may be processed through an initial cure, to provide a partially cured material, which may also be referred to, for example, as a preform, green material, or green cure (not implying anything about the material's color). The green material may then be further cured. Thus, one or more curing steps may be used. The material may be “end cured,” i.e., being cured to that point at which the material has the necessary physical strength and other properties for its intended purpose. The amount of curing may be to a final cure (or “hard cure”), i.e., that point at which all, or essentially all, of the chemical reaction has stopped (as measured, for example, by the absence of reactive groups in the material, or the leveling off of the decrease in reactive groups over time). Thus, the material may be cured to varying degrees, depending upon its intended use and purpose. For example, in some situations the end cure and the hard cure may be the same.
(124) The curing may be done at standard ambient temperature and pressure (“SATP”, 1 atmosphere, 25° C.), at temperatures above or below that temperature, at pressures above or below that pressure, and over varying time periods (both continuous and cycled, e.g., heating followed by cooling and reheating), from less than a minute, to minutes, to hours, to days (or potentially longer), and in air, in liquid, or in a preselected atmosphere, e.g., Argon (Ar) or nitrogen (N.sub.2).
(125) The polysilocarb precursor formulations can be made into non-reinforced, non-filled, composite, reinforced, and filled structures, intermediates and end products, and combinations and variations of these and other types of materials. Further, these structures, intermediates and end products can be cured (e.g., green cured, end cured, or hard cured), uncured, pyrolized to a ceramic, and combinations and variations of these (e.g., a cured material may be filled with pyrolized beads derived from the same polysilocarb as the cured material).
(126) The precursor formulations may be used to form “neat” materials, (by “neat” material it is meant that all, and essentially all of the structure is made from the precursor material or unfilled formulation; and thus, there are no fillers or reinforcements). They may be used to form composite materials, e.g., reinforced products. They may be used to form non-reinforced materials, which are materials that are made of primarily, essentially, and preferably only from the precursor materials.
(127) In making the polysilocarb precursor formulation into a volumetric shape or structure, the polysilocarb formulation can be, for example, sprayed, spray dried, emulsified, polymer emulsification, polymer micro-emulsification, thermally sprayed, molded, flowed, formed, extruded, spun, dropped, injected or otherwise manipulated into essentially any volumetric shape, including the shapes for the proppant, and combinations and variations of these. These volumetric shapes would include, for example, spheres, pellets, rings, lenses, disks, panels, cones, frustoconical shapes, squares, rectangles, trusses, angles, channels, hollow sealed chambers, hollow spheres, blocks, sheets, coatings, films, skins, particulates, beams, rods, angles, columns, fibers, staple fibers, tubes, cups, pipes, and combinations and various of these and other more complex shapes, both engineering and architectural. Additionally, they may be shaped into preforms, or preliminary shapes that correspond to, or with, a final product, such as for example use in or with, a break pad, a clutch plate, a break shoe, a motor, high temperature parts of a motor, a diesel motor, rocket components, turbine components, air plane components, space vehicle components, building materials, shipping container components, and other structures or components.
(128) The polysilocarb precursor formulations may be used with reinforcing materials to form a composite material. Thus, for example, the formulation may be flowed into, impregnated into, absorbed by or otherwise combined with a reinforcing material, such as carbon fibers, glass fiber, woven fabric, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets or components, staple fibers, tow, nanostructures of the above, PDCs, any other material that meets the temperature requirements of the process and end product, and combinations and variations of these. Thus, for example, the reinforcing materials may be any of the high temperature resistant reinforcing materials currently used, or capable of being used with, existing plastics and ceramic composite materials. Additionally, because the polysilocarb precursor formulation may be formulated for a lower temperature cure (e.g., SATP) or a cure temperature of for example about 100° F. to about 400° F., the reinforcing material may be polymers, organic polymers, such as nylons, polypropylene, and polyethylene, as well as aramid fibers, such as NOMEX or KEVLAR.
(129) The reinforcing material may also be made from, or derived from the same material as the formulation that has been formed into a fiber and pyrolized into a ceramic, or it may be made from a different precursor formulation material, which has been formed into a fiber and pyrolized into a ceramic. In addition to ceramic fibers derived from the precursor formulation materials that may be used as reinforcing material, other porous, substantially porous, and non-porous ceramic structures derived from a precursor formulation material may be used.
(130) The polysilocarb precursor formulation may be used to form a filled material. A filled material would be any material having other solid, or semi-solid, materials added to the polysilocarb precursor formulation. The filler material may be selected to provide certain features to the cured product, the ceramic product or both. These features may relate to or be aesthetic, tactile, thermal, density, radiation, chemical, magnetic, electric, and combinations and variations of these and other features. These features may be in addition to strength. Thus, the filler material may not affect the strength of the cured or ceramic material, it may add strength, or could even reduce strength in some situations. The filler material could impart color, magnetic capabilities, fire resistances, flame retardance, heat resistance, electrical conductivity, anti-static, optical properties (e.g., reflectivity, refractivity and iridescence), aesthetic properties (such as stone like appearance in building products), chemical resistivity, corrosion resistance, wear resistance, abrasions resistance, thermal insulation, UV stability, UV protective, and other features that may be desirable, necessary, and both, in the end product or material. Thus, filler materials could include copper lead wires, thermal conductive fillers, electrically conductive fillers, lead, optical fibers, ceramic colorants, pigments, oxides, dyes, powders, ceramic fines, PDC particles, pore-formers, carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes, siloxane, powders, ceramic powders, metals, metal complexes, carbon, tow, fibers, staple fibers, boron containing materials, milled fibers, glass, glass fiber, fiber glass, and nanostructures (including nanostructures of the forgoing) to name a few.
(131) The fill material may also be made from, or derived from the same material as the formulation that has been formed into a cured or pyrolized solid, or it may be made from a different precursor formulation material, which has been formed into a cured solid or semi-solid, or pyrolized solid.
(132) The polysilocarb formulation and products derived or made from that formulation may have metals and metal complexes. Thus, metals as oxides, carbides or silicides can be introduced into precursor formulations, and thus into a silica matrix in a controlled fashion. Thus, using organometallic, metal halide (chloride, bromide, iodide), metal alkoxide and metal amide compounds of transition metals and then copolymerizing in the silica matrix, through incorporation into a precursor formulation is contemplated.
(133) For example, Cyclopentadienyl compounds of the transition metals can be utilized. Cyclopentadienyl compounds of the transition metals can be organized into two classes: Bis-cyclopentadienyl complexes; and Mono-cyclopentadienyl complexes. Cyclopentadienyl complexes can include C.sub.5H.sub.5, C.sub.5Me.sub.5, C.sub.5H.sub.4Me, CH.sub.5R.sub.5 (where R=Me, Et, Propyl, i-Propyl, butyl, Isobutyl, Sec-butyl). In either of these cases Si can be directly bonded to the Cyclopentadienyl ligand or the Si center can be attached to an alkyl chain, which in turn is attached to the Cyclopentadienyl ligand.
(134) Cyclopentadienyl complexes, that can be utilized with precursor formulations and in products, can include: bis-cyclopentadienyl metal complexes of first row transition metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second row transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium); third row transition metals (Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum); Lanthanide series (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); Actinide series (Ac, Th, Pa, U, Np).
(135) Monocyclopentadienyl complexes may also be utilized to provide metal functionality to precursor formulations and would include monocyclopentadienyl complexes of: first row transition metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second row transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium); third row transition metals (Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum) when preferably stabilized with proper ligands, (for instance Chloride or Carbonyl).
(136) Alky complexes of metals may also be used to provide metal functionality to precursor formulations and products. In these alkyl complexes the Si center has an alkyl group (ethyl, propyl, butyl, vinyl, propenyl, butenyl) which can bond to transition metal direct through a sigma bond. Further, this would be more common with later transition metals such as Pd, Rh, Pt, Ir.
(137) Coordination complexes of metals may also be used to provide metal functionality to precursor formulations and products. In these coordination complexes the Si center has an unsaturated alkyl group (vinyl, propenyl, butenyl, acetylene, butadienyl) which can bond to carbonyl complexes or ene complexes of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni. The Si center may also be attached to a phenyl, substituted phenyl or other aryl compound (pyridine, pyrimidine) and the phenyl or aryl group can displace carbonyls on the metal centers.
(138) Metal alkoxides may also be used to provide metal functionality to precursor formulations and products. Metal alkoxide compounds can be mixed with the Silicon precursor compounds and then treated with water to form the oxides at the same time as the polymer, copolymerize. This can also be done with metal halides and metal amides. Preferably, this may be done using early transition metals along with Aluminum, Gallium and Indium, later transition metals: Fe, Mn, Cu, and alkaline earth metals: Ca, Sr, Ba, Mg.
(139) Compounds where Si is directly bonded to a metal center which is stabilized by halide or organic groups may also be utilized to provide metal functionality to precursor formulations and products.
(140) Additionally, it should be understood that the metal and metal complexes may be the continuous phase after pyrolysis, or subsequent heat treatment. Formulations can be specifically designed to react with selected metals to in situ form metal carbides, oxides and other metal compounds, generally known as cermets (e.g., ceramic metallic compounds). The formulations can be reacted with selected metals to form in situ compounds such as mullite, alumino silicate, and others. The amount of metal relative to the amount of silica in the formulation or end product can be from about 0.1 mole % to 99.9 mole %, about 1 mole % or greater, about 10 mole % or greater, about 20 mole percent or greater % and greater. The forgoing use of metals with the present precursor formulas can be used to control and provide predetermined stoichiometries.
(141) Filled materials would include reinforced materials. In many cases, cured, as well as pyrolized polysilocarb filled materials can be viewed as composite materials. Generally, under this view, the polysilocarb would constitute the bulk or matrix phase, (e.g., a continuous, or substantially continuous phase), and the filler would constitute the dispersed (e.g., non-continuous), phase.
(142) It should be noted, however, that by referring to a material as “filled” or “reinforced” it does not imply that the majority (either by weight, volume, or both) of that material is the polysilcocarb. Thus, generally, the ratio (either weight or volume) of polysilocarb to filler material could be from about 0.1:99.9 to 99.9:0.1. Smaller amounts of filler material or polysilocarb could also be present or utilized, but would more typically be viewed as an additive or referred to in other manners. Thus, the terms composite, filled material, polysilocarb filled materials, reinforced materials, polysilocarb reinforced materials, polysilocarb filled materials, polysilocarb reinforced materials and similar such terms should be viewed as non-limiting as to amounts and ratios of the material's constitutes, and thus in this context, be given their broadest possible meaning.
(143) The polysilocarb precursor formulation may be specifically formulated to cure under conditions (e.g., temperature, and perhaps time) that match, e.g., are predetermined to match, the properties of the reinforcing material, filler material or substrate. These materials may also be made from, or derived from, the same material as the polysilocarb precursor formulation that is used as the matrix, or it may be made from a different polysilocarb precursor formulation. In addition to ceramic fibers derived from the polysilocarb precursor formulation materials, porous, substantially porous, and non-porous ceramic structures derived from a polysilocarb precursor formulation material may be used as filler or reinforcing material.
(144) The polysilocarb precursor formulations may be used to coat or impregnate a woven or non-woven fabric, made from for example carbon fiber, glass fibers or fibers made from a polysilocarb precursor formulation (the same or different formulation), to from a prepreg material. Further, a polysilocarb precursor formulation may be used as an interface coating on the reinforcing material, for use either with a polysilocarb precursor formulation as the matrix material. Further, carbon fiber may be heat treated to about 1,400° to about 1,800° or higher, which creates a surface feature that eliminates the need for a separate interface coating, for use with polysilocarb precursor formulations.
(145) Fillers can reduce the amount of shrinkage that occurs during the processing of the formulation into a ceramic, they can be used to provide a predetermined density of the product, either reducing or increasing density, and can be used to provide other customized and predetermined product and processing features. Fillers, at larger amounts, e.g., greater than 10%, can have the effect of reducing shrinkage during cure.
(146) Depending upon the particular application, product or end use, the filler can be evenly distributed in the precursor formulation, unevenly distributed, a predetermined rate of settling, and can have different amounts in different formulations, which can then be formed into a product having a predetermined amounts of filler in predetermined areas, e.g., striated layers having different filler concentration.
(147) Preferably, for a typical filled product, the filler is substantially evenly distributed and more preferably evenly distributed within the end product. In this manner localize stresses or weak points can be avoided. Generally, for a non-reinforced material each filler particle may have a volume that is less than about 0.3%, less than about 0.2%, less than about 0.1%, and less than about 0.05% of the volume of a product, intermediate or proppant. For example, if the product is spherical in shape and the filler is spherical in shape the diameter of the filler should preferable be about 1/10 to about 1/20 of the diameter of the proppant particle, and more preferably the filler diameter should be less than about 1/20 of the diameter of the proppant particle. Generally, the relative amount of filler used in a material should preferable be about 30% to about 65% of the volume of the sphere, e.g., volume %.
(148) Generally, when a small particulate filler, e.g., fines, beads, pellets, is used for the purposes of increasing strength, without the presence of fibers, fabric, etc., generally at least about 2% to at least about 5 volume %, can show an increase in the strength, although this may be greater or smaller depending upon other factors, such as the shape and volume of the product, later processing conditions, e.g., cure time, temperature, number of pyrolysis reinfiltrations. Generally, as the filler level increases from about above 5 volume % no further strength benefits may be realized. Such small particulate filled products, in which appreciable strength benefits are obtained from the filler, and in particular an increase in strength of at least about 5%, at last about 10% and preferably at least about 20% would be considered to be reinforced products and materials.
(149) At various points during the manufacturing process, the polysilocarb structures, intermediates and end products, and combinations and variations of these, may be machined, milled, molded, shaped, broken, drilled or otherwise mechanically processed and shaped.
(150) The precursor formulations are preferably clear or are essentially colorless and generally transmissive to light in the visible wavelengths. They may, depending upon the formulation have a turbid, milky or clouding appearance. They may also have color bodies, pigments or colorants, as well as color filler (which can survive pyrolysis, for ceramic end products, such as those used in ceramic pottery glazes). The precursor may also have a yellow or amber color or tint, without the need of the addition of a colorant.
(151) The precursor formulations may be packaged, shipped and stored for later use in forming products, e.g., proppants, or they may be used directly in these processes, e.g., continuous process to make a proppant. Thus, a precursor formulation may be stored in 55 gallon drums, tank trucks, rail tack cars, onsite storage tanks having the capable of holding hundreds of gals, and shipping totes holding 1,000 liters, by way of example. Additionally, in manufacturing process the formulations may be made and used in a continuous, and semi-continuous processes.
(152) The present inventions, among other things, provide substantial flexibility in designing processes, systems, ceramics, having processing properties and end product performance features to meet predetermined and specific performance criteria. Thus, for example the viscosity of the precursor formulation may be predetermined by the formulation to match a particular morphology of the reinforcing material, the cure temperature of the precursor formulation may be predetermined by the formulation to enable a prepreg to have an extended shelf life. The viscosity of the of the precursor formulation may be established so that the precursor readily flows into the processing head, e.g., a sonic nozzle. The formulation of the precursor formulation may also, for example, be such that the strength of a cured preform is sufficient to allow rough or initial processing of the preform, prior to pyrolysis, e.g., breaking up of a puck to provide small, e.g., about 10 mm diameters to about 10 micron diameters, and potentially smaller to the micron and submicron diameter size.
(153) Custom and predetermined control of when chemical reactions occur in the various stages of the process from raw material to final end product can provide for reduced costs, increased process control, increased reliability, increased efficiency, enhanced product features, and combinations and variation of these and other benefits. The sequencing of when chemical reactions take place can be based primarily upon the processing or making of precursors, and the processing or making of precursor formulations; and may also be based upon cure and pyrolysis conditions. Further, the custom and predetermined selection of these steps, formulations and conditions, can provide enhanced product and processing features through chemical reactions, molecular arrangements and rearrangements, and microstructure arrangements and rearrangements, that preferably have been predetermined and controlled.
(154) It should be understood that the use of headings in this specification is for the purpose of clarity, and are not limiting in any way. Thus, the processes and disclosures described under a heading should be read in context with the entirely of this specification, including the various examples. The use of headings in this specification should not limit the scope of protection afford the present inventions.
(155) Generally, the process form making the present polysilocarb materials involves one or more steps. The starting materials are obtained, made or derived. Precursors are obtained or can be made from starting materials. The precursors are combined to form a precursor formulation. The precursor formulation is then shaped, dropped, extruded, sprayed, formed, molded, etc. into a desired form, which form is then cured, which among other things transforms the precursor formulation into a plastic like material. This cured plastic like material can then be pyrolyzed into a ceramic. It being understood, that these steps may not all be used, that some of these steps may be repeated, once, twice or several times, and that combinations and variations of these general steps may be utilized to obtain a desired product or result.
(156) Processes for Obtaining a Polysilocarb Precursor Formulation
(157) Polysilocarb precursor formulations can generally be made using two types of processes, although other processes and variations of these types of processes may be utilized. These processes generally involve combining precursors to form a polysilocarb precursor formulation. One type of process generally involves the mixing together of precursor materials in preferably a solvent free process with essentially no chemical reactions taking place, e.g., “the mixing process.” The other type of process generally involves chemical reactions to form specific, e.g., custom, polysilocarb precursor formulations, which could be monomers, dimers, trimers and polymers. Generally, in the mixing process essentially all, and preferably all, of the chemical reactions take place during subsequent processing, such as during curing, pyrolysis and both. It should be understood that these terms—reaction type process and the mixing type process—are used for convenience, e.g., a short hand reference, and should not be viewed as limiting. Further, it should be understood that combinations and variations of these two processes may be used in reaching a precursor formulation, and in reaching intermediate, end and final products. Depending upon the specific process and desired features of the product the precursors and starting materials for one process type can be used in the other. These processes provide great flexibility to create custom features for intermediate, end and final products, and thus, typically, either process type, and combinations of them, can provide a specific predetermined product. In selecting which type of process is preferable factors such as cost, controllability, shelf life, scale up, manufacturing ease, etc., can be considered.
(158) The two process types are described in this specification, among other places, under their respective headings. It should be understood that the teachings for one process, under one heading, and the teachings for the other process, under the other heading, can be applicable to each other, as well as, being applicable to other sections and teachings in this specification, and vice versa. The starting or precursor materials for one type of process may be used in the other type of process. Further, it should be understood that the processes described under these headings should be read in context with the entirely of this specification, including the various examples. Thus, the use of headings in this specification should not limit the scope of protection afford the present inventions.
(159) Additionally, the formulations from the mixing type process may be used as a precursor, or component in the reaction type process. Similarly, a formulation from the reaction type process may be used in the mixing type process. Thus, and preferably, the optimum performance and features from either process can be combined and utilized to provide a cost effective and efficient process and end product.
(160) In addition to being commercially available the precursors may be made by way of an alkoxylation type, e.g., ethoxylation process. In this process chlorosilanes are reacted with ethanol in the presences of a catalysis, e.g., HCl, to provide the precursor materials, which materials may further be reacted to provide longer chain precursors. Other alcohols, e.g., Methanol may also be used. Thus, the compounds the formulas of
(161) The Mixing Type Process
(162) Precursor materials may be methyl hydrogen, and substituted and modified methyl hydrogens, siloxane backbone additives, reactive monomers, reaction products of a siloxane backbone additive with a silane modifier or an organic modifier, and other similar types of materials, such as silane based materials, silazane based materials, carbosilane based materials, phenol/formaldehyde based materials, and combinations and variations of these. The precursors are preferably liquids at room temperature, although they may be solids that are melted, or that are soluble in one of the other precursors. (In this situation, however, it should be understood that when one precursor dissolves another, it is nevertheless not considered to be a “solvent” as that term is used with respect to the prior art processes that employ non-constituent solvents, e.g., solvents that do not form a part or component of the end product, are treated as waste products, and both.)
(163) The precursors are mixed together in a vessel, preferably at room temperature. Preferably, little, and more preferably no solvents, e.g., water, organic solvents, polar solvents, non-polar solvents, hexane, THF, toluene, are added to this mixture of precursor materials. Preferably, each precursor material is miscible with the others, e.g., they can be mixed at any relative amounts, or in any proportions, and will not separate or precipitate. At this point the “precursor mixture” or “polysilocarb precursor formulation” is compete (noting that if only a single precursor is used the material would simply be a “polysilocarb precursor” or a “polysilocarb precursor formulation”). Although complete, fillers and reinforcers may be added to the formulation. In preferred embodiments of the formulation, essentially no, and more preferably no chemical reactions, e.g., crosslinking or polymerization, takes place within the formulation, when the formulation is mixed, or when the formulation is being held in a vessel, on a prepreg, or other time period, prior to being cured.
(164) Additionally, inhibitors such as cyclohexane, 1-Ethynyl-1-cyclohexanol (which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane (which may act, depending upon amount and temperature as a reactant or a reactant retardant (i.e., slows down a reaction to increase pot life), e.g., at room temperature it is a retardant and at elevated temperatures it is a reactant), may be added to the polysilocarb precursor formulation, e.g., an inhibited polysilocarb precursor formulation. Other materials, as well, may be added to the polysilocarb precursor formulation, e.g., a filled polysilocarb precursor formulation, at this point in processing, including fillers such as SiC powder, PDC particles, pigments, particles, nano-tubes, whiskers, or other materials, discussed in this specification or otherwise known to the arts. Further, a formulation with both inhibitors and fillers would be considered an inhibited, filled polysilocarb precursor formulation.
(165) Depending upon the particular precursors and their relative amounts in the polysilocarb precursor formulation, polysilocarb precursor formulations may have shelf lives at room temperature of greater than 12 hours, greater than 1 day, greater than 1 week, greater than 1 month, and for years or more. These precursor formulations may have shelf lives at high temperatures, for example, at about 90° F., of greater than 12 hours, greater than 1 day, greater than 1 week, greater than 1 month, and for years or more. The use of inhibitors may further extend the shelf life in time, for higher temperatures, and combinations and variations of these. As used herein the term “shelf life” should be given its broadest possible meaning unless specified otherwise, and would include the formulation being capable of being used for its intended purpose, or performing, e.g., functioning, for its intended use, at 100% percent as well as a freshly made formulation, at least about 90% as well as a freshly made formulation, at least about 80% as well as a freshly made formulation, and at about 70% as well as a freshly made formulation.
(166) Precursors and precursor formulations are preferably non-hazardous materials. They have flash points that are preferably above about 70° C., above about 80° C., above about 100° C. and above about 300° C., and above. They may be noncorrosive. They may have as low vapor pressure, may have low or no odor, and may be non- or mildly irritating to the skin.
(167) A catalyst may be used, and can be added at the time of, prior to, shortly before, or at an earlier time before the precursor formulation is formed or made into a structure, prior to curing. The catalysis assists in, advances, promotes the curing of the precursor formulation to form a preform.
(168) The time period where the precursor formulation remains useful for curing after the catalysis is added is referred to as “pot life”, e.g., how long can the catalyzed formulation remain in its holding vessel before it should be used. Depending upon the particular formulation, whether an inhibitor is being used, and if so the amount being used, storage conditions, e.g., temperature, and potentially other factors, precursor formulations can have pot lives, for example of from about 5 minutes to about 10 days, about 1 day to about 6 days, about 4 to 5 days, about 1 hour to about 24 hours, and about 12 hours to about 24 hours.
(169) The catalysis can be any platinum (Pt) based catalyst, which can for example be diluted to a range from: 1 part per million Pt to 200 parts per million (ppm) and preferably in the 5 ppm to 50 ppm range. It can be a peroxide based catalyst with a 10 hour half life above 90 C at a concentration of between 0.5% and 2%. It can be an organic based peroxide. It can be any organometallic catalyst capable of reacting with Si—H bond, Si—OH bonds, or unsaturated carbon bonds, these catalyst may include: dibutyltin dilaurate, zinc octoate, and titanium organometallic compounds. Combinations and variations of these and other catalysts may be used. Such catalysts may be obtained from ARKEMA under the trade name LUPEROX, e.g., LUPEROX 231.
(170) Further, custom and specific combinations of these and other catalysts may be used, such that they are matched to specific formulation formulations, and in this way selectively and specifically catalyze the reaction of specific constituents. Custom and specific combinations of catalysts may be used, such that they are matched to specific formulation formulations, and in this way selectively and specifically catalyze the reaction of specific constituents at specific temperatures. Moreover, the use of these types of matched catalyst—formulations systems may be used to provide predetermined product features, such as for example, pore structures, porosity, densities, density profiles, and other morphologies of cured structures and ceramics.
(171) In this mixing type process for making a precursor formulation, preferably chemical reactions or molecular rearrangements only take place during the making of the precursors, the curing process of the preform, and in the pyrolizing process. Thus, chemical reactions, e.g., polymerizations, reductions, condensations, substitutions, take place or are utilized in the making of a precursor. In making a polysilocarb precursor formulation preferably no and essentially no, chemical reactions and molecular rearrangements take place. These embodiments of the present mixing type process, which avoid the need to, and do not, utilize a polymerization or other reaction during the making of a precursor formulation, provides significant advantages over prior methods of making polymer derived ceramics. Preferably, in the embodiments of these mixing type of formulations and processes, polymerization, crosslinking or other chemical reactions take place primarily, preferably essentially, and more preferably solely in the preform during the curing process.
(172) The precursor may be methyl hydrogen (MH), which formula is shown in
(173) The precursor may be a siloxane backbone additive, such as vinyl substituted polydimethyl siloxane, which formula is shown in
(174) The precursor may be a siloxane backbone additive, such as vinyl substituted and vinyl terminated polydimethyl siloxane, which formula is shown in
(175) The precursor may be a siloxane backbone additive, such as vinyl substituted and hydrogen terminated polydimethyl siloxane, which formula is shown in
(176) The precursor may be a siloxane backbone additive, such as allyl terminated polydimethyl siloxane, which formula is shown in
(177) The precursor may be a siloxane backbone additive, such as vinyl terminated polydimethyl siloxane, which formula is shown in
(178) The precursor may be a siloxane backbone additive, such as silanol (hydroxy) terminated polydimethyl siloxane, which formula is shown in
(179) The precursor may be a siloxane backbone additive, such as silanol (hydroxy) terminated vinyl substituted dimethyl siloxane, which formula is shown in
(180) The precursor may be a siloxane backbone additive, such as hydrogen (hydride) terminated polydimethyl siloxane, which formula is shown in
(181) The precursor may be a siloxane backbone additive, such as phenyl terminated polydimethyl siloxane, which formula is shown in
(182) The precursor may be a siloxane backbone additive, such as methyl-phenyl terminated polydimethyl siloxane, which formula is shown in 20. This precursor may have a molecular weight (mw) may be from about 500 mw to about 2,000 mw, and may have a viscosity preferably from about 80 cps to about 300 cps. The repeating units are the same. This precursor may be used to provide a toughening agent and to adjust the refractive index of the polymer to match the refractive index of various types of glass, to provide for example transparent fiberglass, as well as, other features and characteristics to the cured preform and ceramic material.
(183) The precursor may be a siloxane backbone additive, such as diphenyl dimethyl polysiloxane, which formula is shown in
(184) The precursor may be a siloxane backbone additive, such as vinyl terminated diphenyl dimethyl polysiloxane, which formula is shown in
(185) The precursor may be a siloxane backbone additive, such as hydroxy terminated diphenyl dimethyl polysiloxane, which formula is shown in
(186) The precursor may be a siloxane backbone additive, such as hydride terminated diphenyl dimethyl polysiloxane, which formula is shown in
(187) The precursor may be a siloxane backbone additive, such as styrene vinyl benzene dimethyl polysiloxane, which formula is shown in
(188) The precursor may be a reactive monomer, such as tetramethyltetravinylcyclotetrasiloxane (“TV”), which formula is shown in
(189) The precursor may be a reactive monomer, such as trivinyl cyclotetrasiloxane, which formula is shown in
(190) The precursor may be a silane modifier, such as vinyl phenyl methyl silane, which formula is shown in
(191) The precursors of
(192) The precursor may be a reaction product of a silane modifier with a siloxane backbone additive, such as phenyl methyl silane substituted MH, which formula is shown in
(193) The precursor may be a reaction product of a silane modifier (e.g.,
(194) The precursor may be a reaction product of a silane modifier (e.g.,
(195) The precursor may be a reaction product of a silane modifier (e.g.,
(196) The precursor may be a reaction product of a silane modifier (e.g.,
(197) The precursor may be a reaction product of a silane modifier (e.g.,
(198) The precursor may be a partially hydrolyzed tertraethyl orthosilicate, which formula is shown in
(199) The precursor may also be a methylsesquisilioxane such as SR-350 available from General Electric Company, Wilton, Conn. The precursor may also be a phenyl methyl siloxane such as 604 from Wacker Chemie AG. The precursor may also be a methylphenylvinylsiloxane, such as H62 C from Wacker Chemie AG.
(200) The precursors may also be selected from the following: SiSiB® HF2020, TRIMETHYLSILYL TERMINATED METHYL HYDROGEN SILICONE FLUID 63148-57-2; SiSiB® HF2050 TRIMETHYLSILYL TERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 68037-59-2; SiSiB® HF2060 HYDRIDE TERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 69013-23-6; SiSiB® HF2038 HYDROGEN TERMINATED POLYDIPHENYL SILOXANE; SiSiB® HF2068 HYDRIDE TERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 115487-49-5; SiSiB® HF2078 HYDRIDE TERMINATED POLY(PHENYLDIMETHYLSILOXY) SILOXANE PHENYL SILSESQUIOXANE, HYDROGEN-TERMINATED 68952-30-7; SiSiB® VF6060 VINYLDIMETHYL TERMINATED VINYLMETHYL DIMETHYL POLYSILOXANE COPOLYMERS 68083-18-1; SiSiB® VF6862 VINYLDIMETHYL TERMINATED DIMETHYL DIPHENYL POLYSILOXANE COPOLYMER 68951-96-2; SiSiB® VF6872 VINYLDIMETHYL TERMINATED DIMETHYL-METHYLVINYL-DIPHENYL POLYSILOXANE COPOLYMER; SiSiB® PC9401 1,1,3,3-TETRAMETHYL-1,3-DIVINYLDISILOXANE 2627-95-4; SiSiB® PF1070 SILANOL TERMINATED POLYDIMETHYLSILOXANE (OF1070) 70131-67-8; SiSiB@ OF1070 SILANOL TERMINATED POLYDIMETHYSILOXANE 70131-67-8; OH-ENDCAPPED POLYDIMETHYLSILOXANE HYDROXY TERMINATED OLYDIMETHYLSILOXANE 73138-87-1; SiSiB® VF6030 VINYL TERMINATED POLYDIMETHYL SILOXANE 68083-19-2; and, SiSiB® HF2030 HYDROGEN TERMINATED POLYDIMETHYLSILOXANE FLUID 70900-21-9.
(201) Thus, in additional to the forgoing specific precursors, it is contemplated that a precursor may be compound of the general formula of
(202) In general, embodiments of formulations for polysilocarb formulations may for example have from about 20% to about 99% MH, about 0% to about 30% siloxane backbone additives, about 1% to about 60% reactive monomers, and, about 0% to about 90% reaction products of a siloxane backbone additives with a silane modifier or an organic modifier reaction products.
(203) In mixing the formulations a sufficient time to permit the precursors to become effectively mixed and dispersed. Generally, mixing of about 15 minutes to an hour is sufficient. Typically, the precursor formulations are relatively, and essentially, shear insensitive, and thus the type of pumps or mixing are not critical. It is further noted that in higher viscosity formulations additional mixing time may be required. The temperature of the formulations, during mixing should be kept below about 45 degrees C., and preferably about 10 degrees C. (It is noted that these mixing conditions are for the pre-catalyzed formulations)
(204) The Reaction Type Process
(205) In the reaction type process, in general, a chemical reaction is used to combine one, two or more precursors, typically in the presence of a solvent, to form a precursor formulation that is essentially made up of a single polymer that can then be cured and if need be pyrolized. This process provides the ability to build custom precursor formulations that when cured can provide plastics having unique and desirable features such as high temperature, flame resistance and retardation, strength and other features. The cured materials can also be pyrolized to form ceramics having unique features. The reaction type process allows for the predetermined balancing of different types of functionality in the end product by selecting function groups for incorporation into the polymer that makes up the precursor formulation, e.g., phenyls which typically are not used for ceramics but have benefits for providing high temperature capabilities for plastics, and styrene which typically does not provide high temperature features for plastics but provides benefits for ceramics.
(206) In general a custom polymer for use as a precursor formulation is made by reacting precursors in a condensation reaction to form the polymer precursor formulation. This precursor formulation is then cured into a preform through a hydrolysis reaction. The condensation reaction forms a polymer of the type shown in
(207) In general, the precursors, e.g.,
(208) Control factors for determining chain length are: the monomers chosen (generally, the smaller the monomers the more that can be added before they begin to coil around and bond to themselves); the amount and point in the reaction where end cappers are introduced; and the amount of water and the rate of addition. Thus, the chain lengths can be from about 180 mw (viscosity about 5 cps) to about 65,000 mw (viscosity of about 10,000 cps), greater than about 1000 mw, greater than about 10,000 mw, greater than about 50,000 mw and greater. Further, the polymerized precursor formulation may, and typically does, have polymers of different molecular weights, which can be predetermined to provide formulation, cured, and ceramic product performance features.
(209) Upon completion of the polymerization reaction the material is transferred into a separation apparatus, e.g., a separation funnel, which has an amount of deionized water that is from about 1.2× to about 1.5× the mass of the material. This mixture is vigorously stirred for about less than 1 minute and preferably from about 5 to 30 sections. Once stirred the material is allowed to settle and separate, which may take from about 1 to 2 hours. The polymer is the higher density material and is removed from the vessel. This removed polymer is then dried by either warming in a shallow tray at 90 C for about two hours; or, preferably, is passed through a wiped film distillation apparatus, to remove any residual water and ethanol. Alternatively, sodium bicarbonate sufficient to buffer the aqueous layer to a pH of about 4 to about 7 is added. It is further understood that other, and commercial, manners of separating the polymer from the material may be employed.
(210) Preferably a catalyst is used in the curing process of the polymer pressure formulations from the reaction type process. The same polymers as used for curing the formulation from the mixing type process can be used. It is noted that unlike the mixing type formulations, a catalyst is not necessarily required. However, if not used, reaction time and rates will be slower. The pyrolysis of the cured material is essentially the same as the cured material from the mixing process.
(211) Curing and Pyrolysis
(212) The preform can be cured in a controlled atmosphere, such as an inert gas, or it can be cured in the atmosphere. The curing can be conducted in reduce pressure, e.g., vacuum, or in reduced pressure flowing gas (e.g., inert) streams. The cure conditions, e.g., temperature, time, rate, can be predetermined by the formulation to match, for example the size of the preform, the shape of the preform, or the mold holding the preform to prevent stress cracking, off gassing, or other problems associated with the curing process. Further, the curing conditions may be such as to take advantage of, in a controlled manner, what may have been previously perceived as problems associated with the curing process. Thus, for example, off gassing may be used to create a foam material having either open or closed structure. Further, the porosity of the material may be predetermined such that, for example, a particular pore size may be obtained, and in this manner a filter or ceramic screen having predetermined pore sizes, flow characteristic may be made.
(213) The preforms, either unreinforced, neat, or reinforced, may be used as a stand alone product, an end product, a final product, or a preliminary product for which later machining or processing may be performed on. The preforms may also be subject to pyrolysis, which converts the preform material into a ceramic.
(214) During the curing process some formulations may exhibit an exotherm, i.e., a self heating reaction, that can produce a small amount of heat to assist or drive the curing reaction, or they may produce a large amount of heat that may need to be managed and removed in order to avoid problems, such as stress fractures. During the cure off gassing typically occurs and results in a loss of material, which loss is defined generally by the amount of material remaining, e.g., cure yield. The formulations and polysilocarb precursor formulations of embodiments of the present inventions can have cure yields of at least about 90%, about 92%, about 100%. In fact, with air cures the materials may have cure yields above 100%, e.g., about 101-105%, as a result of oxygen being absorbed from the air. Additionally, during curing the material shrinks, this shrinkage may be, depending upon the formulation and the nature of the preform shape, and whether the preform is reinforce, neat or unreinforced, from about 20%, less than 20%, less than about 15%, less than about 5%, less than about 1%, less than about 0.5%, less than about 0.25% and smaller.
(215) In pyrolizing the preform, or cured structure or cured material, it is heated to above about 650° C. to about 1,200° C. At these temperatures typically all organic structures are either removed or combined with the inorganic constituents to form a ceramic. Typically at temperatures in the 650° C. to 1,200° C. range the material is an amorphous glassy ceramic. When heated above 1,200° C. the material may from nano crystalline structures, or micro crystalline structures, such as SiC, Si3N.sub.4, SiCN, β SiC, and above 1,900° C. an α SiC structure may form.
(216) During pyrolysis material is loss through off gassing. The amount of material remaining at the end of a pyrolysis set is referred to as char yield (or pyrolysis yield). The formulations and polysilocarb precursor formulations of embodiments of the present inventions can have char yields of at least about 60%, about 70%, about 80%, and at least about 90%, at least about 91% and greater. In fact, with air pyrolysis the materials may have cure yields well above 91%, which can approach 100%. In order to avoid the degradation of the material in an air pyrolysis (noting that typically pyrolysis is conducted in an inert atmospheres) specifically tailored formulations must be used, such as for example, formulations high in phenyl content (at least about 11%, and preferably at least about 20% by weight phenyls), formulations high in allyl content (at least about 15% to about 60%). Thus, there is provided formulations and polysilocarb precursor formulations that are capable of being air pyrolized to form a ceramic and to preferably do so at char yield in excess of at least about 80% and above 88%.
(217) The initial or first pyrolysis step generally yields a structure that is not very dense, and for example, has not reached the density required for its intended use. However, in some examples, such as the use of light weight spheres, the first pyrolysis may be sufficient. Thus, typically a reinfiltration process may be performed on the pyrolized material, to add in additional polysilocarb precursor formulation material, to fill in, or fill the voids and spaces in the structure. This reinfiltrated material is they repyrolized. This process of pyrolization, reinfiltration may be repeated, through one, two, three, and up to 10 or more times to obtain the desired density of the final product. Additionally, with formulations of embodiments of the present inventions, the viscosity of the formulation may be tailored to provide more efficient reinfiltrations, and thus, a different formulation may be used at later reinfiltration steps, as the voids or pores become smaller and more difficult to get the formulation material into it. The high char yields, and other features of embodiments of the present invention, enable the manufacture of completely closed structures, e.g., “helium tight” materials, with less than twelve reinfiltration steps, less than about 10 reinfiltrations steps and less than five reinfiltrations steps. Thus, by way of example, an initial inert gas pyrolysis may be performed with a high char yield formulation followed by four reinfiltration air pyrolysis steps.
(218) Upon curing the polysilocarb precursor formulation a cross linking reaction takes place that provides a cross linked structure having, among other things, an —R.sub.1—Si—C—C—Si—O—Si—C—C—Si—R.sub.2— where R.sub.1 and R.sub.2 vary depending upon, and are based upon, the precursors used in the formulation.
(219) Embodiments of the present inventions have the ability to utilize precursors that have impurities, high-level impurities and significant impurities. Thus, the precursors may have more than about 0.1% impurities, more than about 0.5%, more than about 1% impurities, more than about 5% impurities, more than about 10% impurities, and more than about 50% impurities. In using materials with impurities, the amounts of these impurities, or at least the relative amounts, so that the amount of actual precursor is known, should preferably be determined by for example GPC (Gel Permeation Chromatography) or other methods of analysis. In this manner the formulation of the polysilocarb precursor formulation may be adjusted for the amount of impurities present. The ability of embodiments of the present invention to utilize lower level impurity materials, and essentially impure materials, and highly impure materials, provides significant advantages over other method of making polymer derived ceramics. This provides two significant advantages, among other things. First, the ability to use impure, lower purity, materials in embodiments of the present inventions, provides the ability to greatly reduce the cost of the formulations and end products, e.g., cured preforms, cured parts, and ceramic parts or structures. Second, the ability to use impure, lower purity, materials in embodiments of the present inventions, provides the ability to have end products, e.g., cured preforms, cured parts, and ceramic parts or structures, that have a substantially greater consistence from part to part, because variations in starting materials can be adjusted for during the formulation of each polysilocarb precursor formulation.
(220) Turning to
(221) The tower 6101 has wall 6102 containing heating units, as well as, insolation and control devices for the heating units. In the embodiment of
(222) Although two temperature zones and six nozzles are utilized in the embodiment of
(223) The following examples are provided to illustrate various embodiments of oil field treatments, hydraulic fracturing treatments, processes, precursors, batches, cured preform proppants, synthetic proppants, PDC proppants, and PsDC proppants of the present inventions. These examples are for illustrative purposes, and should not be viewed as, and do not otherwise limit the scope of the present inventions. The percentages used in the examples, unless specified otherwise, are weight percents of the total batch, preform or structure.
EXAMPLES
Example 1
(224) Using a tower forming and cure system, a polysilocarb batch having 75% MH, 15% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 8 foot curing tower. The temperature at the top of the tower is from 495-505° C. the temperature at the bottom of the tower is 650° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. A collection pan at the bottom of the tower is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 2 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 2
(225) Using a tower forming and cure system, a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 8 foot curing tower. The temperature at the top of the tower is from 495-505° C. the temperature at the bottom of the tower is 650° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. A collection pan at the bottom of the tower is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 2 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 2a
(226) Turning to
Example 2b
(227) Turning to
Example 2c
(228) Turning to
Example 3
(229) Using a tower forming and cure system, a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 8 foot curing tower. The temperature at the top of the tower is from 345° C. the temperature at the bottom of the tower is 550° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. The collection pan is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 3 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 4
(230) PsDC proppants are made using a tower cure system. 50% by volume fly ash is added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide). This batch is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 18 foot curing tower. The temperature at the top of the tower is from 200-500° C. the temperature at the bottom of the tower is from 200-600° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. The collection pan is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 3 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 5
(231) 40% by volume AL.sub.2O.sub.3 having a diameter of 0.5 μm is added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide). Using a tower cure system, this batch is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 18 foot curing tower. The temperature at the top of the tower is from 200-500° C. the temperature at the bottom of the tower is from 200-600° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. The collection pan is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 3 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 6
(232) A polysilocarb batch having 70% of the MH precursor (molecular weight of about 800) and 30% of the TV precursor are mixed together in a vessel and put in storage for later use. The polysilocarb batch has good shelf life and room temperature and the precursors have not, and do not react with each other. The polysilocarb batch has a viscosity of about 15 cps. 28% of an about 80 micron to about 325 mesh SiC filler is added to the batch to make a filled polysilocarb batch, which can be kept for later use. Just prior to forming and curing 10 ppm of a platinum catalyst is added to each of the polysilocarb batches and this catalyzed batch is dropped on a tray to form droplets which are cured in an air oven at about 125° C. for about 30 minutes. The cured drop structures are spherical type structures with densities of about 1.1-1.7 g/cc, diameters of about 200 microns to about 2 mm, and crush strengths of about 3-7 ksi.
Example 7
(233) A polysilocarb batch having 70% of the MH precursor (molecular weight of about 800) and 30% of the TV precursor are mixed together in a vessel and put in storage for later use. The polysilocarb batch has good shelf life and room temperature and the precursors have not, and do not react with each other. The polysilocarb batch has a viscosity of about 15 cps. 21% of a silica fume (about 325 mesh) are added to the batch to make a filled polysilocarb batch, which can be kept for later use. Just prior to forming into preform proppants, 10 ppm of a platinum catalyst is added to the polysilocarb batch and these catalyzed batches are dropped into the curing tower and air cured. The cured drop structures are spherical type structures with densities of about 1.1-1.7 g/cc, diameters of about 200 microns, and (API/ISO) crush strengths of about 7 k psi.
Example 8
(234) A polysilocarb batch having 75% of the MH precursor (molecular weight of about 800) and 25% of the TV precursor are mixed together in a vessel and put in storage for later use. The polysilocarb batch has good shelf life and room temperature and the precursors have not, and do not react with each other. The polysilocarb batch has a viscosity of about 18 cps. 40% of a silica fume to about 325 mesh silica filler is added to the batch to make a filled polysilocarb batch, which can be kept for later use. Prior to forming and curing 10 ppm of a platinum catalyst is added to each of the polysilocarb batch and this batch is formed into spherical proppants under similar forming and curing conditions to those of the forming and curing tower in Example 1.
Example 9
(235) A polysilocarb batch having 10% of the MH precursor (molecular weight of about 800), 73% of the STY (
Example 10
(236) A polysilocarb batch having about 70% MH, 20% TV precursor, 10% VT (molecular weight of about 6000), and 1% of the OH terminated precursor of the formula of
Example 11
(237) A polysilocarb batch has 75% MH, 15% TV, 10% VT and a viscosity of about 65 cps. 10 ppm of a platinum and peroxide catalyst mixture is added to this batch and drops of the catalyzed batch are dripped into a hot air column having a temperature of about 375° C. and fall by gravity for about a distance of 8 ft in the air column. The cured spheres from the bottom of the air column are pyrolized in an inert atmosphere at 1,000° C. for about 60 minutes. The pyrolized round spheres have a very uniform size (e.g., monosize distribution), density of about 2.0-2.1 g/cc, a diameter of about 400-800 microns, and a crush strength of about (API/ISO) 4-5.5 k psi.
Example 12
(238) A polysilocarb batch having 70% of the MH and 30% of the VT having a molecular weight of about 500 and about 42% of a submicron and a 325 mesh silica are mixed together in a vessel and put in storage for later use. The polysilocarb batch has good shelf life and room temperature and the precursors have not, and do not react with each other. The polysilocarb batch has a viscosity of about 300 cps. PsDCs are are made from this batch following the methods of Example 1.
Example 13
(239) PsDCs having the following characteristics:
(240) TABLE-US-00004 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.00 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 2.39 ISO Crush Analysis (>10% fines) >5000
Example 14
(241) PsDCs having the following characteristics.
(242) TABLE-US-00005 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.10 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 2.89 ISO Crush Analysis (>10% fines) >5000
Example 15
(243) PsDCs having the following characteristics.
(244) TABLE-US-00006 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.20 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 3.47 ISO Crush Analysis (>10% fines) >5000
Example 16
(245) PsDCs having the following characteristics.
(246) TABLE-US-00007 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.30 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 4.14 ISO Crush Analysis (>10% fines) >5000
Example 17
(247) PsDCs having the following characteristics.
(248) TABLE-US-00008 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.40 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 4.90 ISO Crush Analysis (>10% fines) >5000
Example 18
(249) PsDCs having the following characteristics.
(250) TABLE-US-00009 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.50 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 5.78 ISO Crush Analysis (>10% fines) >5000
Example 19
(251) PsDCs having the following characteristics.
(252) TABLE-US-00010 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.60 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 6.78 ISO Crush Analysis (>10% fines) >5000
Example 20
(253) PsDCs having the following characteristics.
(254) TABLE-US-00011 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.70 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 7.92 ISO Crush Analysis (>10% fines) >10,000
Example 21
(255) PsDCs having the following characteristics.
(256) TABLE-US-00012 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.80 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 9.22 ISO Crush Analysis (>10% fines) >10,000
Example 22
(257) PsDCs having the following characteristics.
(258) TABLE-US-00013 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 1.90 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 10.71 ISO Crush Analysis (>10% fines) >10,000
Example 23
(259) PsDCs having the following characteristics.
(260) TABLE-US-00014 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 2.00 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 12.40 ISO Crush Analysis (>10% fines) >10,000
Example 24
(261) PsDCs having the following characteristics.
(262) TABLE-US-00015 Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05 g/cc) 2.10 Sphericity/Roundness greater than .95 Clusters (%) 0 Particle Distribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@ <.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F. Settling Rate 14.32 ISO Crush Analysis (>10% fines) >10,000
Example 25
(263) The PsDCs of Example 24 are made having a predetermined mesh size of from about 8 to about 200, with 95% of the particle size distribution being within mesh of the predetermined value. 4,000,000 pounds of this proppant are mixed with 1 million gallons of slick water fracturing fluid for a fracturing treatment of an unconventional shale formation.
Example 26
(264) The PsDCs of Example 24 are made having a predetermined mesh size of from about 8 to about 200, with 95% of the particle size distribution being within 8 mesh of the predetermined value. 7,000,000 pounds of this proppant are mixed with 2 million gallons of slick water fracturing fluid for a fracturing treatment of an unconventional shale formation.
Example 27
(265) The PsDCs or Example 24 are made having a predetermined mesh size of greater than 200, with 95% of the particle size distribution being within 8 mesh of the predetermined value. 4,000,000 pounds of this proppant are mixed with 1 million gallons of fracturing fluid for a fracturing treatment of a conventional formation.
Example 28
(266) The PsDCs or Example 24 are made having a predetermined mesh size of greater than 200, with 95% of the particle size distribution being within 5 mesh of the predetermined value. 7,000,000 pounds of this proppant are mixed with 2 million gallons of fracturing fluid for a fracturing treatment of an unconventional shale formation.
Example 29—Fracturing
(267) Using embodiments of the PsDC of these examples, e.g., Example 2, 35, 42, 49, 53, 54, and 55 the following fracture plan is carried out on a formation.
(268) Interval #1
(269) TABLE-US-00016 Fracture Half-Length (ft) 263 Propped Half-Length (ft) 204 Total Fracture Height (ft) 307 Total Propped Height (ft) 238 Depth to Fracture Top (ft) 5449 Depth to Propped 5518 Fracture Top (ft) Depth to Fracture Bottom (ft) 5756 Depth to Propped 5756 Fracture Bottom (ft) Equivalent Number of 1.0 Max. Fracture Width (in) 0.71 Multiple Fracs Fracture Slurry Efficiency** 0.74 Avg. Fracture Width (in) 0.39 Avg. Proppant 1.51 Concentration (lb/ft.sup.2)
(270) Fracture Geometry Summary*—Interval #2
(271) TABLE-US-00017 Fracture Half-Length (ft) 244 Propped Half-Length (ft) 193 Total Fracture Height (ft) 308 Total Propped Height (ft) 244 Depth to Fracture Top (ft) 5638 Depth to Propped 5702 Fracture Top (ft) Depth to Fracture Bottom (ft) 5946 Depth to Propped 5946 Fracture Bottom (ft) Equivalent Number of 1.0 Max. Fracture Width (in) 0.68 Multiple Fracs Fracture Slurry Efficiency** 0.74 Avg. Fracture Width (in) 0.41 Avg. Proppant 1.52 Concentration (lb/ft.sup.2)
(272) Fracture Geometry Summary*—Interval #3
(273) TABLE-US-00018 Fracture Half-Length (ft) 252 Propped Half-Length 197 (ft) Total Fracture Height (ft) 305 Total Propped Height 238 (ft) Depth to Fracture Top (ft) 5882 Depth to Propped 5949 Fracture Top (ft) Depth to Fracture Bottom (ft) 6187 Depth to Propped 6186 Fracture Bottom (ft) Equivalent Number of 1.0 Max. Fracture Width 0.69 Multiple Fracs (in) Fracture Slurry Efficiency** 0.73 Avg. Fracture Width 0.39 (in) Avg. Proppant 1.52 Concentration (lb/ft.sup.2)
(274) Fracture Conductivity Summary*—Interval #1
(275) TABLE-US-00019 Avg. Conductivity** 757.0 Avg. Frac Width (Closed 0.104 (mD .Math. ft) on prop) (in) Dimensionless 37.09 Ref. Formation 0.1 Conductivity** Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factor at Stress (mD) Apparent Damage 0.00 Prop Perm with 82103 Factor*** Prop Damage (mD) Total Damage 0.50 Prop Perm with 82103 Factor Total Damage (mD) Effective Propped 196 Proppant Embedment 0.008 Length (ft) (in)
(276) Fracture Conductivity Summary*—Interval #2
(277) TABLE-US-00020 Avg. Conductivity** 770.7 Avg. Frac Width (Closed 0.104 (mD .Math. ft) on prop) (in) Dimensionless 39.90 Ref. Formation 0.1 Conductivity** Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factor at Stress (mD) Apparent Damage 0.00 Prop Perm with Prop 82103 Factor*** Damage (mD) Total Damage 0.50 Prop Perm with Total 82103 Factor Damage (mD) Effective Propped 186 Proppant 0.008 Length (ft) Embedment (in)
(278) Fracture Conductivity Summary*—Interval #3
(279) TABLE-US-00021 Avg. Conductivity** 749.4 Avg. Frac Width (Closed 0.104 (mD .Math. ft) on prop) (in) Dimensionless 38.05 Ref. Formation 0.1 Conductivity** Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factor at Stress (mD) Apparent Damage 0.00 Prop Perm with Prop 82103 Factor*** Damage (mD) Total Damage 0.50 Prop Perm with Total 82103 Factor Damage (mD) Effective Propped 189 Proppant 0.008 Length (ft) Embedment (in)
(280) Fracture Pressure Summary*—Interval #1
(281) TABLE-US-00022 Model Net Pressure** (psi) 727 BH Fracture Closure 5050 Stress (psi) Observed Net Pressure** (psi) 0 Closure Stress 0.898 Gradient (psi/ft) Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi) Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)
(282) Fracture Pressure Summary*—Interval #2
(283) TABLE-US-00023 Model Net Pressure** (psi) 707 BH Fracture Closure 5050 Stress (psi) Observed Net Pressure** (psi) 0 Closure Stress 0.867 Gradient (psi/ft) Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi) Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)
(284) Fracture Pressure Summary*—Interval #3
(285) TABLE-US-00024 Model Net Pressure** (psi) 694 BH Fracture Closure 5050 Stress (psi) Observed Net Pressure** (psi) 0 Closure Stress 0.834 Gradient (psi/ft) Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi) Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)
(286) Operations Summary*—Interval #1
(287) TABLE-US-00025 Total Clean Fluid Pumped 869.7 Total Proppant Pumped 205,800 (bbls) (klbs) Total Slurry Pumped (bbls) 994.1 Total Proppant in Fracture 69,500 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923 (hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751 Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.6 Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2 Secondary Fluid Type Secondary Proppant Type
(288) Operations Summary*—Interval #2
(289) TABLE-US-00026 Total Clean Fluid Pumped 849.0 Total Proppant Pumped 205,800 (bbls) (klbs) Total Slurry Pumped (bbls) 971.6 Total Proppant in Fracture 68,300 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923 (hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751 Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.3 Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2 Secondary Fluid Type Secondary Proppant Type
(290) Operations Summary*—Interval #3
(291) TABLE-US-00027 Total Clean Fluid Pumped 833.2 Total Proppant Pumped 205,800 (bbls) (klbs) Total Slurry Pumped (bbls) 953.5 Total Proppant in Fracture 67,000 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923 (hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751 Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.1 Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2 Secondary Fluid Type Secondary Proppant Type
(292) Model Calibration Summary
(293) TABLE-US-00028 Crack Opening Coefficient 8.50e−01 Width Decoupling Coefficient was 1.00e+00 calculated internally Tip Effects Coefficient 1.00e−04 Tip Radius Fraction 1.00e−02 Tip Effects Scale Volume (bbls) 100.0 Proppant Drag Effect Exponent 8.0 CLE Outside Payzone 1.00 Multiple fractures settings start (V/L/O) 1.0/1.0/1.0 Multiple fractures settings end (V/L/O) 1.0/1.0/1.0
(294) Hydraulic Fracture Growth History*—Interval #1
(295) TABLE-US-00029 Fracture Avg. Model Fracture Fracture Width at Fracture Net Equivalent End of Stage Time Half-Length Height Well Width Pressure Slurry Number of Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) Efficiency Multifracs 1 Main 29:45 223 220 0.498 0.251 645 0.70 1.0 frac pad 2 Main 31:42 228 228 0.506 0.253 646 0.70 1.0 frac slurry 3 Main 33:49 234 236 0.513 0.255 646 0.70 1.0 frac slurry 4 Main 41:23 251 260 0.537 0.267 650 0.71 1.0 frac slurry 5 Main 53:09 257 283 0.593 0.311 678 0.72 1.0 frac slurry 6 Main 69:22 262 303 0.691 0.379 718 0.74 1.0 frac slurry 7 Main 72:56 263 307 0.711 0.394 727 0.74 1.0 frac flush
(296) Hydraulic Fracture Growth History*—Interval #2
(297) TABLE-US-00030 Fracture Avg. Model Fracture Fracture Width at Fracture Net Equivalent End of Stage Time Half-Length Height Well Width Pressure Slurry Number of Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) Efficiency Multifracs 1 Main 29:45 214 219 0.485 0.254 634 0.69 1.0 frac pad 2 Main 31:42 218 226 0.492 0.257 635 0.70 1.0 frac slurry 3 Main 33:49 221 233 0.505 0.265 640 0.70 1.0 frac slurry 4 Main 41:23 227 255 0.542 0.291 656 0.71 1.0 frac slurry 5 Main 53:09 234 285 0.595 0.331 676 0.73 1.0 frac slurry 6 Main 69:22 242 304 0.668 0.400 703 0.74 1.0 frac slurry 7 Main 72:56 244 308 0.680 0.413 707 0.74 1.0 frac flush
(298) Hydraulic Fracture Growth History*—Interval #3
(299) TABLE-US-00031 Fracture Fracture Avg. Model Half- Fracture Width at Fracture Net Equivalent End of Stage Time Length Height Well Width Pressure Slurry Number of Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) Efficiency Multifracs 1 Main 29:45 211 216 0.474 0.245 613 0.68 1.0 frac pad 2 Main 31:42 216 224 0.481 0.247 614 0.68 1.0 frac slurry 3 Main 33:49 221 231 0.489 0.250 614 0.68 1.0 frac slurry 4 Main 41:23 238 256 0.516 0.263 619 0.69 1.0 frac slurry 5 Main 53:09 246 280 0.572 0.306 645 0.71 1.0 frac slurry 6 Main 69:22 251 301 0.669 0.375 685 0.73 1.0 frac slurry 7 Main 72:56 252 305 0.689 0.389 694 0.73 1.0 frac flush
(300) Propped Fracture Properties by Distance from the Well at Fracture Center at Depth of 5603 ft—Interval #1
(301) TABLE-US-00032 Frac Fracture Con- Prop System Distance System ductivity Frac System Conc Prop from Well Width* per Frac** Conductivity*** per Frac Conc**** (ft) (in) (mD .Math. ft) (mD .Math. ft) (lb/ft.sup.2) (lb/ft.sup.2) 20.4 0.617 1106.6 1106.6 1.55 1.55 40.8 0.611 1573.0 1573.0 2.18 2.18 61.2 0.601 1546.7 1546.7 2.15 2.15 81.6 0.588 1520.1 1520.1 2.11 2.11 102.0 0.570 1480.5 1480.5 2.06 2.06 122.5 0.547 1318.5 1318.5 1.85 1.85 142.9 0.519 1224.8 1224.8 1.73 1.73 163.3 0.485 1039.5 1039.5 1.49 1.49 183.7 0.442 616.9 616.9 0.93 0.93 204.1 0.390 0.0 0.0 0.00 0.00
(302) Propped Fracture Properties by Distance from the Well at Fracture Center at Depth of 5792 ft—Interval #2
(303) TABLE-US-00033 Frac Fracture Con- Prop System Distance System ductivity Frac System Conc Prop from Well Width* per Frac** Conductivity*** per Frac Conc**** (ft) (in) (mD .Math. ft) (mD .Math. ft) (lb/ft.sup.2) (lb/ft.sup.2) 19.3 0.628 1566.0 1566.0 2.17 2.17 38.6 0.622 1580.7 1580.7 2.19 2.19 58.0 0.612 1553.1 1553.1 2.15 2.15 77.3 0.597 1521.9 1521.9 2.11 2.11 96.6 0.578 1474.4 1474.4 2.05 2.05 115.9 0.554 1304.3 1304.3 1.83 1.83 135.2 0.524 1222.6 1222.6 1.73 1.73 154.5 0.487 1051.9 1051.9 1.50 1.50 173.9 0.441 737.4 737.4 1.09 1.09 193.2 0.384 0.0 0.0 0.00 0.00
(304) Propped Fracture Properties by Distance from the Well at Fracture Center at Death of 6034 ft—Interval #3
(305) TABLE-US-00034 Frac Fracture Con- Prop System Distance System ductivity Frac System Conc Prop from Well Width* per Frac** Conductivity*** per Frac Conc**** (ft) (in) (mD .Math. ft) (mD .Math. ft) (lb/ft.sup.2) (lb/ft.sup.2) 19.7 0.612 1569.8 1569.8 2.18 2.18 39.4 0.607 1556.2 1556.2 2.16 2.16 59.1 0.597 1529.8 1529.8 2.12 2.12 78.8 0.583 1507.9 1507.9 2.10 2.10 98.5 0.565 1465.3 1465.3 2.04 2.04 118.2 0.543 1302.1 1302.1 1.83 1.83 137.9 0.514 1219.2 1219.2 1.72 1.72 157.5 0.480 1039.7 1039.7 1.49 1.49 177.2 0.437 678.4 678.4 1.01 1.01 196.9 0.384 0.0 0.0 0.00 0.00
(306) Treatment Schedule
(307) TABLE-US-00035 Elapsed Clean Prop Stage Slurry Stage Time Fluid Volume Conc Prop. Rate Proppant Stage # Type min:sec Type (gal) (ppg) (klbs) (bpm) Type Wellbore Fluid LINEAR_20_GW- 6050 32 1 Main 29:45 VIKING_D_3500 50000 0.00 0.0 40.00 frac pad 2 Main 31:42 VIKING_D_3500 3000 1.2 3.6 40.00 Example 2 frac slurry 3 Main 33:49 VIKING_D_3500 3000 2.0 2.2 40.00 Example 2 frac slurry 4 Main 41:23 VIKING_D_3500 10000 3.6 36.0 40.00 Example 2 frac slurry 5 Main 53:09 VIKING_D_3500 15000 4.2 63.0 40.00 Example 2 frac slurry 6 Main 69:22 VIKING_D_3500 20000 4.8 96 40.00 Example 2 frac slurry 7 Main 72:56 LINEAR_20_GW- 6000 0.00 0.0 40.00 frac 32 flush
(308) Proppant and Fluid
(309) TABLE-US-00036 Material Quantity Units VIKING_D_3500 2404.8 bbls LINEAR_20_GW-32 142.9 bbls Example 2 343.00 klbs
(310) Leakoff Parameters
(311) TABLE-US-00037 Reservoir type User Spec Reservoir fluid 3.80e−04 compressibility (1/psi) Filtrate to pore fluid perm. 10.00 Reservoir Viscosity 0.03 ratio, Kp/Kl (cp) Reservoir pore pressure 2635 Porosity 0.10 (psi) Initial fracturing pressure 5563 Gas Leakoff 100.00 (psi) Percentage (%)
(312) Reservoir Parameters
(313) TABLE-US-00038 Reservoir Temperature (° F.) 176.00 Perforated Interval and Initial Frac Depth are for Interval #1 Depth to center of Perfs (ft) 5624 Perforated interval (ft) 7 Initial frac depth (ft) 5624
(314) Layer Parameters
(315) TABLE-US-00039 Top of Stress Young's Pore Fluid zone Stress Gradient modulus Poisson's Total Ct Perm. Layer # (ft) (psi) (psi/ft) (psi) ratio (ft/min½) (mD) 1 0.0 5238 0.932 2.0e+06 0.25 0.000e+00 0.00e+00 2 5620.0 4692 0.832 3.0e+06 0.20 2.208e−03 1.00e−01 3 5660.0 5350 0.932 2.0e+06 0.25 0.000e+00 0.00e+00 4 5820.0 4859 0.832 3.0e+06 0.20 2.208e−03 1.00e−01 5 5860.0 5550 0.932 2.0e+06 0.25 0.000e+00 0.00e+00 6 6050.0 5050 0.832 3.0e+06 0.20 2.208e−03 1.00e−01 7 6090.0 5676 0.932 2.0e+06 0.25 0.000e+00 0.00e+00
(316) Lithology Parameters
(317) TABLE-US-00040 Fracture Composite Top of zone Toughness Layering Layer # (ft) Lithology (psi .Math. in½) Effect 1 0.0 Shale 2000 1.00 2 5620.0 Sandstone 1000 1.00 3 5660.0 Shale 2000 1.00 4 5820.0 Sandstone 1000 1.00 5 5860.0 Shale 2000 1.00 6 6050.0 Sandstone 1000 1.00 7 6090.0 Shale 2000 1.00
(318) Casino Configuration
(319) TABLE-US-00041 Length Casing ID Casing OD Weight (ft) Segment Type (in) (in) (lb/ft) Grade 6500 Cemented 4.950 5.500 15.500 K-55 Casing
(320) Perforated Intervals
(321) TABLE-US-00042 Interval #1 Interval #2 Interval #3 Top of Perfs - TVD (ft) 5620 5820 6052 Bot of Perfs - TVD (ft) 5627 5827 6059 Top of Perfs - MD (ft) 5620 5820 6052 Bot of Perfs - MD (ft) 5627 5827 6059 Perforation Diameter (in) 0.320 0.320 0.320 # of Perforations 7 7 7
(322) Path Summary
(323) TABLE-US-00043 Pipe Segment Length MD TVD Dev Ann OD Ann ID ID Type (ft) (ft) (ft) (deg) (in) (in) (in) Casing 6052 6052 6052 0.0 0.000 0.000 4.950
(324) Model Input Parameters
(325) TABLE-US-00044 3D Reservoir Data Fracture Model User-Defined Entry Lithology-Based Run From Job-Design Data Fracture Vertical Orientation Proppant Proppant Run Fracture and Transport Model Convection Wellbore Models Growth after Allow General Iteration Shut-in Backstress Ignore Heat Transfer Ignore Effects Acid Fracturing FracproPT Leakoff Model Lumped-Parameter Model (Default) (Default)
(326) Fracture Growth Parameters (3D User-Defined)
(327) TABLE-US-00045 Parameter Value Default Crack Opening Coefficient 8.50e−01 8.50e−01 Tip Effects Coefficient 1.00e−04 1.00e−04 Channel Flow Coefficient 1.00e+00 1.00e+00 Tip Radius Fraction 1.00e−02 1.00e−02 Tip Effects Scale Volume (bbls) 100.0 100.0 Fluid Radial Weighting Exponent 0.00e+00 0.00e+00 Width Decoupling Coefficient was 1.00e+00 1.00e+00 calculated internally
(328) Proppant Model Parameters
(329) TABLE-US-00046 Parameter Value Default Minimum Proppant Concentration (lb/ft.sup.2) 0.20 0.20 Minimum Proppant Diameter (in) 0.0080 0.0080 Minimum Detectable Proppant 0.20 0.20 Concentration (ppg) Proppant Drag Effect Exponent 8.0 8.0 Proppant Radial Weighting Exponent 0.2500 0.2500 Proppant Convection Coefficient 10.00 10.00 Proppant Settling Coefficient 1.00 1.00 Quadratic Backfill Model ON ON Tip Screen-Out Backfill Coefficient 0.50 0.50 Stop Model on Screenout ON ON Reset Proppant in Fracture after Closure ON ON
(330) Low Level Parameters
(331) TABLE-US-00047 Parameter Value Default Perm. Contrast: Distance Effect 3.0 1.0 Perm. Contrast: Containment Effect 3.0 1.0 Perm. Contrast: Permeability Level 1.00 1.00 Perm. Contrast Model: FracproPT Default YES Fluid <gel> Bulk Modulus (psi) 3.000e+10 3.000e+10 Proppant Bulk Modulus (psi) 3.000e+06 3.000e+06 Fluid (gel) Bulk Coefficient of Thermal 3.000e−04 3.000e−04 Expansion (1/deg. F.) Effect of Proppant on Length Growth 1.00 1.00 Fraction of BRACKET FRAC Proppant that is 0.5 0.5 INVERTA-FRAC by Volume Remember Position of Proppant Banks after NO NO closure on Proppant Allow Slippage NO NO Reset Fluid Leakoff after Frac Closure NO NO Minimum Volume Limit Value 0.20 0.20 Center Shifting Option: Fracture Always Stays Connected to Perfs X Stages can Move from Perfs after Shut-in X Fracture can Move from Perfs after Shut-in Fracture can Move from Perfs at any Time Stage Splitting Volume Threshold (bbls) 200.0 200.0 Stage Splitting Leakoff Compensation (bbls) 5.0 5.0
(332) Initial Leakoff and Closure
(333) TABLE-US-00048 Parameter Value Default Initial Leakoff Area Multiplier Coefficient 1.000 1.000 Initial Leakoff Area from Last Simulation (ft.sup.2) 4268.528 n/a Closure Leakoff Area Multiplier Coefficient 0.025 0.025 Default Shut-in Model YES YES Shut-in Tip Weighting Coefficient for Leakoff 1.00 1.00 Shut-in Tip Weighting Exponent for Leakoff 1.00 1.00 Minimum Shut-in Volume (bbls) 100.0 100.0 Model Proppant in Flow-back YES YES Model Wall-building Viscosity Effect YES NO
(334) Miscellaneous Growth Parameters
(335) TABLE-US-00049 Parameter Value Default Set Minimum Fracture Height NO NO Model Very Small Fractures NO NO Model Head Effects in Fracture NO NO Model Fracture Center Shifting YES NO Near-Wellbore Friction Exponent 0.50 0.50
Example 30
Enhanced Hydrocarbon Recovery Using PsDCs
(336) Turning to
Example 30A
(337) Still using
(338) This enlarged surface areas 6220a, 6220b result in increased initial flows of hydrocarbons by at least about 5%, at least about 10%, at least about 20%, at least about 40% and more over the smaller areas 6210a, 6210b that are obtained with prior proppants.
(339) The PsDC fracture well may also maintain the increased flow, and experience less degradation of flow or production over time, when compared to a fractured using prior proppant. Thus, the PsDC fractured well may provide natural gas production of at least about 200 Mcf/day, at least about 800 Mcf/day, at least about 1,200 Mcf/day or more for at least about 12 months, at least about 18 months, at least about 24 months or more.
(340) Turning to
Example 31
(341) A proppant is made from the following precursor batch: 70% Methyl Hydrogen Fluid; 20% Tetravinyltetramethylcyclotetrasiloxane; and 10% Vinyl Terminated Polydimethylsiloxane (200 cps, ˜9400 Mw, SiSiB® VF6030 VINYL TERMINATED POLYDIMETHYL SILOXANE 68083-19-2)
(342) Using a tower system, this batch is formed from a sonic nozzle having an internal diameter of 0.180 inches into droplets that fall from the nozzle into and through an 18 foot curing tower. The temperature at the top of the tower is from 200-500° C. the temperature at the bottom of the tower is from 200-600° C. There are no discrete temperature zones in the tower. Airflow up the tower is by convection. The collection pan is maintained at 110° C. The forming and curing are done in air. The preform proppants are removed from the pan and post (hard) cured at 200° C. in air for 3 hours. The hard cured preform proppants are pyrolized at 1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is 86%.
Example 32
(343) Studies by Coulter & Wells (e.g. SPE JPT, June 1972, pp. 643-650) have demonstrated that as little as 5% added fines, from prior art proppants, can reduce propped fracture conductivity by 50%. The API (ISO) test classifies a proppant according to the stress at which <10% fines is generated; for example an API (ISO) 7 k proppant would produce <10% fines at 7000 psi. Embodiments of PsDCs, however, exhibit surprising and exceptionally improved conductivities for materials having the same API (ISO) crush strength, when compared to prior art proppants.
(344) Thus, and surprisingly, these embodiments of PsDCs have a substantially different behavior from prior art proppants. It is believed and theorized that the PsDCs have a different failure mechanism than prior art proppants.
(345) Thus, it is presently theorized that embodiments of the PsDCs upon failure exhibit fines that are larger and more jagged than the fines that are produced upon the failure of prior art proppants. Additionally, it is presently theorized that charge, e.g., the electrostatic charge of the PsDCs, could be potentially providing the ability to hold the fines together, and thus may provide one of may explanations for the enhanced flow and flow back characteristics of embodiments of the PsDC proppants.
(346) Thus, for example, turning to
(347) Regardless of the failure mechanism, fluid flow, or hydraulic mechanisms taking place, the PsDCs exhibit surprising and exceptional improved conductivities over prior art proppants.
Example 33
(348) A polysilocarb formulation has 40% MHF, 40% TV, and 20% VT and has a hydride to vinyl molar ratio of 1.12:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 34
(349) A polysilocarb formulation has 42% MHF, 38% TV, and 20% VT and has a hydride to vinyl molar ratio of 1.26:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 35
(350) A polysilocarb formulation has 46% MHF, 34% TV, and 20% VT and has a hydride to vinyl molar ratio of 1.50:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 36
(351) A polysilocarb formulation has 49% MHF, 31% TV, and 30% VT and has a hydride to vinyl molar ratio of 1.75:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 37
(352) A polysilocarb formulation has 51% MHF, 49% TV, and 0% VT and has a hydride to vinyl molar ratio of 1.26:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 38
(353) A polysilocarb formulation has 55% MHF, 35% TV, and 10% VT and has a hydride to vinyl molar ratio of 1.82:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 39
(354) A polysilocarb formulation has 52% MHF, 28% TV, and 20% VT and has a hydride to vinyl molar ratio of 2.02:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 40
(355) A polysilocarb formulation has 55% MHF, 25% TV, and 20% VT and has a hydride to vinyl molar ratio of 2.36:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 41
(356) A polysilocarb formulation has 65% MHF, 25% TV, and 10% VT and has a hydride to vinyl molar ratio of 2.96:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 42
(357) A polysilocarb formulation has 70% MHF, 20% TV, and 10% VT and has a hydride to vinyl molar ratio of 3:93:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 43
(358) A polysilocarb formulation has 72% MHF, 18% TV, and 10% VT and has a hydride to vinyl molar ratio of 4.45:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 44
(359) A polysilocarb formulation has 75% MHF, 17% TV, and 8% VT and has a hydride to vinyl molar ratio of 4.97:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 45
(360) A polysilocarb formulation has 95% MHF, 5% TV, and 0% VT and has a hydride to vinyl molar ratio of 23.02:1, and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations.
Example 46
(361) Using the reaction type process a precursor formulation was made using the following formulation. The temperature of the reaction was maintained at 72° C. for 21 hours. This precursor formulation may be used to make a strong synthetic proppant.
(362) TABLE-US-00050 Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant or Solvent Mass Total MW solvent Silane of Si of EtOH Methyltriethoxysilane 0.00 0.0% 178.30 — 0.00% — — (FIG. 46) Phenylmethyldiethoxysilane 0.00 0.0% 210.35 — 0.00% — — (FIG. 47) Dimethyldiethoxysilane 56 7.2% 148.28 0.38 17.71% 0.38 0.76 (FIG. 51) Methyldiethoxysilane (FIG. 48) 182 23.2% 134.25 1.36 63.57% 1.36 2.71 Vinylmethyldiethoxysilane 64 8.2% 160.29 0.40 18.72% 0.40 0.80 (FIG. 49) Triethoxysilane (FIG. 53) 0.00 0.0% 164.27 — 0.00% — — Hexane in hydrolyzer 0.00 0.0% 86.18 — Acetone in hydrolyzer 0.00 0.0% 58.08 — Ethanol in hydrolyzer 400.00 51.1% 46.07 8.68 Water in hydrolyzer 80.00 10.2% 18.00 4.44 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 47
(363) Using the reaction type process a precursor formulation was made using the following formulation. The temperature of the reaction was maintained at 61° C. for 21 hours. This precursor formulation may be used to make a strong synthetic proppant.
(364) TABLE-US-00051 Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant or Solvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane (FIG. 54) 145.00 18.5% 240.37 0.60 34.58% 0.60 1.81 Phenylmethyldiethoxysilane 0.00 0.0% 210.35 — 0.00 — — (FIG. 47) Dimethyldiethoxysilane 0.00 0.0% 148.28 0.57 32.88% 0.57 1.55 (FIG. 51) Methyldiethoxysilane (FIG. 48) 77.00 9.8% 134.25 — 0.00% — — Vinylmethyldiethoxysilane 91.00 11.6% 160.29 0.57 32.54% 0.57 1.14 (FIG. 49) Trimethyethoxysilane (FIG. 57) 0.00 0.0% 118.25 — 0.00% — — Acetone in hydrolyzer 395.00 50.3% 58.08 6.80 Ethanol in hydrolyzer 0.00 0.0% 46.07 — Water in hydrolyzer 76.00 9.7% 18.00 4.22 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 48
(365) Using the reaction type process a precursor formulation was made using the following formulation. The temperature of the reaction was maintained at 61° C. for 21 hours. This precursor formulation may be used to make a strong synthetic proppant.
(366) TABLE-US-00052 Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant or Solvent Mass Total MW solvent Silane of Si of EtOH ltriethoxysilane (FIG. 54) 0.00 0.00% 240.37 — 0.0% — — Phenylmethyldiethoxysilane 145.00 18.4% 210.35 0.69 34.47% 0.69 1.38 (FIG. 47) Dimethyldiethoxysilane 0.00 0.00% 148.28 — 0.00% — — (FIG.51) Methyldiethoxysilane (FIG. 48) 88.00 11.2% 134.25 0.66 32.78% 0.66 1.31 Vinylmethyldiethoxysilane 105.00 13.3% 160.29 0.66 32.76% 0.66 1.31 (FIG. 49) Trimethyethoxysilane (FIG. 57) 0.00 0.0% 118.25 — 0.00% — — Acetone in hydrolyzer 375.00 47.5% 58.08 6.46 Ethanol in hydrolyzer 0.00 0.0% 46.07 — Water in hydrolyzer 75.00 9.5% 18.00 4.17 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 49
(367) The treatment of pyrolized polysiloxane materials, such as for example, proppants and other volumetric shapes, with silanes, anti-static agents and combinations of these has the ability to increase, and significantly increase the strength of the pyrolized materials.
(368) Thus, treating composition may optionally contain generally used, e.g., typical, additives such as rheology modifiers, fillers, coalescents such as glycols and glycol ethers to aid in proppant storage stability, antifoaming agents such as Drew L-139 (commercially available from Drew Industries, a division of Ashland Chemical), antistatic agents such as Emerstat 6660A (commercially available from Cognis) or Katex 6760 (from Pulcra Chemicals), dust suppression agents, and/or other generally used, e.g., typical, additives. Additives may be present in the coatings composition from trace amounts (such as <about 0.1% by weight the total composition) up to about 5.0% by weight of the total composition.
(369) The preferable treating solution contains a silane, Silquest A1100 from Momentive and has the following chemical formula, H.sub.2NCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3.
(370) To treat proppant the following procedure may be utilized. Wash the Proppant in water (current procedure) to remove fines, Wash the Proppant in Silane/Antistat aqueous solution for 5 min (at 25 C). Remove Proppant and save all the excess Silane/Antistat solution for multiple use. Dry the Proppant at 105-110 C for 30 mins-1 hr (preferably it should be completely dry).
(371) By way of example, 40 mesh proppant having a crush strength of 13,200 psi was treated using the above procedure and exhibited crush strengths that exceeded 17,600 psi, and more. The fine percentage for these silane treated proppants was less than 1.7%, and lower.
Example 50
Off Shore Hydrocarbon Recovery
(372) In PsDC hydraulic fracturing treatments of offshore deep water wells is conducted using embodiments of the proppants of these examples, e.g., Example 2, 16, 17, 18, 21, 23, 35, 42, 49, 53, 54, and 55.
(373) Existing proppants, and in particular generally used higher strength proppants, that typically have specific gravities of 2.5 and greater (e.g.,
(374) The low specific gravity, e.g., less than 2.5, and more preferably less than 2.0, and low specific gravity to high strength ratio, provided by the synthetic proppants of the present inventions, greatly reduces the weight of the column of fracturing fluid providing the ability to back off, circulate, reverse flow, and otherwise control the movement of the fracturing fluid, and thus solves this developing, significant and potentially severe problem with prior proppants, as E&P activities move into deeper and deeper waters.
Example 50a
(375) Turning to
Example 50b
(376) Turning to
Example 51
(377) In a PsDC hydraulic fracturing treatment the PsDC proppants are added in a controlled manner, and at a controlled lbs/gal, using volumetric metering devices.
Example 52
(378) In a PsDC hydraulic fracturing treatment the PsDC proppants are added using volumetric metering devices. The proppant is metered into the high pressure line, in a controlled manner. In this manner the pumps are not required to pump fracturing fluid containing proppant.
Example 53
(379) A PsDC proppant of the type of Example 42 has the following features: high in strength resulting in less crushing, optimizing conductivity and minimizing fines generation; lower specific gravity enabling the proppant to travel further into the formation, creating longer propped fracture half-lengths and more propped surface area, resulting in greater access to reserves in place generating higher initial production (IP) and increased estimated ultimate recovery (EUR); performs well at temperatures to >2,000° F. (1,100° C.), enabling usage in virtually all O&G reservoirs; is round and has a uniform mesh distribution, maximizing conductivity and increasing the free flow of formation liquids; lowers total well costs per unit of production; not harmful to the environment and could reduce the number of wells producers must drill given its ability to access more of the reserves in place.
(380) The proppant has a sieve analysis (% retained) of +35 Mesh/420 microns—0.1%; −35+40 mesh/354 microns—72.8%; −40+45 mesh/297 microns—27.1%; −45 mesh/250 microns—0%. The proppant has a roundness of about 1.0, a sphericity of about 1.0, a bulk density of 75.15 (lbs/ft.sup.3) 1.20 (g/cc), a specific gravity of 1.98, an absolute volume of 0.61 (gal/lb), a solubility in 12/3 HCl/HF Acid (% weight loss) 5.7, API crush test, % of fines generated @ 15,000 psi 0.3.
(381) The proppant has the long term conductivity data of Tables 4a and 4b
(382) TABLE-US-00053 TABLE 4a Closure Stress (psi) md-ft (millidarcy- 2 lbs/ft.sup.2 40 mesh feet) @ 250° F. 2,000 2,743 4,000 2,510 6,000 2,228 8,000 1,697 10,000 1,607 12,000 1,544 14,000 1,366 15,000 1,228
(383) TABLE-US-00054 TABLE 4b Closure stress (psi) 2 lbs/ft3 40 mesh Darcies @ 250° F. 2,000 133 4,000 124 6,000 113 8,000 86 10,000 84 12,000 82 14,000 74 15,000 67
Example 54
(384) An embodiment of the proppant of Example 39 has a bulk density of 1.17 g/cc, a specific gravity of 1.93, a particle size distribution of 0.1% at 35 mesh, 75.2% at 40 mesh, 24.6% at 45 mesh, and 0.1% at 50 mesh, and an ISO Crush Analysis (% fines) 4 lb/ft.sup.2 @ 15,000 psi of 0.6. The sample exhibits exceptional long term conductivity performance data as shown in Table 5.
(385) TABLE-US-00055 TABLE 5 Pack Height (Test cell Time Total test plate Stress (hrs) @ time Conductivity Permeability separation) (psi) stress (hrs) (md-ft) (Darcy) (in) 1,000 24 24 2263 111 0.246 2,000 50 74 1977 99 0.240 4,000 50 124 1841 93 0.237 6,000 50 174 1940 100 0.233 8,000 50 224 1769 93 0.229 10,000 50 274 1762 94 0.226 12,000 50 324 1638 89 0.221 14,000 50 374 1381 77 0.215 15,000 50 424 1187 68 0.209
Example 55
(386) An embodiment of the proppant of Example 35 has a bulk density of 1.24 g/cc, a specific gravity of 1.95, a particle size distribution of 0.1% at 35 mesh, 91.6% at 40 mesh, 8.2% at 45 mesh, and 0.1% at 50 mesh, and an ISO Crush Analysis (% fines) 4 lb/ft.sup.2 @ 15,000 psi of 0.4. A 400× photograph of these proppants is shown in
(387) TABLE-US-00056 TABLE 6 Pack Height (Test cell Time Total plate Stress (hrs) @ test time Conductivity Permeability separation) (psi) stress (hrs) (md-ft) (Darcy) (in) 1,000 24 24 2777 127 0.262 2,000 50 74 2344 110 0.256 4,000 50 124 2051 98 0.251 6,000 50 174 1912 93 0.247 8,000 50 224 1681 82 0.245 10,000 50 274 1916 94 0.244 12,000 50 324 1717 86 0.240 14,000 50 374 1461 75 0.233 15,000 50 424 1247 65 0.229
Example 56
(388) Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formed into pucks. The pucks are cures and pyrolized to a ceramic. The ceramic pucks are broken apart, into small particles. The particles are sieved if need be, to have the majority of all particles smaller than 100 mesh. These particles are not spherical, are irregular and varied in shape, and have planar surfaces. These particles are PsDC proppants
Example 57
(389) Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formed into pucks. The pucks are cures and pyrolized to a ceramic. The ceramic pucks are broken apart, into small particles. The particles are sieved if need be, to have the majority of all particles smaller than 200 mesh. These particles are not spherical, are irregular and varied in shape, and have planar surfaces. These particles are PsDC proppants
Example 58
(390) Embodiments of the proppants of these examples, e.g., Examples 56, 57, 59 and 60, are used in a hydraulic fracture treatment of an unconventional shale well. The fractures are propped with a monolayer or partial monolayer distribution of proppant. It is theorized that a self-bridging diverting phenomena takes place in situ. Prior proppants, now generally in use, do not get very far from the well bore due to settling because of their density. Embodiments of proppants of the present inventions can accomplish this due to, among other things, their size and lower density.
Example 59
(391) Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formed into small spheres using emulsion polymerization techniques. The precursor formulation is emulsified using water, alcohol, glycol, or any polar liquid having a low partition coefficient, and in which the precursor formulation is not soluble, as the emulsifier. Once formed the emulsion is broken and the small sphere are cured and pyrolized into PsDC proppants. The spheres are smaller than 100 mesh.
Example 60
(392) Embodiments of a PsDC formulations are formed into small spheres using emulsion polymerization techniques. The precursor formulation is emulsified using water, alcohol, glycol, or any polar liquid having a low partition coefficient, and in which the precursor formulation is not soluble, as the emulsifier. Once formed the emulsion is broken and the small sphere are cured and pyrolized into PsDC proppants. The spheres are smaller than 100 mesh. In other embodiments the spheres are smaller than 150 mesh. In other embodiments the spheres are smaller than 200 mesh, and smaller.
Example 61
(393) A jack-up off shore rig has fracturing equipment operationally associated with it. The rig is located above the surface of a body of water having a depth of 200 feet. A riser extends down from the rig to a BOP on the sea floor, and has a length of about 200 feet. A borehole extends below the sea floor into the earth to a fracture area at a MD of about 8,000 feet. The proppant of Example 55 is used to perform a hydraulic fracturing treatment on the fracturing area.
(394) It is noted that there is no requirement to provide or address the theory underlying the novel and groundbreaking conductivities, performance or other beneficial features and properties that are the subject of, or associated with, embodiments of the present inventions. Nevertheless, various theories are provided in this specification to further advance the art in this important area, and in particular in the important area of hydrocarbon exploration and production. These theories put forth in this specification, and unless expressly stated otherwise, in no way limit, restrict or narrow the scope of protection to be afforded the claimed inventions. These theories many not be required or practiced to utilize the present inventions. It is further understood that the present inventions may lead to new, and heretofore unknown theories to explain the conductivities, fractures, drainages, resource production, and function-features of embodiments of the methods, articles, materials, devices and system of the present inventions; and such later developed theories shall not limit the scope of protection afforded the present inventions.
(395) The various embodiments of formulations, batches, devices, systems, proppants, PsDCs, methods, hydraulic fracture treatments, hydrocarbon recovery, activities and operations set forth in this specification may be used for various oil field operations, other mineral and resource recovery fields, as well as other activities and in other fields. Additionally, these embodiments, for example, may be used with: oil field systems, operations or activities that may be developed in the future; and with existing oil field systems, operations or activities which may be modified, in-part, based on the teachings of this specification. Further, the various embodiments set forth in this specification may be used with each other in different and various combinations. Thus, for example, the configurations provided in the various embodiments of this specification may be used with each other; and the scope of protection afforded the present inventions should not be limited to a particular embodiment, configuration or arrangement that is set forth in a particular embodiment, example, or in an embodiment in a particular Figure.
(396) Although this specification focuses on proppants, it should be understood that the formulations, material systems, small volumetric shapes, and methods of making them, taught and disclosed herein, may have applications and uses for many other activities in addition to hydraulic fracturing, for example, as pigments and additives.
(397) The invention may be embodied in other forms than those specifically disclosed herein without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive.