Drill cuttings with a drying agent
11667568 · 2023-06-06
Assignee
Inventors
Cpc classification
C04B18/06
CHEMISTRY; METALLURGY
C04B2111/00112
CHEMISTRY; METALLURGY
C04B18/049
CHEMISTRY; METALLURGY
C04B14/00
CHEMISTRY; METALLURGY
C04B28/02
CHEMISTRY; METALLURGY
C04B18/049
CHEMISTRY; METALLURGY
C04B18/06
CHEMISTRY; METALLURGY
C04B18/0472
CHEMISTRY; METALLURGY
C04B28/02
CHEMISTRY; METALLURGY
C04B2111/00612
CHEMISTRY; METALLURGY
Y02W30/91
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
International classification
Abstract
Described are stabilized materials and methods and systems for providing said stabilized materials. The system includes a first unit for mixing a first combination that includes a quantity of drill cuttings and a drying agent. The system may include a second unit for mixing the first combination with at least a binder and/or a surface acting agent and providing a second combination. The second combination is formed when the first combination is caused to have a reduced moisture content, transitioning from a first state to a second state. The reduced moisture content in the second state is at least 20% less than the moisture content of the drill cuttings. The first combination in a second state is a stabilized material. The first combination in a second state may be a dried material. The binder and/or a surface acting agent with or without additional additives are not introduced until the first combination is in the second state.
Claims
1. A method of preparing a stabilized material that is substantially friable, the method comprising: combining a drying agent and a quantity of drill cuttings to form a first combination that does not include a pozzolan that would cause the stabilized material to be substantially non-friable, the quantity of drill cuttings having a moisture content between about 1% and about 45% by weight prior to combining, the drying agent in the first combination being in an amount greater than about 1% and less than a first upper weight percentage by weight of the drill cuttings, the drying agent causing the first combination to achieve a first state such that the liquid content of the first combination is less than the liquid content of the drill cuttings prior to combining; causing the first combination to achieve a second state, the second state having liquid content that is at least the first upper weight percentage by weight less than the liquid content of the drill cuttings prior to combining; such that the causing the first combination to achieve the second state causes formation of the stabilized material that is substantially friable, wherein the drying agent has an alkaline pH, wherein causing the first combination to achieve the second state includes waiting following the combining of the drying agent and the quantity of drill cuttings to form the first combination that does not include the pozzolan that would cause the stabilized material to be substantially non-friable, and wherein the first combination in the second state is the stabilized material that is substantially friable.
2. The method of claim 1, wherein the drying agent is a byproduct of a calcination reaction.
3. The method of claim 1, wherein the drying agent is in an amount between about 5% and to about 12% by weight based on the total weight of the first combination.
4. The method of claim 1, wherein the liquid content of the quantity of drill cuttings prior to combining is between about 5% and about 15% by weight.
5. The method of claim 1, wherein the drying agent is in an amount from about 5% and about 10% by weight of the quantity of the drill cuttings.
6. The method of claim 1, wherein the waiting is for at least seven days.
7. The method of claim 1, wherein the drying agent includes calcium carbonate.
8. The method of claim 1, wherein the drying agent includes less than 10% by weight crystalline silica.
9. The method of claim 1, wherein the drying agent is a non-pozzolan.
10. The method of claim 1, wherein the first upper weight percentage is 20% by weight.
11. A method of preparing a stabilized material, the method comprising: combining ingredients consisting of a drying agent and a quantity of drill cuttings to form a first combination, the quantity of drill cuttings having a moisture content between about 1% and about 45% by weight prior to combining, the drying agent in the first combination being in a first amount by weight of the drill cuttings, the drying agent causing the first combination to achieve a first state substantially without pozzolanic reaction such that the moisture content of the first combination is less than the moisture content of the drill cuttings prior to combining; causing the first combination to achieve a friable second state, the friable second state having moisture content that is a second amount by weight less than the moisture content of the drill cuttings prior to combining, the second amount having a greater absolute magnitude than the first amount; such that the causing the first combination to achieve the second state causes formation of the stabilized material that is friable, wherein causing the first combination to achieve the second state includes waiting.
12. The method according to claim 11, wherein the waiting is for at least seven days.
13. The method according to claim 11, wherein the first amount by weight of the drill cuttings comprises between about 1% and to about 20% by weight of the drill cuttings.
14. The method according to claim 11, wherein the second amount is at least about 20% by weight.
15. The method according to claim 11, wherein the drying agent has an alkaline pH, wherein the drying agent includes calcium carbonate, wherein the drying agent includes less than 10% by weight crystalline silica.
16. The method according to claim 11, wherein the drying agent is a non-pozzolan.
17. A method of preparing a friable stabilized material, the method comprising: combining a drying agent and a quantity of drill cuttings to form a first combination, the quantity of drill cuttings having a moisture content between about 1% and about 45% by weight prior to combining, the drying agent in the first combination being in an amount between about 1% and to about 20% by weight of the drill cuttings, the drying agent causing the first combination to achieve a first state such that the moisture content of the first combination is less than the moisture content of the drill cuttings prior to combining; causing the first combination to achieve a friable second state, the friable second state having moisture content that is at least about 20% by weight less than the moisture content of the drill cuttings prior to combining; such that first combination that has achieved the friable second state is the stabilized material that is friable, wherein the drying agent has an alkaline pH, wherein causing the first combination to achieve the second state includes waiting; and causing the friable stabilized material to be spread out on a ground surface.
18. The method of claim 17, wherein the drying agent includes calcium carbonate and wherein the drying agent includes less than 10% by weight crystalline silica.
19. The method of claim 17, wherein the waiting is for at least 36 hours.
20. A method of preparing a stabilized material that is substantially friable, the method comprising: combining (i) a drying agent that does not include a pozzolan that would cause the stabilized material to be substantially non-friable and (ii) a quantity of drill cuttings that does not include the pozzolan that would cause the stabilized material to be substantially non-friable, to form a first combination that does not include the pozzolan that would cause the stabilized material to be substantially non-friable, the quantity of drill cuttings having a liquid content between about 1% and about 45% by at least one of weight and volume prior to combining, the drying agent in the first combination being in an amount greater than about 1% and less than a first upper percentage by at least one of weight and volume of the drill cuttings, the drying agent causing the first combination to achieve a first state such that the liquid content of the first combination is less than the liquid content of the drill cuttings prior to combining; causing the first combination to achieve a second state, the second state having liquid content that is at least the first upper percentage by at least one of weight and volume less than the liquid content of the drill cuttings prior to combining; such that the causing the first combination to achieve the second state causes formation of the stabilized material that is substantially friable, wherein the drying agent has an alkaline pH, wherein the drying agent includes calcium carbonate, wherein the drying agent includes less than 10% by weight crystalline silica, wherein causing the first combination to achieve the second state includes waiting following the combining of (i) the drying agent that does not include the pozzolan that would cause the stabilized material to be substantially non-friable and (ii) the quantity of drill cuttings that does not include the pozzolan that would cause the stabilized material to be substantially non-friable to form the first combination that does not include the pozzolan that would cause the stabilized material to be substantially non-friable, and wherein the first combination in the second state is the stabilized material that is substantially friable.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) For a more complete understanding of the description provided herein and the advantages thereof, reference is now made to the brief description below, taken in connection with the accompanying drawing and detailed description.
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DETAILED DESCRIPTION
(9) Although making and using various embodiments are discussed in detail below, it should be appreciated that as described herein are provided many inventive concepts that may be embodied in a wide variety of contexts. Embodiments discussed herein are merely representative and do not limit the scope of the invention.
(10) Described herein are systems and methods of making stabilized and/or recycled materials and the materials themselves. The stabilized and/or recycled materials are suitable for re-use, such as a sub base, meeting performance criteria and/or standards for a sub base or as a sandy, non-plastic road material. The stabilized and/or recycled materials are suitable for re-use, such as a sub grade road material, meeting performance criteria and/or standards for a sub grade road material. The stabilized and/or recycled materials provided herein may be on-site recycled materials that are stabilized in accordance with State and Federal road and highway requirements and suitable for use as a road material. The stabilized and/or recycled materials may be deemed as non-hazardous recycled materials for re-use. The stabilized and/or recycled materials will include drill cuttings that require stabilization, due to the fact that the drill cuttings contained an amount of contaminant or pollutant requiring stabilization.
(11) The drill cuttings requiring stabilization may include drill cuttings that have or have not been separated from the drilling mud or drilling fluids; the drilling mud may be synthetic, aqueous based or non-aqueous based. With or without separation of drill cuttings from drilling mud, drill cuttings will have fines and course aggregate saturated with moisture, the moisture derived at least in part from the drilling mud. Such drill cuttings may also be referred to as aggregated drill cuttings. It is not uncommon for said drill cuttings to contain, even after separation, about 5 to about 10% moisture, or about 5 to about 15% moisture, or about 5 to about 40% moisture, or about 1 to about 45% moisture, or up to about 15% moisture, or up to 20% moisture, or up to 25% moisture, or up to 30% moisture, or up to 35% moisture, or up to 45% moisture, and from about 5 to about 25% hydrocarbons (e.g., diesel, oil, and other hydrocarbon sources), or about 5 to about 15% of said hydrocarbons. Of course other ranges therein and amounts are possible. The hydrocarbon fraction as well as the non-hydrocarbon fractions will often contain other potential contaminants or pollutants. With the methods described herein moisture is initially removed from the drill cuttings and without being bound by theory, said initial moisture removal is integral in allowing the stabilization and re-use described herein, including providing said material with the described structural integrity; said methods include, in addition to moisture removal, removal and/or stabilization of hydrocarbons and other contaminants from within the drill cuttings. Hydrocarbons are, thus, believed to be not only contained by said methods and systems, also to be removed at least in part from the drill cuttings. Additional potential contaminants or pollutants in the drill cuttings include metals (e.g., chromium, copper, cesium, nicked, lead, barium and zinc, as representative examples) as well as contaminating salts, chlorides, or chlorine, as examples. These additional potential contaminants or pollutants are also contained and/or controlled by the methods described herein.
(12) With said methods, the drill cuttings are initially combined with one or more drying agents. The drill cuttings do not require any further modification prior to initially combining with the one or more drying agents. For example, prior to initially combining with the one or more drying agents the drill cuttings do not need to be thermally treated. The drill cuttings do not need to be further subjected to processes that liberate gases and/or evaporate liquids prior to initially combining with the one or more drying agents. The drill cuttings do not need to be further screened prior to initially combining with the one or more drying agents. The drill cuttings do not need to be further milled prior to initially combining with the one or more drying agents. The drill cuttings do not need to be formed into a fine powder prior to initially combining with the one or more drying agents. The drill cuttings do not need to be compressed and/or pelletized prior to initially combining with the one or more drying agents. The drill cuttings when combined with the one or more drying agents are generally provided as wet drill cuttings or as mud-like or as slurry-like aggregated drill cuttings.
(13) In some embodiments, the drill cuttings may be initially screened to remove drilling mud (or a portion thereof) in processes known to those of skill in the art (e.g., conveying on shakers with screens for recycling at least a portion of the mud). In some embodiments, the drilling mud has been at least partially removed from the drill cuttings, which offers an opportunity for the drilling mud to be recycled. In some embodiments, one may further subject the drill cuttings or at least a portion of the drill cuttings to a grinder that reduces the size of at least some of the aggregates in the drill cuttings prior to initially combining with the one or more drying agents. In some embodiments, it may be preferred that a portion of the aggregates in the drill cuttings are larger than another portion of the drill cuttings. This combination of larger and smaller sized aggregates will, in some embodiments, increase the overall strength of the final material produced, which includes material formed by the methods described herein and/or when solidified. Having a combination of larger and smaller sized aggregates allows a lock-in fit with the different sized aggregates and between the different sized aggregates, providing less gaps between aggregates when later formed as a re-used and/or solidified material.
(14) The drying agent will have an alkaline pH, a high amount of calcium carbonate and a low pozzolanic activity. In some embodiments, the amount of calcium carbonate is greater than about 40 wt. %. In some embodiments, the amount of calcium carbonate is greater than about 50 wt. % or is greater than about 60 wt. % or is greater than about 70 wt. % or is greater than about 80 wt. % or is greater than about 90 wt. %. The calcium content may be contained in a combination of calcium carbonate and/or calcium oxide. The drying agent has, itself, only a very low or even negligible amount of moisture and is capable of moisture absorption. In some embodiments, the drying agent will have only a low or very low amount of crystalline silica. In many embodiments, the amount of crystalline silica is from 0 to about 10 wt. %. In some embodiments, the amount of crystalline silica is less than about 10 wt. %, or is less than about 9 wt. %, or is less than about 8 wt. %, or is less than about 7 wt. %, or is less than about 6 wt. %, or is less than about 5 wt. %. In some embodiments the amount of crystalline silica is negligible, or is from about 0 to about 5 wt. % or is from about 0 to about 4 wt. %, or is from about 0 to about 3 wt. %, or is from about 0 to about 2 wt. %, or is from about 0 to about 1 wt. %. In some embodiments, the drying agent will have an amount of silicon dioxide that is less than or is a lot less than other ashes (combustion by products), such as Class F fly ash, blast furnace slag and bottom ash. In some embodiments, the drying agent will be an ash with a lower amount of silicon dioxide. A representative examples of a drying agent is kiln dust or at least partially calcined kiln feed which is removed from and collected, for example, in a dust collector during the manufacture of cement or lime. In one or more forms the kiln dust is cement kiln dust or lime kiln dust. Preferably the cement kiln dust when used is from the manufacture of Type I Portland cement. Other representative examples of a drying agent include but are not limited to stacking dust and lime, each having an alkaline pH. Class C fly ash having a much reduced silicon dioxide amount (e.g., when not considered pozzolanic, not considered a strong cementitious reactant) may also be used. Still further, the drying agent may be or may include caliche preferably in powdered or particulated form, which typically has a calcium carbonate content of about or greater than about 70% or 80%. Still further, the drying agent may be or may include natural hydraulic lime in powdered or particulated form.
(15) The drying agent is introduced generally as a fine particulate material. The particulates will have a size in a range from about 0.5 microns to about 800 microns and generally less than about 1000 microns. Various ranges therein may be provided, without limitation when desired. Such ranges may include but are not limited to 0.5 microns to about 10 microns or from about 0.5 microns to about 20 microns or from about 1 micron to about 100 microns or from about 20 microns to about 200 microns or from about 100 or about 200 microns to about 800 or about 1000 microns or from about 20 microns to about 500 microns or from about 100 microns to about 1000 microns.
(16) When more than one drying agent is introduced, overall properties of the one or more drying agent will be such that, in total, the amount of calcium oxide is greater than as described above (e.g., greater than about 40 wt. %). In addition, in total, the moisture content of the one or more drying agents will be very low or even negligible. In total, the one or more drying agents will be capable of moisture absorption. Moreover, in total, the amount of crystalline silica in the one or more drying agents should not be more than about 10 wt. %, or the total amount of crystalline silica will be less than about 10 wt. %. Similarly, in total, the drying agent(s) should not be considered strong pozzolans, or agents considered to behave as a strong cementitious reactant.
(17) When the one or more drying agent is initially introduced to the aggregated drill cuttings, the combination with drill cuttings is generally considered to be in a first state. The first state is generally depicted as having a moisture content defined primarily as being dryer than or having a moisture content that is less than that of the drill cuttings. Thus, the moisture content of the first state may be from about 1 to about 10%, or from about 5 to about 15%, or from about 5 to about 40%, or from about 1 to about 40%, or from about 1 to about 45%, or up to about 15%, or up to 20%, or up to 25%, or up to 30%, or up to 35%, or up to 45%. Collectively, the drying agent(s) and the drill cuttings together form a first combination.
(18) The amount of drying agent(s) introduced with the drill cuttings may range from about 0.5% to about 20% of the quantity of drill cuttings, or in any various range therein. For example, the drying agent(s) may be in an amount (based on weight of drill cutting) ranging from about 3% to about 15% or from about 5% to about 10%, or from about 5% to about 15%, or up to about 10%, based on the quantity (by weight) of the drill cuttings.
(19) Generally, the one or more drying agent is combined with the drill cuttings using a unit for blending, such as a mixer, blender, blending device or other similar unit or means for blending that is known in the art for blending or combining aggregate materials. A suitable example is a pug mill having a hopper or feed assembly through which the drying agent and the drill cuttings are fed. Another example is a unit or machine comprising an auger screw. A further example is a skid steer comprising at least a mixer or mixing unit. Said machinery may be centrally stationed or may be local, such as near a drilling site, and one or more may be moveable and/or portable. In some embodiments, the drill cuttings and drying agent(s) are introduced into the unit for blending; this may be done in series (with no particular order) as represented with
(20) In some embodiments, the combining (blending or comingling) of the components described herein, which includes the one or more drying agent and the aggregated drill cuttings, may be performed at an ambient temperature. In addition, in some embodiments, the unit of blending or utilizing the means for blending may include a heater or cooler compartment or means for heating or cooling, so that the methods described herein include one or more steps of heating and/or cooling. Said heating and/or cooling may, depending in part on the configuration and means for heating or cooling, be performed prior to, during and/or after blending. As such, the one or more steps of heating and/or cooling may take place prior to forming the first combination, at the time of forming the first combination or after forming the first combination, when a temperature change is desired or is necessitated. As depicted in
(21) With any further addition of heat (when desired, and which may occur prior to, during or after blending), it will always be at a temperature less or much less than a temperature used to thermally cure a hydraulic material (e.g., less or much less than about 140 degrees C.). With cooling (hen desired, and which may occur prior to, during or after blending), the temperature will always be a temperature that does not promote freezing. In some embodiments, cooling temperatures assist when outside temperatures are very high. For example, cooling temperatures may be applied to reduce the temperature after blending, such as to keep temperatures near or within about 20 degrees of the initial temperature (e.g., prior to the blending).
(22) Output after blending (e.g.,
(23) As such, as described herein, output after blending, such as described with
(24) Moisture reduction and/or removal described herein, as depicted in Stage A,
(25) Optimum reduction in moisture content is achieved when the output after blending utilizing the unit for blending is allowed to rest for a period of time. Thus, in some embodiments, the output having the reduced moisture content is obtained when the first combination has a reduced moisture state with a desired reduction in moisture content, or has achieved the desired reduction in moisture content in the second state. The reduction in moisture content includes a reduction in moisture as compared with the initial drill cuttings, and may include a transition in moisture level or moisture content from a first state to a second state, as depicted in boxes 10 and 12 of
(26) To cause the first combination to achieve the second state, the output may rest at an ambient temperature or at a higher than ambient temperature. The higher temperature should be less than a temperature that is used to thermally cure a hydraulic material (e.g., less or much less than about 140 degrees C.). The higher temperature may be sufficient to completely or nearly completely dry the output, thereby lessening the time for resting. The higher temperature may be achieved by introducing additional heat to the output. If output is allowed to simply rest, the rest period may be about 24 hours or at least 30 hours or about 72 hours, or at least a few days, or up to a week, or may be greater than a week. The rest period may also be at least for a week (e.g., at least about seven days), or may be more than a few weeks. In some embodiments, the output may simply rest (generally without introducing additional heat) for some period of time before further use. This period of time may be about at least five days to ten days for drill cuttings obtained from a drill hole and provided as an output. In some embodiments, the rest period may be at least about seven days for output that originated from a drill or well hole. Longer periods are effective as well. There does not appear to be a detrimental effect when the output rests for longer periods. The output when caused to achieve the second state remains particulated, considered (using jargon) to be crumbly, and is no longer aggregated in the large aggregated masses or as an aggregated slurry. The output when in the second state, does not solidify on its own and does not readily aggregate (form a larger cohesive mass) on its own. For example, the output when in a second state does not re-aggregate into large aggregated masses, such as when the particulates of the second state are pressed together by hand. Achieving the second state provides a composition with structural integrity and strength. Thus, when the first combination in the second state is used (
(27) In one or more embodiments, the second state is a friable state. In one or more embodiments, the output after blending, when in a second state (with a period of rest), is a particulated output and will not on its own form a molded cohesive mass, such as, for example, when a quantity of the output is gently pressed together (e.g., by hand). In one or more embodiments, the output in a second state is when the moisture content is less than optimum moisture for compaction (e.g., in accordance with the American Association of State Highway and Transportation Officials (AASHTO), T-99 or T-180). In some embodiments, the output is best in a second state when the moisture content is about 3 to about 5 percentage points less than optimum moisture content for compaction (e.g., in accordance with the AASHTO T-99 or T-180). In some embodiments, the output in a second state is when the moisture content is more than about 5 percentage points less, or more than about 6 percentage points less, or more than about 7 percentage points less, or more than about 8 percentage points less, or more than about 9 percentage points less, or more than about 10 percentage points less, or from between about 8 and about 10 percentage points less than optimum moisture for compaction, such as in accordance with AASHTO T-99 or T-180.
(28) In view of the methods described herein, reduction in moisture (e.g., reduced moisture content) of the drill cuttings is due in part from evaporation. Reduction in moisture is due in part from absorption. Some moisture reduction may also be due in part from drainage. The drained moisture, however, will not typically contain an amount of contaminant or pollutant that must be contained or further treated. When desired, a means for collecting the drained moisture is also acceptable and may be included with the described method.
(29) The output, which, when caused to form a first combination in a second state, has a reduced moisture content from that of the aggregated (initial) drill cuttings and is a stabilized material, as depicted in
(30) For re-use, the stabilized and/or recycled material, that is, the material having the reduced moisture state (after utilizing the unit of blending with output therefrom forming the first combination and then causing the second state), may be a stabilized and/or recycled material suitable as a sub base or a sandy, non plastic material, meeting the performance criteria of a sub base or a sandy, non plastic material. For example, said stabilized and/or recycled material can have a compressive strength of between about 25 to 100 psi, or may have a compressive strength of at least 35 psi for use as a sub base or as a sandy, non plastic material.
(31) For re-use, the stabilized and/or recycled material, that is, the material having the reduced moisture state (after utilizing the unit of blending with output therefrom forming the first combination and then causing the second state), may be used after achieving the second state. This final material as described herein may have a compressive strength that is at least about 35 psi. Said final material having a compressive strength of at least 35 psi is suitable for use as a sub base road material or as a sandy non plastic road material.
(32) In additional embodiments the material having the reduced moisture state (second state) may be further blended with one or more additional components (e.g.,
(33) With introduction of the additional components, such as binder(s) and/or surface acting agent(s), re-wetting of the first combination (in the second state) is necessary in order to form a second combination that will solidify (e.g.,
(34) A second combination having the one or more additional components, such as binder(s) and/or surface acting agent(s), is required to form a solidified stabilized and/or recycled material. For hydration reactions, re-wetting or re-hydration includes a transition from the reduced moisture state to a wetted state, which occurs before solidification. This described process is contrasted against preparations disclosed by others, in which their output after blending, even when performed with a so-called drying agent, does not provide a comparative combination having a reduced moisture content as described herein, and therefore, has instead a higher moisture content than what is described herein. Said alternative preparations do not disclose transitioning from a first state to a second state, in which the second moisture state is a dried or a friable state. The reduction in moisture content described herein to a dried or friable state ensures adequate stabilization and/or solidification thereafter. In preparations disclosed by others that do not cause the transition from the first state to the second state, moisture of these so-called comparative combinations will already have moisture content that is several percentage points higher than the optimum moisture content for compaction (e.g., in accordance with AASHTO T-99 or T-180), meaning that these other so-called comparative combinations (those disclosed by others) will start with have a higher moisture content in said preparations that are going to be solidified.
(35) As described herein, when fully blended as the second combination, a final material (e.g., a stabilized and/or recycled material for re-use) will have been or will undergo re-wetting (re-hydration or re-moistening or melt before undergoing a solidification reaction, such as a curing, hardening, hydration reaction, hydraulic reaction, and/or non-hydraulic reaction, thermal decomposition, evaporation, etc.) As long as at least one binder (with or without additional components, such as surface active agent(s), fillers, fibers, polymers, additives, etc.) is introduced in the manner described herein with or in a re-wetting step (such as in Stage B of
(36) In additional embodiments, when fully blended as the second combination, a final material (e.g., a stabilized and/or recycled material for re-use) will be blended with a binder that hardens or solidifies without addition of water. Such binders are often provided as emulsions. As depicted in
(37) When fully solidified, the final material described herein (e.g., after solidification and/or rewetting and curing/hardening) may have a compressive strength that exceeds 150 psi. The compressive strength may also be about or greater than about 200 psi. The compressive strength may be as high as 400 psi or higher. The compressive strength obtained is consistent with the compressive strength that is obtained from a solidified hydraulic material formed without the output described herein (that is, without the combination of drill cuttings and one or more drying agent). Thus, knowing a compressive strength of the binder described herein (in which the binder is a binder material, such as a hydraulic binder) will provide an estimate of the compressive strength of a final material described herein. For example,
(38) In the methods described herein, forming the second combination may be performed by the same unit for blending that is used to provide the first combination, or a second blending unit may be used, in which the second blending unit or unit for blending is the same or different or in line. Thus, like the first unit for blending, the second unit of blending may also be a mixer, blending device, blender or other similar unit or device that is known in the art for blending aggregate materials. The second unit for blending may, in some embodiments, include a heater or cooler or a compartment for heating or cooling prior to, during and/or after blending. For example, the second unit for blending may be a pug mill having a hopper or feeder into which output from the previous blending (e.g., first combination in the second state) is introduced, in addition to the binder and/or the surface active agent and/or additional components. Said introduction may be simultaneous, in batches, with or without water, and/or interrupted with additions of water. The second unit for blending may be a tiller or an auger-type screw, or other unit or machine having blades that can blend said first combination in the second state with the binder and/or the surface active agent and/or additional components. For example, in some embodiments, the first combination is provided on the ground, or in a pallet or on a sheet or on a liner and the binder and/or the surface active agent and/or additional components may be introduced to a surface of the first combination in the second state and then further combined to form the second combination by introducing the second unit of blending to the same surface that has the first combination thereon. The combining may occur before or after the introduction of water. Representative examples are depicted in
(39) Blending to form the second combination may be performed at an ambient temperature or may be blended under thermal conditions, in which the temperature is a temperature below that used to thermally cure the components, or at a temperature that facilitates the hydraulic reaction (which is generally between 120 and 160 or 170 degrees C., and generally not greater than about 160 or 170 degrees C.) or that facilitates the solidification reaction.
(40) Suitable binders that serve as hydraulic binders include, but are not limited to cementitious binders, such as Sorel cement, Portland cement, pozzolana cement, gypsum cement, high alumina content cement, slag cement, silica cement, an asphalt (or asphalt-like) binder and various combinations thereof. In some embodiments, the binder as a hydraulic binder is or includes ASTM Type I Portland cement. In some embodiments, the binder, such as hydraulic binder, is introduced alone or with other components, in dry form or as a slurry. The said other components may be pre-blended with the hydraulic binder, added upstream (prior to) or downstream (after), either in wet or dry form. In some instances, the binder, such as a hydraulic binder, is added dry for better mixing. Water is then re-introduced after blending to promote the hydraulic reaction. In other instances, the hydraulic binder is added in batches, intermixed with quantities of water, which may assist in reducing dust when blending. In addition, in some embodiments a combination of binders is blended. Fillers and/or fibers may also be included. For example, filler and fibers that increase overall strength without compromising other desired properties may be used with the at least one binder. Non-hydraulic binders may also be used, such as ones that require a catalyst to initiate curing. Additional binders may be those that form a putty or are used for mortar. A binder may be or may include one or more thermoplastic resins, and/or thermoset resins. The binder may be a petroleum based binder (e.g., asphalt).
(41) Examples of the described invention are provided below. All examples were found to be compliant with environmental standards for stabilized and/or remediated materials and may be deemed a recycled nonhazardous material for re-use, using a 7-day leachate test, a metals analysis and a chemistry analysis.
(42) In a first example, drill cuttings in an initial state were retrieved from a drill site and combined with a drying agent on day 1, the combination was found to have a reduced moisture content (first state), which was less than the moisture content (initial moisture state) of the drill cuttings. The drill cutting themselves had varying starting (initial) moisture levels; however, moisture content always decreased after addition of the drying agent. In these examples, after incorporating the drying agent, the combination was friable, and were dried in an oven to achieve the second state. Thus, essentially, the composition transitioned from a liquid, slurry state to a dry, particulated state. Other suitable means for reducing the moisture content are acceptable, as has been previously described. The representative drying agent used was cement kiln dust and was incorporated at about 10% by weight of the total quantity of the drill cuttings.
(43) After the above combination achieved the second state, a hydraulic binder was added to the combination of drill cuttings and drying agent. The hydraulic binder was added in varying amounts, either as 4 wt. % (F-4), 8 wt. % (F-8) or 10 wt. % (F-10), in addition to water. These additions were made on day 4. For one example, a hydraulic binder in an amount of 6 wt. % (F-6) followed by water was added on day 2, after approximately 72 hours. For all examples, the hydraulic binder was Type I Portland cement and was added dry to form a homogeneous mixture with the first combination. Water was added in these representative examples to rewet and rehydrate and initiate the hydraulic reaction. The formulations for each of F-4, F-6, F-8 and F-10 are provided in TABLE 1.
(44) TABLE-US-00001 TABLE 1 combination hydraulic water (g) binder (g) (g) F-4 1332 53 50 F-6 1294 78 52 F-8 1331 106 72 F-10 1346 135 77
(45) F-4, F-6, F-8 and F-10 as stabilized materials were allowed to undergo a hydraulic reaction at room temperature. Before solidification, samples were extracted from each of the stabilized materials and formed into small round shaped articles. Each article was about 2¼ inches in diameter and about 3 inches thick. Two samples were extracted for F-8 and F-10, hence the tables below show F-8-A and F-8-B (TABLE 4) and F-10-A and F-10-B (TABLE 5). At periodic time points, the sample articles were evaluated to determine loss of moisture during solidification and curing, as depicted in TABLES 2, 3, 4, and 5, respectively. Each data represents an average of n=3. Wet density was measured by weighing. Dry density was measured after adding the hydraulic binder and compacting in accordance with AASHTO), T-99.
(46) TABLE-US-00002 TABLE 2 wet density dry density (lb/ft.sup.3) (lb/ft.sup.3) F-4 Day 1 130 — F-4 Day 2 129 — F-4 Day 4 127 128 F-4 Day 7 — 127
(47) TABLE-US-00003 TABLE 3 wet density dry density (lb/ft.sup.3) (lb/ft.sup.3) F-6 Day 2 130 — F-6 Day 7 — 125
(48) TABLE-US-00004 TABLE 4 wet density dry density (lb/ft.sup.3) (lb/ft.sup.3) F-8-A Day 3 — 116 F-8-A Day 6 — 115 F-8-B Day 1 129 118 F-8-B Day 2 127 — F-8-B Day 3 126 — F-8-B Day 6 125
(49) TABLE-US-00005 TABLE 5 wet density dry density (lb/ft.sup.3) (lb/ft.sup.3) F-10-A Day 3 — 117 F-10-A Day 6 — 117 F-10-B Day 1 130 118 F-10-B Day 2 127 — F-10-B Day 3 126 — F-10-B Day 6 125
(50) The data in TABLES 2-5-show that each stabilized material that underwent a hydraulic reaction by exhibited a loss of moisture, regardless of the amount of hydraulic binder that was incorporated therein. The dry density provides an indication of the relative strength of each of the stabilized material at that time period because of a known correlation between dry density and strength, as previously described, and shown in TABLE 6. Thus, when only dry density values have been evaluated, compressive strength may be predicted.
(51) Referring again to
(52) TABLE-US-00006 TABLE 6 dry density compressive (lb/ft.sup.3) moisture strength (psi) C-4 118 12.3 237 C-6 115 13.4 338 C-8 117 12.45 548
(53) Additional samples from each of the stabilized examples F-4, F-6, F-8 and F-10, were evaluated utilizing 7-day leachate tests, for petroleum hydrocarbons, in accordance with Laboratory Procedures for Analysis of Exploration & Production Waste, for parameters under Louisiana Administrative Code 43:XIX, subpart 1, and analyzed in accordance with Texas Commission on Environmental Quality, TCEQ Method 1005. These data are presented in TABLE 7, in which MDL is method detection limit, SQL is sample detection level, and MQL is method quantification limit. The results in TABLE 7 were compared to known samples of 1-choloroctadecane and 1-chlorooctane, each of which presented results having a greater than 97% accuracy level. The results of TABLE 7 demonstrate that none of the stabilized and/or recycled materials were found to leach detectable amounts of hydrocarbons.
(54) TABLE-US-00007 TABLE 7 MDL SQL MQL Result (mg/dL) F-4 C6-C12 1.05 0.10 1.0 <0.10 C12-C28 0.96 0.10 1.0 <0.10 C28-C35 1.13 0.11 1.0 <0.11 F-6 C6-C12 1.05 0.10 0.98 <0.10 C12-C28 0.96 0.09 0.98 <0.09 C28-C35 1.13 0.11 0.98 <0.11 F-8 C6-C12 1.05 0.10 0.98 <0.10 C12-C28 0.96 0.09 0.98 <0.09 C28-C35 1.13 0.11 0.98 <0.11 F-10 C6-C12 1.05 0.11 1.0 <0.11 C12-C28 0.96 0.10 1.0 <0.10 C28-C35 1.13 0.11 1.0 <0.11
(55) Metals testing was performed on the stabilized materials of examples F-4, F-6, F-8 and F-10, in which samples were retrieved after addition of the hydraulic binder and a period of solidification for 7 days. These testings were in accordance with Environmental Protection Agency, EPA Method 6010B and EPA Method 7471B. Data are presented in TABLE 8 and show that the stabilized and recycled materials did not release potentially contaminating metals that are in excess of standards set by the EPA.
(56) TABLE-US-00008 TABLE 8 MDL SQL MQL Result (mg/kg) F-4 arsenic 0.162 0.004 0.022 1.10 barium 0.206 0.005 0.022 2.03 cadmium 0.137 0.003 0.022 0.03 chromium 0.245 0.005 0.022 0.67 lead 0.126 0.003 0.022 1.82 mercury 0.005 0.005 0.034 — selenium 0.156 0.003 0.022 0.09 silver 0.211 0.005 0.022 0.01 F-6 arsenic 0.162 0.004 0.022 1.01 barium 0.206 0.005 0.021 2.11 cadmium 0.137 0.003 0.022 0.02 chromium 0.245 0.005 0.022 0.55 lead 0.126 0.003 0.022 1.69 mercury 0.005 0.026 0.178 2.29 selenium 0.156 0.003 0.022 0.08 silver 0.211 0.005 0.022 0.01 F-8 arsenic 0.162 0.004 0.022 0.97 barium 0.206 0.005 0.021 1.95 cadmium 0.137 0.003 0.022 0.02 chromium 0.245 0.005 0.022 0.68 lead 0.126 0.003 0.022 1.69 mercury 0.005 0.026 0.172 3.34 selenium 0.156 0.003 0.022 0.09 silver 0.211 0.005 0.022 0.03 F-10 arsenic 0.162 0.003 0.020 0.87 barium 0.206 0.004 0.020 2.89 cadmium 0.137 0.003 0.020 0.02 chromium 0.245 0.005 0.020 0.61 lead 0.126 0.003 0.020 1.47 mercury 0.005 0.025 0.164 2.17 selenium 0.156 0.003 0.020 0.08 silver 0.211 0.004 0.020 0.01
(57) Chloride testing was performed on the stabilized and recycled examples F-4, F-6, F-8 and F-10, in which samples were retrieved after addition of the hydraulic binder and a period of solidification for 7 day. These tests were in accordance with Environmental Protection Agency, EPA Method 300A. Data presented in TABLE 9 show that the stabilized and recycled materials did not release potentially contaminating chloride that exceed standards set by the EPA Environmental Protection Agency.
(58) TABLE-US-00009 TABLE 9 MDL SQL MQL Result F-4 solids (%) 0.1 0.1 91.4 chloride (mg/dL) 0.05 0.05 0.1 68.0 F-6 solids (%) 0.1 0.1 91.7 chloride (mg/dL) 0.05 0.05 0.1 89.0 F-8 solids (%) 0.1 0.1 91.7 chloride (mg/dL) 0.05 0.05 0.1 110 F-10 solids (%) — — — chloride (mg/dL) 0.05 0.05 0.1 68.5
(59) Together, the data shows that the stabilized and recycled materials were safe and complied with federal and state standards for cementitious base materials. As such, the materials described herein can be used safely as a road base material or as a filling material, such as for a well, drill hole or borehole.
(60) In another example, drill cuttings were obtained from a drilling site near Premont, Tex. The drill cuttings were generally large, irregularly shaped, sticky or muddy globs or large aggregated masses, as depicted in
(61) TABLE-US-00010 TABLE 10 hydrocarbon MDL SQL MQL Result (mg/L) C6-C12 0.5 0.5 5.01 <0.5 C12-C28 0.5 0.5 5.01 <0.5 C28-C35 0.5 0.5 5.01 <0.5
(62) TABLE-US-00011 TABLE 11 metal MDL SQL MQL Result (mg/L) arsenic 0.002 0.002 0.01 <0.002 barium 0.007 0.007 0.01 0.128 cadmium 0.001 0.001 0.01 0.002 chromium 0.003 0.003 0.01 0.0116 lead 0.004 0.004 0.01 <0.004 mercury 0.0002 0.0002 0.0005 <0.0002 selenium 0.002 0.002 0.01 <0.002 silver 0.001 0.001 0.05 0.019
(63) TABLE-US-00012 TABLE 12 MDL SQL MQL Result chloride 0.05 1.00 3.20 143.0 (mg/L) pH 8.89 (pH unit)
(64) The remaining output material after blending (i.e., material forming the first combination) was laid on a surface of soil, the output material was generally laid to a depth of about six inches. One exemplary output had a surface of about 4700 square yards. This surface and depth is merely representative. For example, the surface may be of any dimension. The depth may be any desired depth, ranging at least from about a few inches to as many as several feet or more. Thereafter, the output was allowed to rest for about 7 days (though more or less days, in accordance with the description above, is acceptable). Only after resting, was the output rehydrated by first adding to the surface, both cement and water (e.g., added from tankers having suitable spreaders), followed by blending (e.g., with a tiller or rotor other suitable blending tool or machine) to combine the output with the cement and water in order to form the second combination to initiate the hydraulic reaction. When fully blended, the blended material was allowed to cure for 7 days (the period of time depending, in part, on the type of hydraulic binder). The top surface, after curing, may also be sealed or otherwise surface treated, coated and/or painted in any desired manner, as is understood in the art, such as to further minimize long-term wear and surface abrasion. Suitable surface treatments to the stabilized or recycled materials described herein, such as when formed as a road surface include a bituminous surface treatment, chipseal, thin membrane surface, and sealing coats, to give examples.
(65) A core sample from the above-described stabilized or recycled road base material was drilled and measured for hydrocarbons (in accordance with Laboratory Procedures for Analysis of Exploration & Production Waste for parameters under Louisiana Administrative Code 43:XIX, subpart 1, and analyzed in accordance with Texas Commission on Environmental Quality, TCEQ Method 1005), for metals (in accordance with Environmental Protection Agency, EPA Method 6010 or 7470 [for mercury] and EPA Method 1312), for chloride (per Environmental Protection Agency, EPA Method 300A), and pH (in accordance with Environmental Protection Agency, EPA Method 9045). Data are provided in TABLES 13, 14 and 15.
(66) TABLE-US-00013 TABLE 13 hydrocarbon MDL SQL MQL Result (mg/L) C6-C12 0.5 0.05 0.5 <0.05 C12-C28 0.5 0.05 0.5 <0.05 C28-C35 0.5 0.05 0.5 <0.05
(67) TABLE-US-00014 TABLE 14 metal MDL SQL MQL Result (mg/L) arsenic 0.002 0.002 0.01 <0.002 barium 0.007 0.007 0.01 0.197 cadmium 0.001 0.001 0.01 <0.001 chromium 0.003 0.003 0.01 0.0178 lead 0.004 0.004 0.01 <0.004 mercury 0.0002 0.0002 0.0005 <0.0002 selenium 0.002 0.002 0.01 <0.002 silver 0.001 0.001 0.05 <0.001
(68) TABLE-US-00015 TABLE 15 MDL SQL MQL Result pH 9.78 (pH unit)
(69) The TABLES 10, 11 and 12 illustrate output materials prior to solidification. TABLES 13, 14 and 15 illustrate materials after solidification. Together, the data show that these stabilized materials were safe and complied with federal and state standards for cementitious base materials suitable for use as a sub base or as a road material.
(70) The stabilized or recycled materials described herein may be used safely as a road base material and/or as a filling material, such as for a well, drill hole or borehole. As either a road base material or a filling material, the stabilized or recycled materials described herein may be applied to a soil surface, a subsurface or other type of surface that may include a cementitious component, an asphalt component or other structural component. For example, a stabilized or recycled material described herein may be one layer, or provided as a number of layers, for a road comprising one or a number of components, including a base, a treated base (permeable or otherwise), a hot mix, and a cement top.
(71) In TABLE 16, stabilized materials processed as described herein were obtained from seven drill wells in southern Texas at various locations in the Eagle Ford Shale region, each of which were drilled on similar dates (or within three months of each other). For TABLE 16, drill cuttings were processed in batches as the drill cuttings were removed from the well and after drilling mud was recaptured by a shaker system. In brief, drill cuttings from a single well were processed in batches, each batch included blending or comingling the drill cuttings taken off the shaker system with about 10 wt. % drying agent (range: 8 wt. % to 12 wt. %, using cement kiln dust) (forming the first combination) and stacking to rest on a surface or in a pit for at least three days or at least seven days or more after blending to provide a stabilized material in a second state; the average amount of days for resting varied with the number of days it took finish the well and collect all the drill cuttings from the well. The batches were generally stacked together in one pit. One well took up to a few days to retrieve all the drill cuttings. On average, and preferably at a minimum, the stabilized material had rested for about seven days or more, after which a sample (in a dried or friable state, second state) was removed and tested in accordance with the test methods identified in TABLE 16. All samples provided values below the standards, thereby considered stabilized and suitable for re-use or for recycling.
(72) TABLE-US-00016 TABLE 16 Result (mg/L) Test Method hydrocarbon C6-C12 <0.09 TCEQ 1005 C12-C28 <0.10 TCEQ 1005 C28-C35 <0.05 TCEQ 1005 benzene <0.004-0.185 1312/8021B metal arsenic <0.002-01 EPA 1312/6010 barium 0.347-1.433 EPA 1312/6010 cadmium <0.001-0.005 EPA 1312/6010 chromium 0.0067-0.215 EPA 1312/6010 lead <0.004-0.01 EPA 1312/6010 mercury <0.0002-0.002 (ppm) EPA 1312/6010 selenium 0.004-0.01 EPA 1312/6010 silver <0.001-0.01 EPA 1312/6010 zinc <0.01 SW 6010B chloride 245-364 (mg/L) EPA 300 pH 8.37-11.5 (pH unit) EPA 9045
(73) Stabilized materials from six of the seven drill wells identified in TABLE 16 were further evaluated for compressive strength, in which a representative compressive strength value for a well sample is shown in TABLE 17. For TABLE 17, a sample was taken at any time after resting for about seven days. Once taken, each sample was tested 7 days after it was sent, in accordance with Tex 120E, in which each sample when compacted for testing had a generally uniform diameter of about 6 inches, an area of about 28.3 inches and a height that ranged from about 7.69 to 8 inches. Maximum loading of the samples was between 1275 and 3400 and pounds (lbs). The moisture content (moisture %) at time of molding was also measured, as provided in TABLE 17. These moisture content amounts represented a reduction in moisture of at least 20% based on the initial moisture content of the drill cuttings (before addition of the drying agent). The values in TABLE 17 confirm that the stabilized materials met the requirements for and were suitable as a sub base road material, having a compressive strength at least greater than 35 psi.
(74) TABLE-US-00017 TABLE 17 Height Dry density Strength Moisture (inch) (lb/ft.sup.3) (psi) (%) B-3 7.88 101.7 43 19.5 B-4 7.75 105.2 57 17.9 D-12 7.88 105.1 111 18.0 D-13 8 103.1 114 18.0 D-14 7.94 101.6 50 18.5 D-15 7.69 104.1 44 19.2
(75) In TABLE 18, further stabilized materials were evaluated by processing as described above for TABLE 16. These stabilized materials were obtained by using drill cuttings from eleven different drill wells in southern Texas at various locations in the Eagle Ford Shale region, each of which were drilled on similar dates (or within three months of each other). The values in TABLE 18 show the range of values that were obtained from the eleven drill wells and confirm that these stabilized materials when processed as described herein were safe, complying with federal and state standards as stabilized materials suitable for use as a sub base or as a road material or as a recycled material. Compressive strength data for these samples are provided in TABLE 19 for stabilized material obtained from ten of the drill sites, using testing as described with TABLE 17. Maximum load of the samples in TABLE 19 was up to about 3000 lbs. (between about 1075 and about 2475 lbs). The moisture content measured at time of molding represented a reduction in moisture of at least 20% based on the initial moisture content of the drill cuttings (before addition of the drying agent). Data from TABLE 19 also confirms that these stabilized materials met the requirements for and were suitable as a sub base road material, having a compressive strength of at least greater than 35 psi.
(76) TABLE-US-00018 TABLE 18 Result (mg/L) Test Method hydrocarbon C6-C12 <2 TCEQ 1005 C12-C28 <2-14 TCEQ 1005 C28-C35 <2 TCEQ 1005 benzene <0.004 SW 8260B metal arsenic <0.01 SW 6010B barium 0.319-0.96 SW 6010B cadmium <0.005 SW 6010B chromium 0.0054-0.016 SW 6010B lead <0.01 SW 6010B mercury <0.002 (ppm) EPA 245.1/7470 selenium <0.02 SW 6010B silver <0.01-0.02 SW 6010B zinc <0.01 SW 6010B chloride 97-503 (mg/L) EPA 300 pH 10.2-11.6 (pH unit) EPA 4500
(77) TABLE-US-00019 TABLE 19 Height Dry density Strength Moisture (inch) (lb/ft.sup.3) (psi) (%) AT-9 7.88 106.2 46 16.5 AT-10 7.89 105.4 66 15.3 G-1 8.38 99.4 84 20.4 K-3 7.63 103.1 39 17.5 K-4 7.50 104.5 42 17.5 K-5 7.75 101.3 36 17.7 K-6 7.25 101.8 41 17.1 M-8 8.13 100.9 79 19.6 R-1 8.13 99.4 62 20.8 T-1 7.94 104.2 36 15.9
(78) In further examples, drill cuttings were processed as described with TABLE 16 from twenty-five additional drill well sites in southern Texas at various locations in the Eagle Ford Shale region, each of which were drilled on similar dates (or within three months of each other). The values in TABLE 20 show the range of values that were obtained for the stabilized materials processed independently from the 25 additional drill wells and confirm that these stabilized materials when processed as described herein were safe, complying with federal and state standards as stabilized materials suitable for use as a sub base or as a road material or as a recycled material. For TABLE 21, drill cuttings were processed in a similar manner as described with TABLE 16, with compressive strength data provided in TABLE 21. Samples in TABLE 21 were tested in accordance with AASHTO T-99 and ASTM standards (D698) for a Proctor compaction test. The maximum load was up to about 1000 lb (amount ranged between about 510 and about 1030 lbs), in which each sample had a diameter of about 4 inches, an area of about 12.5 inches, and a height that ranged from about 4.5 inches to about 4.7 inches. TABLE 21 also provides the moisture content (moisture %) measured at the time of molding, which was a reduction in moisture of at least 20% based on the initial moisture content of the drill cuttings (before addition of the drying agent). Data from TABLE 21 confirms that these stabilized materials met the requirements for and were suitable as a sub base road material, having a compressive strength of 35 psi or greater.
(79) TABLE-US-00020 TABLE 20 Result (mg/L) Test Method hydrocarbon C6-C12 <2-2.5 TCEQ 1005 C12-C28 <2-36 TCEQ 1005 C28-C35 <2 TCEQ 1005 metal arsenic <0.01 SW 6010B barium 0.352-1.18 SW 6010B cadmium <0.005 SW 6010B chromium 0.005-0.015 SW 6010B lead <0.01 SW 6010B mercury <0.002 (ppm) EPA 245.1/7470 selenium <0.02 SW 6010B silver <0.01 SW 6010B zinc <0.01 SW 6010B chloride 80-679 (mg/L) EPA 300 pH 10.7-11.9 (pH unit) EPA 4500
(80) TABLE-US-00021 TABLE 21 Height Dry density Strength Moisture (inch) (lb/ft.sup.3) (psi) (%) AL-11 4.53 95.2 62 16.9 AL-12 4.59 104.6 41 11.1 AL-13 4.65 109.8 56 9.5 BR-20 4.59 109.4 46 9.9 BR-21 4.68 114.1 55 9.5 BL-5 4.58 107.7 39 8.4 BL-6 4.59 102.7 48 10.3 CS-17 4.60 110.1 72 11.0 CS-33 4.68 106.9 79 10.1 GL-1 4.69 117.1 67 8.0 GL-2 4.72 115.6 45 8.2 J-11 4.55 123.3 68 6.5 J-12 4.67 109.7 63 9.8 J-13 4.55 120.9 65 6.7 KS-3 4.57 117.2 38 8.8 ML-37 4.60 108.4 82 10.2 N-11-1 4.53 116.8 65 7.3 N-33-1 4.51 117.9 35 8.8 N-33-2 4.62 109.4 54 11.4 N-2-1 4.63 119.3 65 7.2 N-2-2 4.60 117.2 51 7.4 P-4 4.62 112.8 52 6.7 U-7 4.63 108.4 41 10.7 U-9 4.62 109.7 100 8.9 W-1 4.53 118.0 38 9.0
(81) In TABLE 22, stabilized materials were processed as described with TABLE 16 and were obtained from a further eight drill wells in southern Texas at various locations in the Eagle Ford Shale region, each of which were drilled on similar dates (or within two to three months of each other). The values in TABLE 22 show the range of values that were obtained from the eight drill wells and confirm that these stabilized materials when processed as described herein were safe, complying with federal and state standards as stabilized materials suitable for use as a sub base or as a road material or as a recycled material. Compressive strength testing data of stabilized materials prepared from seven of the well sites is provided in TABLE 23, in which samples were processed in accordance with AASHTO T-99 and ASTM standards (D698) for a Proctor compaction test, in which samples had a diameter of about 4 inches, an area of about 12.5 inches, and a height that was about 4.6 to 4.7 inches. Maximum load was up to 1000 lbs (between about 460 and about 950 lbs). TABLE 23 also provides moisture content (moisture %) measured at the time of molding, which was a reduction in moisture of at least 20% based on the initial moisture content of the drill cuttings (before addition of the drying agent). Data from TABLE 23 confirms that these stabilized materials met the requirements for and were suitable as a sub base road material, having a compressive strength of 35 psi or greater.
(82) TABLE-US-00022 TABLE 22 Result (mg/L) Test Method hydrocarbon C6-C12 <2 TCEQ 1005 C12-C28 <2-2.4 TCEQ 1005 C28-C35 <2 TCEQ 1005 metal arsenic <0.01 SW 6010B barium 0.414-0.988 SW 6010B cadmium <0.005 SW 6010B chromium 0.005-0.014 SW 6010B lead <0.01 SW 6010B mercury <0.002 (ppm) EPA 245.1/7470 selenium <0.02 SW 6010B silver <0.01 SW 6010B zinc <0.01 SW 6010B chloride 74-526 (mg/L) EPA 300 pH 11.0-12.0 (pH unit) EPA 4500
(83) TABLE-US-00023 TABLE 23 Height Dry density Strength Moisture (inch) (lb/ft.sup.3) (psi) (%) CS-64 4.65 115.6 62 5.7 N-34-2b 4.6 114.8 69 7.6 N-34-2 4.68 114.9 48 10.1 N-37-1 4.65 112.6 35 8.6 N-42-4 4.63 116.3 60 7.6 N-53-1 4.58 118.4 72 7.1 P-5 4.65 116.9 39 7.8
(84) Any of the stabilized materials from the examples may be used alone (once stabilized as described above) or in combination with binder(s) described herein and/or surface acting agent(s) described herein. Used alone, the stabilized materials may be dumped, spread out on a surface or on the ground (either soil or other sub surface) to a desired thickness and rolled to apply a density to the stabilized material. A plurality of layers may be laid down, one above the other. In some embodiments, each layer (when more than one) may have a thickness that is less than ten inches or less than eight inches. Each layer (when more than one layer is applied) may generally be at least 2 inches, or 3 inches, and often is at least 4 inches. There is no limit to the number of layers comprised of the stabilized materials described herein that may be applied to a surface. Said one or more layers may be further treated, pigmented, or modified, e.g., for surface water repellence, etc.
(85) In another example of further processing stabilized materials, the stabilized materials, once stabilized as described herein (caused to achieve the second state) are spread out to a desired thickness. The spreading may be on a prepared road surface, dirt, or other type of surface to which a stabilized material may be laid out on. In one example, when laying out as a road material, the layer thickness after spreading may be between about 4 inches and about 8 inches. The layer when spread is rolled. This may then be used a road base. This will have strength of at least 35 psi. Alternatively, the rolled layer may be wetted and/or plowed, with or without cutting ruts therein. When wetting, a surface acting agent may be included. This may then be blended using an appropriate blending unit to blend the surface acting agent with at least a top surface of the layer, which may include a few inches to half the depth or even to the full depth of the layer. This layer of stabilized material may also serve as a suitable surface for driving on, including large trucks and/or construction equipment. The process may be repeated in order to achieve a plurality of layers. To solidify (the one or plurality of layers), before the previously described blending or after said blending, a binder (e.g., a cementitious binder, such as a cement or Type I Portland cement, with appropriate additives suitable for a road) may be applied thereon or spread out onto the wetted surface. With cement, a sufficient amount may be included for a final concentration of cement to be between about 4 wt. % and about 10 wt. %. In some embodiments, the final amount of cement may be about 6 wt. %. Upon spreading the binder or cement, a mixer is directed over the surface, mixing the surface as well as mixing to a desired depth below the surface. The depth may, in some embodiments, be up to about 6 inches, or may be more than six inches, or less than six inches. After mixing, water or an aqueous solution (one that is suitable for use and for a next mixing with the binder, when already applied thereon) is sprayed on the surface of the mixture. In some instances this water aqueous solution, rather than the prior wetting, may include the surface acting agent. The surface acting agent when included (in either wetting step) is typically included to a final concentration of up to about 1%, or may be up to about 0.5% or may be up to about 0.1%, or in any amount therein (generally not more than about 0.5 wt. % or not more than about 1 wt. %). After addition of the water or aqueous solution (with or without the surface action agent), there is further mixing, the mixing here is often either to the full depth of the layer or near the full depth of the layer. Following mixing, the layer may optionally be compacted with a compactor and/or graded. In some embodiments, there may optionally be another mixing, in which mixing is generally not to the full depth, and may be only about or less than about half the depth of the layer. A further compaction may or may not occur thereafter, at which time the road may already be ready for use or may be allowed to set for several days (up to about 10 days) before allowing heavy traffic. Said preparation as described is a road material suitable for heaving construction equipment and heavy traffic thereon. Said preparation may include additional steps or fewer steps as desired in order to achieve a solidified and stabilized material that may serve as a road material or as a base material for a road. Other uses are also acceptable with the stabilized materials described herein.
(86) When the stabilized or recycled materials described herein include a cementitious binder, the stabilized and solidified materials may be used in addition to or as replacement to a cement treated base (permeable or other treated base). When the stabilized or recycled materials described herein include an asphalt containing binder, such stabilized and solidified materials may be used in addition to or as replacement to an asphalt treated base (permeable or other treated base). When the stabilized or recycled materials described herein include a binder suitable for a lean concrete base or sub base, such stabilized and solidified materials when finally formed may be used in addition to or as replacement to a lean concrete base or sub base. When the stabilized or recycled materials described herein include a binder suitable for a lime treated base or sub base, such stabilized and recycled materials when fully formed may be used in addition to or as replacement to a lime treated base or sub base.
(87) Although representative processes and articles have been described in detail herein, those skilled in the art will recognize that various substitutions and modifications may be made without departing from the scope and spirit of what is described and defined by the appended claims.