Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
  • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
  • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00034—Physico-chemical characteristics of the mixtures
  • C04B2111/00146—Sprayable or pumpable mixtures

Definitions

• the present invention generally relates to additives for particulate materials, such as cementitious materials and non-cementitious materials. More specifically, the present invention relates to compositions that may improve the flow properties of dry particulate cementitious and non-cementitious materials and related methods of synthesis and use.
• Cementitious materials such as hydraulic cements, slag, fumed silica, fly ash and the like having various particle size distributions are often dry-blended and placed in storage tanks.
• the storage tanks containing the cementitious materials are often transported by land or sea to locations where the cementitious materials are to be used. During such transportation, the cementitious materials are subjected to vibrations and as a result, under static conditions, the materials can become tightly packed.
• significant portions of the tightly packed materials may unintentionally be left behind in the storage tanks or clumps of the packed materials may become lodged in transfer conduits. Beyond the cost of the unusable cementitious materials, costly removal and disposal procedures may be required to remove the packed materials from the storage tanks or transfer conduits.
• Treatments have been developed to reduce the likelihood that cementitious and non-cementitious materials will pack by improving or preserving the flow properties of the materials.
• Certain treatments involve blending dry particulate cementitious and/or non-cementitious materials with an additive.
• One such additive comprises a particulate solid adsorbent material having a flow inducing chemical adsorbed thereon.
• these additives are dry-blended with cementitious and/or non-cementitious materials at a point in time before packing is likely to occur, e.g., before the materials are shipped or stored.
• the dry-blending step occurs at a location other than the location where the cementitious or non-cementitious materials are ultimately utilized.
• an additive may be dry-blended with cementitious materials in a warehouse before the blend is transported to a second location where it is used in a cementing operation.
• additives comprising a flow inducing chemical adsorbed onto a particulate solid adsorbent material may improve the flow properties of cementitious and non-cementitious materials
• certain undesirable properties of the additives may complicate or limit their use.
• known additives may conglomerate and/or freeze at relatively high temperatures.
• the additives may begin to conglomerate at temperatures as high as 60° F.
• additives may freeze at temperatures as high as 55° F.
• an additive When completely frozen, an additive may lose its free-flowing, powder-like consistency and take the form of a solid, rock-like mass.
• an additives' low freezing point may be most problematic prior to the point when the additive is dry-blended with another material, e.g. when the additive is still in a relatively pure form. Due to the low freezing point of some additives, in cold climates the additives may have to be produced and/or stored in climate-controlled facilities, e.g., climate-controlled warehouses.
• the additives may freeze and become at least temporarily unusable, because they cannot be dry-blended with cementitious or non-cementitious materials in a frozen state.
• the freezing points of the individual components of the additive may be even higher than the freezing point of the finished additive, e.g., certain components may have freezing points above 60° F, so the components may freeze while the additive is being manufactured, making it difficult or impossible to produce the finished additive.
• the present invention generally relates to additives for particulate materials, such as cementitious materials and non-cementitious materials. More specifically, the present invention relates to compositions that may improve the flow properties of dry particulate cementitious and non-cementitious materials and related methods of synthesis and use.
• the present invention provides compositions comprising: a particulate solid adsorbent material; a flow inducing chemical; water; and ethylene glycol.
• the present invention provides methods comprising: providing a flow enhancing additive comprising a flow inducing chemical, a solid adsorbent particulate material, ethylene glycol, and water; providing a cementitious material, a non- cementitious material, or a mixture of cementitious and non-cementitious material; and blending the flow enhancing additive with the cementitious material, the non-cementitious material, or the mixture of cementitious and non-cementitious material.
• the present invention provides methods comprising: providing a cementitious material, a non-cementitious material, or a mixture of cementitious and non-cementitious material comprising a flow enhancing additive, wherein the flow enhancing additive comprises a flow inducing chemical, a solid adsorbent particulate material, ethylene glycol, and water; allowing the cementitious material, non-cementitious material, or the mixture of cementitious and non-cementitious material to interact with a sufficient amount of water to form a pumpable slurry; and placing the pumpable slurry in a subterranean formation.
• FIGURE 1 shows the change in the viscosity of a cement slurry over time.
• FIGURE 2 shows the change in the viscosity of a cement slurry over time.
• the present invention generally relates to additives for particulate materials, such as cementitious materials and non-cementitious materials. More specifically, the present invention relates to compositions that may improve the flow properties of dry particulate cementitious and non-cementitious materials and related methods of synthesis and use.
• the present invention relates to additives for cementitious and non-cementitious materials and related methods of using cementitious and non-cementitious materials which comprise these additives.
• the present invention generally provides compositions that may impart desired flow properties to dry particulate cementitious materials, non-cementitious materials, or a mixture of a cementitious and non-cementitious materials. These compositions are broadly referred to herein as "flow enhancing additives.”
• the flow enhancing additives of the present invention may have a lower freezing point than previously known flow enhancing additives.
• the freezing point of the flow enhancing additives may be downwardly adjustable to a desired temperature by varying the relative amounts of the substances that make up the additives.
• One benefit of a depressed freezing point may be that the flow enhancing additive may be stored at temperatures at which previously known additives conglomerate or freeze into a solid mass. In particular, the need for climate- controlled storage of concentrated forms of the flow enhancing additives may be eliminated.
• the flow enhancing additives of the present invention may comprise a particulate solid adsorbent material, a flow inducing chemical, ethylene glycol, and water.
• Particulate solid adsorbent materials that are suitable for use in the flow enhancing additives of the present invention may comprise any particulate adsorbent solid that does not negatively interact with other components of the flow enhancing additive.
• suitable particulate solid adsorbent materials are capable of adsorbing the flow inducing chemical(s) utilized in the flow enhancing additive.
• adsorbent materials include, but are not limited to, precipitated silica, zeolite, talcum, diatomaceous earth fuller's earth, derivatives thereof, and combinations thereof. Of these, precipitated silica is presently preferred.
• a commercially available precipitated silica that is suitable for use in the flow enhancing additives of the present invention is available under the tradename "Sipernat-22TM" from Degussa GmbH of Dusseldorf, Germany.
• Flow inducing chemicals that are suitable for use in the present invention may comprise any chemical that interacts or reacts with cementitious and/or non- cementitious materials in such a way that a relative increase in the flow properties of the cementitious and/or non-cementitious materials may be observed.
• preferred flow inducing chemicals produce polar molecules.
• suitable flow inducing chemicals include, but are not limited to, organic acids such as alkyl and/or alkene carboxylic acids and sulfonic acids, salts of the foregoing acids formed with weak bases, acid anhydrides such as sulfur dioxide, carbon dioxide, sulfur trioxide, nitrogen oxides and similar compounds, derivatives thereof, and combinations thereof.
• the flow inducing chemical is adsorbed onto the particulate solid adsorbent material utilized in the flow enhancing additive.
• One preferred flow inducing chemical for use in accordance with the present invention is glacial acetic acid.
• certain particulate solid adsorbent materials may serve as suitable flow inducing chemicals by reducing the tendency of the cementitious or non-cementitious materials to pack.
• the solid adsorbent material utilized in the flow enhancing additive may serve a dual-function as the solid adsorbent material and the flow inducing chemical.
• the flow inducing chemical may not be adsorbed onto the solid adsorbent material, because the solid adsorbing material and the flow inducing chemical are one in the same.
• the ability of particulate solid adsorbent materials to reduce packing of cementitious and/or non-cementitious materials may be the result of the formation of a solid crystal lattice structure between the particulate materials.
• the weight ratio of particulate solid adsorbent material to flow enhancing chemical in the flow inducing additive is generally in the range of from about 90:10 to about 10:90, more preferably in the range of from about 75:25 to about 25:75. Other ranges may be suitable as well.
• the particulate solid adsorbent material and the flow enhancing chemical are present in approximately equal amounts by weight.
• the water used in the flow enhancing additives of the present invention may comprise fresh water, saltwater ⁇ e.g., water containing one or more salts dissolved therein), brine, seawater, or combinations thereof.
• the water may be from any source, provided that it does not contain components that might adversely affect the stability and/or performance of the additives of the present invention.
• Ethylene glycol may be present in the flow enhancing additive in an amount ranging from about 10% to about 150% by weight of the water present in the flow enhancing additive. According to some embodiments, the ethylene glycol may be present in an amount ranging from about 10% to about 100% by weight of the water. In some embodiments, the total combined amount of ethylene glycol and water present in the flow enhancing additive is an amount sufficient to lower the freezing point of the flow enhancing additive to a desired temperature.
• the relative amounts of ethylene glycol and water and/or the total combined amount of ethylene glycol and water present in the flow enhancing additive may depend upon a number of factors, including the flow inducing chemical utilized in the flow enhancing additive, the particulate solid adsorbent material utilized in the flow enhancing additive, the relative amounts of flow inducing chemical to particulate solid adsorbent material, the freezing points of the particulate solid adsorbent material and the flow enhancing chemical in the absence of ethylene glycol and water, and the desired freezing point of the flow enhancing additive.
• a person of ordinary skill in the art may be able to appreciate the relative amounts of ethylene glycol and water and/or the total combined amounts of ethylene glycol and water necessary to lower the freezing point of the flow enhancing additive to a desired temperature.
• the flow enhancing additives of the present invention may have a lower freezing point than combinations of similar amounts of particulate solid adsorbent material and flow inducing chemical in the absence of water and ethylene glycol.
• the mechanism by which the freezing point of a flow enhancing additive of the present invention is depressed is not fully understood, it is thought that the water present in the flow enhancing additive may form hydrogen bounds with the flow inducing chemical so that the freezing point of the flow inducing chemical is lowered.
• the ethylene glycol may interact with the water to lower the freezing point of the water. It is believed that this system of interactions is responsible for depressing the overall freezing point of the flow enhancing additive.
• the flow enhancing additives of the present invention are dry-blended with cementitious materials.
• the cementitious material may be any cementitious material that is suitable for use in cementing operations.
• Cementitious materials that are suitable for use in the present invention include, but are no limited to, hydraulic cements, slag, fumed silica, fly ash, mixtures thereof, and the like.
• a variety of hydraulic cements are suitable for use, including those comprising calcium, aluminum, silicon, oxygen, and/or sulfur, which may set and harden by reaction with water.
• Such hydraulic cements include, for example, Portland cements, pozzolanic cements, gypsum cements, high alumina content cements, silica cements, high alkalinity cements, slag cements, Sorel cements, cement kiln dust, vitrified shale, derivatives thereof, and combinations thereof.
• Portland cements pozzolanic cements
• gypsum cements high alumina content cements
• silica cements high alkalinity cements
• slag cements Sorel cements
• cement kiln dust vitrified shale, derivatives thereof, and combinations thereof.
• cementitious material comprises a hydraulic cement that comprises a Portland cement.
• the flow enhancing additives of the present invention are dry-blended with non-cementitious materials.
• Non-cementitious materials suitable for use in the present invention include any non-cementitious materials which would not adversely interact with the flow enhancing additives of the present invention.
• Particularly suitable non-cementitious materials include non-cementitious materials which have a tendency to demonstrate reduced flow properties over some period of time in the absence of a flow enhancing additive.
• suitable non-cementitious materials for use with the flow enhancing additives of the present invention include, but are not limited to, barite, bentonite, lost circulation materials, tensile strength enhancers, elastomers, metal oxides, gypsum, derivatives thereof, combinations thereof, and the like.
• any suitable method for making the flow enhancing additives of the present invention may be employed.
• the present invention provides methods of making a flow enhancing additive having a depressed freezing point comprising adsorbing a flow inducing chemical on a particulate solid adsorbent material, providing ethylene glycol and water in the presence of the flow inducing chemical, and allowing the water to interact with the flow inducing chemical and the ethylene glycol.
• one or more of the flow inducing chemical, ethylene glycol, and water may be premixed before the mixture is exposed to the particulate solid adsorbent material.
• the flow inducing chemical, ethylene glycol, and water are premixed and then the mixture is exposed to particulate solid adsorbent materials so that the flow inducing chemical adsorbs onto the particulate solid adsorbent materials.
• the flow inducing chemical is first exposed to the particulate solid adsorbent material, and ethylene glycol and water are later added and evenly distributed therein.
• ethylene glycol and water may be added to a pre-made flow enhancing composition.
• a pre-made flow enhancing composition is commercially available under the trade name "EZ-FLO" from Halliburton Energy Services, Inc. of Duncan, Oklahoma.
• Still another aspect of the invention provides methods of using a flow enhancing additive to improve the flow properties of cementitious and/or non-cementitious materials comprising: providing a flow enhancing additive comprised of a flow inducing chemical, a solid adsorbent particulate material, ethylene glycol, and water; providing a cementitious material, a non-cementitious material, or a mixture of cementitious and non- cementitious material; and blending the flow enhancing additive with the cementitious material, the non-cementitious material, or the mixture of cementitious and non-cementitious material.
• the amount of flow enhancing additive blended with the cementitious or non-cementitious material is an amount in the range of from about 0.005% to about 5% by weight of the cementitious or non-cementitious materials, more preferably in the range of from about 0.01% to about 1%, and most preferably in an amount in the range of from about 0.02% to about 0.5%.
• the amount of flow enhancing additive blended with the cementitious and/or non- cementitious material is an amount sufficient to improve or preserve the flow properties of the material after a period of storage in a storage tank.
• the flow enhancing additives of the present invention may be dry- blended with cementitious and/or non-cementitious materials through any method known in the art to be suitable for dry-blending.
• the flow enhancing additive is dry-blended with cementitious and/or non-cementitious materials by boxing the materials.
• boxing comprises alternating between blowing portions of cementitious and/or non-cementitious materials and portions of flow enhancing additive into a common container.
• the contents of the common container are then transferred from the common container to a second container.
• the contents are then repeatedly transferred from container to container so that a relatively homogenous mixture of flow enhancing additive and cementitious and/or non-cementitious materials is achieved.
• the contents of the second container are transferred back to the common container, then back to the second container, and so forth, until the material has been transferred at least four times.
• the blend may be stored in storage tanks without substantial deterioration of the flow properties of the cementitious and/or non-cementitious materials or the undesirable consequences of the flow enhancing additive freezing.
• the blend may be conveyed from the storage tank by mechanical or pneumatic means without unintentionally leaving a significant portion of the blend in the storage tank.
• significant portion is defined herein to mean a portion of the stored blend that is above 15% of the total volume thereof.
• an amount of water sufficient to form a pumpable slurry may be added to the blend.
• the pumpable slurry may be placed in a subterranean formation.
• the pumpable slurry may be placed in the subterranean formation in conjunction with a subterranean cementing operation or another subterranean treatment. Any means known in the art for placing a slurry into a subterranean formation may be suitable for use in the present invention, including, but not limited to, pumping, injecting, flowing, and hydrajetting.
• Some embodiments of the present invention comprise the steps of providing a cementitious and/or non-cementitious material comprising a flow enhancing additive, wherein the flow enhancing additive further comprises a flow inducing chemical adsorbed onto a solid adsorbent particulate material, ethylene glycol, and water; allowing the cementitious or non-cementitious material to interact with a sufficient amount of water to form a pumpable slurry; and placing the cementitious and/or non-cementitious material in a subterranean formation.
• a flow enhancing additive comprising a flow inducing chemical adsorbed onto a solid adsorbent material, ethylene glycol, and water might have a depressed freezing point compared to similar additives comprising only a flow inducing chemical adsorbed onto a solid adsorbent material
• experimental samples were prepared in 300 mL bottles, the bottles were secured with a lid, and stored in a 10° F freezer as follows: Sample 1, representing a control sample, contained 30 grams of EZ-FLO obtained from Halliburton Energy Services of Duncan, Oklahoma. The bottle was placed in the freezer overnight and froze into a solid, rock-like mass. Upon thawing, the sample regained its free-flowing properties.
• Sample 2 was prepared by placing 30 grams of EZ-FLO (from the same batch used to prepared Sample 1), 5 grams of water, and 1.5 grams of ethylene glycol in a bottle and hand shaking to evenly distribute the materials. After one night in the freezer, Sample 2 remained free flowing. Sample 2 was returned to the freezer, and after two more days (three total days of cold-storage), the flow properties of Sample 2 were visibly unchanged. To prepare Sample 3, 30 more grams of EZ-FLO were added to the three day-old Sample 2, and the materials were combined through hand shaking. After 24 hours in the freezer, most of Sample 3 was still free flowing, but some material stuck to the sides of the container.
• Samples 1 and 3 contained only Portland cement and no additives.
• Samples 2, 4, and 5 contained additive in an amount weighing about .07% of the weight of the cement.
• the cements used in the samples were Class G Portland cements purchased from the Norcem Cement Company of Norway and Dykerhoff AG of Germany.
• the composition of the additives varied according to the sample.
• the additive that was used in Sample 2 was pure EZ-FLO product obtained from Halliburton Energy Services, Inc. of Duncan, Oklahoma.
• the additive that was used in Sample 4 was prepared by mixing 30 grams of EZ-FLO product with 6 grams of a 30% ethylene glycol solution (i.e., 30% ethylene glycol by weight of the water present in the ethylene glycol solution).
• the additive that was used in Sample 5 was prepared by mixing 30 grams of EZ-FLO product with 6 grams of a 50% ethylene glycol solution
• the flask was continuously rotated for the number of counts required for the cement blend in the flask to show initial and then complete separation between the particles of the blend. After the cement blend decompacted, the flask containing the cement blend was shaken vigorously and the cement blend was re-swirled for 5 seconds whereupon the test was repeated. This procedure was repeated for a total of three or 4 tests, as indicated in Table 2, which shows the results of each test. AU tests were performed at room temperature.
• Additive is glycol in added to Cement in the Rotations an amount of about ethylene Rotations until until
• Additive is glycol in added to Cement in an the Rotations amount of about .07% ethylene Rotations until until
• Sample 12 serving as a control sample, comprised only Class G cement.
• Sample 13 comprised Glass G cement and .07% of pre-made EZ-FLO by weight of the cement.
• Sample 14 was prepared by mixing 150 grams glacial acetic acid with 50 grams of water and 15 grams of ethylene glycol ⁇ i.e., a 30% ethylene glycol solution), and placing the mixture in an atomizer.
• an atomizer was then use to apply this mixture to 150 grams of "Sipernat-22TM" precipitated silica that was continuously stirred in a 2 quart blender jar at a rate of 3000 rpm. After all of the acetic acid/water/ethylene glycol mixture was applied to the precipitated silica to create a flow enhancing additive, the flow enhancing additive was added to Glass G cement in an amount of about .07% by weight of the cement.
• the pack set index that was created using samples 12, 13, 14, and 15 is shown in Table 3.
• an atomizer may be an effective means for introducing the liquid components of a flow enhancing additive to the solid components of the flow enhancing additive.
• Samples 15 and 16 were prepared and subjected to the pack set test described above.
• Sample 15 contained only Joppa Class A cement from LaFarge North America.
• Sample 16 contained Class A Joppa cement and an additive in an amount weighing about .07% by weight of the cement.
• the additive was prepared by mixing 30 grams of pre-made EZ-FLO product with 6 grams of ethylene glycol solution.
• the ethylene glycol solution was comprised of water and 30% ethylene glycol by weight of the water.
• Table 4 the additive was effective to decrease packing of the Joppa Class A cement.
• Additive is glycol in added to Cement in the Rotations an amount of about ethylene Rotations until until
• Slurry 2 contained 700 grams of a standard cement, 325.9 grams of water, and 0.5 grams of a mixture of EZ-FLO and ethylene glycol solution, wherein the mixture of EZ-FLO and ethylene glycol solution was prepared by combining 30 grams of EZ-FLO and 6 grams of a solution of water and 30% ethylene glycol by weight of the water.
• the temperature of the slurries was adjusted to about 80° F and the pressure was adjusted from an initial pressure of about 1000 psi to about 3000 psi. The temperature and pressure were then kept relatively constant for the duration of the test. Over time, the viscosity of both slurries, as measured in Bearden units (Bc), increased sharply. Therefore, according to this embodiment, the presence of ethylene glycol in Slurry 2 did not prevent a desirable increase in the viscosity of the slurry over time.
• Bearden units Bc
• every range of values (of the form, "from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b") disclosed herein is to be understood as referring to the power set (the set of all subsets) of the respective range of values, and set forth every range encompassed within the broader range of values.
• the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Structural Engineering (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=39689316

Family Applications (1)

Country Status (3)

Family Cites Families (7)

• 2008
  • 2008-03-11 EP EP08718693A patent/EP2125655A2/de not_active Withdrawn
  • 2008-03-11 WO PCT/GB2008/000847 patent/WO2008113975A2/en not_active Ceased
  • 2008-03-11 CA CA002680392A patent/CA2680392A1/en not_active Abandoned

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events