Dual function proppants.
Abstract
Se proporcionan apuntalantes para utilizarlos en los pozos de petróleo y gas fracturados o empacados con gradilla/empacados frac, con un componente removedor de contaminantes para separar uno o más de los contaminantes que se encuentran en el agua/hidrocarburo subterráneo de un pozo de producción. Los sólidos apuntalantes que limpian el agua/hidrocarburo pueden ser utilizados como partículas discretas en una formulación de apuntalante, como un recubrimiento sobre sólidos del apuntalante en los poros de un sólido apuntalante poroso o como parte de la estructura interna del apuntalante. El componente para remover contaminantes separa los contaminantes, especialmente los contaminantes disueltos, en el agua o hidrocarburo subterráneo, antes de que el agua/hidrocarburo salga del pozo. Para aquellos componentes para remover contaminantes que pueden ser regenerados, como pueden ser las resinas de intercambio iónico, una cantidad medida de una solución ácida para regeneración puede ser inyectada en el estrato fracturado para la regeneración y recuperación cuando el pozo reinicie su producción.

Term
5.9 yearsleft in the term
Expires 31 August 2032.
- Priority
- Filed
- Granted
- Today
- Expires
13 claims: 3 independent, 10 dependent
- 1REIVINDICACIONES 1. Un método para eliminar metales pesados de agua e hidrocarburos contaminados en un estrato de pozo fracturado, el método está caracterizado porque comprende:introducir en el estrato una formulación apuntalante que comprende partículas sólidas de apuntalante asociadas con un componente para eliminación de contaminantes para eliminar al menos una parte de los contaminantes de metal pesado en los fluidos contaminados, en donde el componente para eliminación de contaminantes comprende (a) un recubrimiento insoluble en las partículas de apuntalante que comprende una porción química de eliminador de contaminante con una afinidad funcional para impurezas en el estrato y que comprende al menos una porción ácido sulfónico, porción ácido carboxílico, porción fenólica, porción aminoácido, porción glicolamina, porción poliamina, porción amina cuaternaria o porción polihidroxílica, y (b) partículas secundarias que comprenden una resina de intercambio iónico o un tamiz molecular que está ligado a una superficie exterior de las partículas de apuntalante con un recubrimiento insoluble. IMPI reivindicación El método de conformidad con la 1, caracterizado además porque el segundo sólido de partículas pequeñas es un tamiz molecular natural.
- 23. El método de conformidad con la reivindicación 1, caracterizado además porque el segundo sólido de partículas pequeñas es un tamiz molecular sintético.
- 34. El método de conformidad con la reivindicación 1, caracterizado además porque el segundo sólido de partículas pequeñas es una resina de intercambio iónico.
- 45. El método de conformidad con la reivindicación 1, caracterizado además porque el componente de eliminación está dispuesto en poros de las partículas sólidas de apuntalante.
- 56. Una formulación de apuntalante útil para eliminar metales pesados de agua e hidrocarburos obtenidos/producidos de un estrato de pozo fracturado de producción de petróleo y gas, la formulación de apuntalante está caracterizada porque comprende:(a) una pluralidad de sólidos de apuntalante particulados asociados con (b) un componente para eliminación de contaminantes en para eliminar al menos una parte de contaminantes de metales pesados en agua e hidrocarburos producidos de un estrato del pozo fracturado, en donde el componente para eliminación de contaminantes comprende (a) un recubrimiento insoluble en las partículas de apuntalante que comprende una porción IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTUAL química de eliminador de contaminante con una afinidad funcional para impurezas en el estrato y que comprende al menos una porción ácido sulfónico, porción ácido carboxílico, porción fenólica, porción aminoácido, porción glicolamina, porción poliamina, porción amina cuaternaria o porción polihidroxílica, y (b) partículas secundarias que comprenden una resina de intercambio iónico, o un tamiz molecular que está ligado a una superficie exterior de las partículas de apuntalante con un recubrimiento insoluble.
- 67. La formulación de apuntalante de conformidad con la reivindicación 6, caracterizada además porque los sólidos de apuntalante particulado comprenden poros en los cuales el componente de eliminación está dispuesto en al menos una parte de éste.
- 78. La formulación de apuntalante de conformidad con la reivindicación 6, caracterizada además porque los sólidos de apuntalante particulado comprenden un recubrimiento de apuntalante insoluble.
- 89. La formulación de apuntalante de conformidad con la reivindicación 6, caracterizada además porque el componente para eliminación de contaminantes es un segundo sólido de partículas pequeñas que está ligado a una superficie exterior del apuntalante particulado con el recubrimiento. IMPI (TWTnVTO MfJUCANO DE LA MONEDAD INDUSTRIAL
- 910. La formulación de apuntalante de conformidad con la reivindicación 9, caracterizada además porque el segundo sólido de partículas pequeñas es un tamiz molecular natural.
- 1011. La formulación de apuntalante de conformidad con la reivindicación 9, caracterizada además porque el segundo sólido de partículas pequeñas es un tamiz molecular sintético.
- 1112. La formulación de apuntalante de conformidad con la reivindicación 9, caracterizada además porque el segundo sólido de partículas pequeñas es una resina de intercambio iónico.
- 1213. La formulación de apuntalante de conformidad con la reivindicación 6, caracterizada además porque el componente para eliminación de contaminantes tiene una capacidad de intercambio catiónico para eliminar metales pesados normalmente radioactivos del agua e hidrocarburos.
- 1314. Un método para eliminar metales pesados de agua e hidrocarburos contaminados en un estrato de pozo fracturado, el método está caracterizado porque comprende:introducir en un pozo un paquete de grava o partículas sólidas de lecho arenoso de filtro asociadas con un componente para eliminación de contaminantes para eliminar al menos una parte de los contaminantes de IMPI INSII lUTO DE LA PROPIEtMS industria* metales pesados en el agua e hidrocarburos contaminados, en donde el componente para eliminación de contaminantes funcional para impurezas en el estrato y que comprende al menos una porción ácido sulfónico, porción ácido carboxílico, porción fenólica, porción aminoácido, porción glicolamina, porción poliamina, porción amina cuaternaria, o porción polihidroxílica, y (b) partículas secundarias que comprenden una resina de intercambio iónico o un tamiz molecular que está ligado a una superficie exterior de las partículas de apuntalante con un recubrimiento insoluble. IMPI INSTITUTO meiucah· DS LA INDUSTRIA»
Independent claims13
382 paragraphs in 72 sections, as filed
(54) Title: DOUBLE FUNCTION SUPPORTERS.
(54) Title: DUAL FUNCTION PROPPANTS.
(57) Summary
Proppants are provided for use in fractured or rack-packed / frac-packed oil and gas wells, with a contaminant remover component to separate one or more of the contaminants found in the water / underground hydrocarbon from a production well. The water / hydrocarbon cleaning proppant solids can be used as discrete particles in a proppant formulation, as a coating on proppant solids in the pores of a porous proppant solid or as part of the internal proppant structure. The contaminant removal component separates the contaminants, especially the dissolved contaminants, from the groundwater or hydrocarbon before the water / hydrocarbon exits the well. For those components to remove contaminants that can be regenerated, such as ion exchange resins, a measured amount of an acidic regeneration solution can be injected into the fractured stratum for regeneration and recovery when the well resumes production.
(57) Abstract
Proppants for use ¡n fractured or gravel packed / frac packed oil and gas wells are provided with a contaminant removal component to remove one or more of the contaminants found ¡n subterranean water / hydrocarbon from a production well. The water / hydrocarbon cleaning proppant solids may be used as discrete partióles na proppant formulated, as a coating on proppant solids in pores of a porous proppant solid or as part of the proppant's internal structure. The contaminant removal component removes contaminants, especially dissolved contaminants, ¡n the subterranean water or hydrocarbon before the water / hydrocarbon leaves the well. For those contaminant removal components that can be regenerated, such as on exchange resins, a measured quantity of an acidic regenerated solution can be injected into the fractured stratum for regenerated and recovered when the well resumes production.
<img file="MX359509B_D0001.tif" />
IMPI i. Wlwsws 3w<sup>v</sup> ' ***
PATENT TITLE No. 359509
<td>Headlines):</td><td>PREFERRED TECHNOLOGY, LLC</td>
<td>Home:</td><td>One Radnor Corporate Center, 100 Matsonford Road, Suite 101, Radnor, Pennsylvania, 19087, USA</td>
<td>Denomination:</td><td>DOUBLE-FUNCTION PROPORTERS.</td>
Classification;
CIP: CPC:
Inventor (s):
E21B43 / 02
C0 ^ <8/64; C09K8 / 68; C09K8 / 80 ;; Q09K8 / 90; C09K8 / 536; C09K8 / 805; £ 21 ^ 43/04; E21B43 / 267
ROBERT MCDANIEL; AVIS LL $ YD tyCOHAJRY
Number:
MX / a / 2014/002156
Validity: Twenty years
<img file="MX359509B_D0002.tif" />
International:
012
Number:
13/224,726 <sub>F</sub> ’ » <
_________________j <sup>F</sup> ' ' <sup>J</sup>
Vetadmienfo Date »31 of igoltó ¿032
Expedition date; £ 8 of September ^ tri8
The reference patent is granted in full ento ^ g | tioul «H °. F fraccn ^ jX 0 ·· ϊτζα; ιόη Ift.-y 89 <fe the Law d ». the Industrial Property.
Pursuant to article 23 of the Industrial Property Law, the presyiülpáteniJ ^ n ^ pn? validity of twenty years, renewable, counted from the date of filing of the international application, it will be subject to the Augu st of the tar®B $ ai® manteher in force jos' d0réehos
The subscriber of the present tilujplo does so with a basis of β / ΐφ arranged by fosíarUcUfos ^ fra / Wcnwrtl and 7<sup>or</sup> bis 2 efe ia'Law of Industrial Property (Official Gazette of the Federarán (ÓÓ-N 27 / () 6 (, 1991, refotmapá <C®d8 / 1994, · 26/10/1996, 12/26/1997, 05/17/1989, 01/26/2004, 06/16/2005, 01/25/2006, 05/06/2009, 01/06/2010, '* ÚW * 01 (Xjá / 0MN10. 27 / (1 / 201¾ CWfi4 / & 12, ¢ 1/06/2016 ¢ 13/03/2618): articles 1 ', 3 »section V subsection a), 4<sup>or </sup>and 12 “sections I and III of the Regulations.,. deis tostjUiio Mexicano d * la Prófcná ^ ii Industrial 14/12 / 1.9 (9, amended on 07/01/2002, 07/15/2004,
07/28/2004 and 09/07/2007): articles 1 *,? *, 4 *. 5 * fraction Incido a), 16 fractions Ly-1fl y3Ó del ,, Estádúte Ordínico of the Mexican Institute of Industrial Property (DOF 12/27/1999, 'rWoffliaáó el (0/10/2002, 2W7 / 2QQ4¿W ®W04 and 09 /13/20 61) * tí, 4 “and 5 ° Clause a) of the Agreement that delegates powers to the Deputy Directors General, Copt ^^ ry ^ pctore ^ Divisionales. Titilar of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subaltOMMP ^ el JnSitutb ^ βΜ ^ ι® ΙίΊ ^^ ώίΜΙϊ '^ βΙίΝβΙ. (0.0 F. 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007). '
This letter is signed with an advanced electronic signature (FIEL), which is based on merit in articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 fraction III, 2 fraction V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.
THE DIVISIONAL DIRECTOR OF PATENTS
NAHANNY CANAL REYES
<img file="MX359509B_D0003.tif" />
Original string:
NAHANNY MARISOL CANAL REYES | 00001000000403252793 | Administration Service
Tax | 1695 || MX / 2018/83588 | MX / a / 2014/002156 | PCT Patent Title | 1223 | GAGViPage (s) | hewLLtkthRNeeu67ZHwWtt¡8KSk =
Digital stamp:
ipwM5U2FLGfvQzfYMh8ZvyVZjDyUJnk / X8TvwsV4hvtlxKDwm2Wzun / PQHsmog3JLhOf2pWdbDf1CJqUaa + RLyub6f
IWgeKqPOEwK¡HkEtmB54JROLqOj1Z / 9 / JgOEqMGxibcgxLJRwzOxq3lfo7yKxX9 / d05ye82BzXkbs5VBxSxUt7Ph3x
G2qNqRUcrgWljyoBnBsllTezHybDDWblkPvLptCmiRacc46rEeSfKey7pOsnH + / 4DgNgdCZsvMCLRdJXE9pZsQUXJJXUJJXXJJXUXJJUXJJUX
Aív'ióINo. 550. Ριϊυ i! 'Ii.O'ic Sama Manu lepepan, X * /.;!> In * ili: <>. 1f.> Ü2 ·:.: ·. <HiCIñid liü I.ÍUXIí tí> 5) í.33 hiíZOO / job rnx / impi
<img file="MX359509B_D0004.tif" />
MX / 2018/83588
35qso <?
<img file="MX359509B_D0005.tif" />
IMPI
MKICANO INSTITUTE OF U ntOHEBAJD INDUSTXUl
<img file="MX359509B_D0006.tif" />
DOUBLE-FUNCTION BRANCHES
CROSS REFERENCE TO RELATED REQUESTS
This application claims the priority benefit of US Ser. Patent Application No. 13 / 224,726 filed on September 2, 2011, the content of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The invention relates to a method of removing dissolved contaminants, especially heavy metals and naturally occurring radioactive materials (NORM), in water and hydrocarbons produced from a fractured oil or gas well, as well as the composition, production method and methods to use the proppant composition in the fracturing and production of the well.
BACKGROUND OF THE INVENTION
Hydraulic fracturing is a technique often used to increase the efficiency and productivity of oil and gas wells. Overly simplified, the process involves the introduction of a water-based or petroleum-based emulsion to fracture the fluid in the well and the use of fluid pressure to fracture and
<img file="MX359509B_D0007.tif" />
break the stratum of the well. The cracks allow oil and gas to flow more freely from the stratum, thereby increasing production rates in an efficient manner.
There are many detailed techniques involved in fracturing wells, but one of the most important is the use of a proppant solid to keep the stratum cracks open as oil, gas, water, and other fluids found in the well flow through the cracks. The proppant is carried out in the well with the fracturing fluid which may itself contain a variety of viscosity improvers, gelling agents, surfactants, etc. These additives also improve the ability of the fracturing fluid to bring the proppant to the desired depth and location of the stratum. The fracturing fluid for a particular well may or may not use the same formulation for each depth in the stratum.
The water produced during oil and gas operations constitutes the most prolific by-product in the industry. By volume, water production represents approximately 98 percent of the non-energy related fluids produced from the
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY oil and gas operations, producing approximately 14 billion barrels of water annually.
According to the American Petroleum Institute (API), more than 18 billion barrels of waste fluids are generated from oil and gas production in the United States. Such waste materials often dissolve in groundwater with a ratio of water to oil produced of about 10 barrels of water produced per barrel of oil. This contaminated water can include ionic contaminants that include salt, hydrocarbons, heavy metals (eg. , zinc, lead, manganese, boron, copper, mercury, chromium, arsenic, strontium, and aluminum), corrosive acids or bases of dissolved sulfides and sulfates, scale (eg insoluble barium, calcium and strontium compounds), radionuclides of natural origin (p. (eg uranium, thorium, cadmium, radium, lead 210 and their disintegration products) often referred to as Naturally Radioactive Materials (NORMS), sludges (oily, loose material, often containing silica and barium compounds) and dissolved radon gas. In general, the produced waters are re-injected into deep wells or discharged to non-potable coastal waters.
IMPI
<img file="MX359509B_D0008.tif" />
Excluding transportation costs, the discharge of wastewater can cost as much as $ 2 per barrel. Such costs must be taken into account in the global economy of a gas field.
NORMS contaminants are a topic of particular concern. Oil and gas NORM is created in the production process, when fluids are produced from deposits that carry sulfates to the surface of the Earth's crust. Barium, calcium, and strontium are larger compounds, and smaller atoms, such as Radio 226 and Radio 228, can fit into the void spaces of the compound and be carried through the fluids produced. As fluids get closer to the surface, changes in temperature and pressure cause Barium, Calcium, Strontium, and Radio sulfates to precipitate out of the solution and form scale on the inside, or sometimes on the outside, of the chain and / or termination covers. The use of the tubular pipe termination string in the production process that are contaminated with NORM does not cause a health hazard if the fouling is within the tubular chain and the tubular chain remains at the bottom of the wellbore. The improved concentrations of radio 226 and 228 and the degradation products (such as
<img file="MX359509B_D0009.tif" />
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX359509B_D0010.tif" />
Lead 210) can also occur in sludge that accumulates in oilfield wells, tanks, and lagoons. Radon gas in natural gas streams is also concentrated as NORM in processing activities. Radon decays to lead 210, then to Bismuth 210, Polonium 210, and stabilizes with Lead 206. Radon decay elements are produced as a glossy film on the inner surface of inlet, unit treatment, pump and valve lines associated with propylene, ethane and propane processing systems.
Contaminated water produced from a well must be reused or treated to remove contaminants, especially heavy metals. Oil wells are not, however, normally located adjacent to substantial water treatment facilities. Contaminated water must be captured and transported to treatment facilities or portable facilities must be taken to the well. Exemplary systems include activated carbon packed beds for removal of organic compounds, permanent or portable ion exchange columns, electrodialysis and similar forms of membrane separation, freeze / thaw separation, and flash evaporation.
IMPI /
INSTITUTO MEXICANO V rjf LA PHOrlEDAO t industrial spraying, and combinations of these. All of these options are relatively expensive with the volumes of water produced from a production well.
Some type of on-site treatment could potentially be very helpful in supplementing or, in some cases, replacing surface-based purification treatments. Intentionally, it would be desirable if a propping composition passing in the fractured well bed could provide a crack propping function as well as an ability to remove at least some portion of the ionic and dissolved contaminants before they were produced at the surface.
A publication that suggests the use of a dual function proppant is Tanguay et al. WO 2010/049467. The proppant described in this published application has a polycarbodiimide or polyurethane coating that optionally contains organic compounds, microorganisms, and petroleum processing catalysts. As the coating dissolves over a 4 hour period, the compounds, microorganisms, or catalysts are slowly released into the crude oil.
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
US Patent No. 6,528,157 describes a coated proppant that includes a fibrous material that extends out of the proppant coating. This diffuse proppant is said to be useful to act as a physical screen or physical screen to prevent backflow of sand, proppants, or other particles from the fractured stratum. The fibers can be any of the commercially available short fiber types such as ground glass fibers, ground ceramic fibers, ground carbon fibers, and synthetic fibers that have a softening point above the typical temperature of the coating sand. , p. eg, at least about 200 ° F so as not to degrade, soften or agglomerate.
US Patent No. 7,754,659 teaches the addition of magnetic particles to the exterior of a proppant substrate for the purpose of improving the resistance to return of the coated proppant flow from the fractured underground layer.
BRIEF DESCRIPTION OF THE INVENTION
It would be desirable to have a proppant that could act as a proppant as well as perform filtration, cleaning, or otherwise remove
IMPI
MEXICAN INITIMATE OF INDUSTRIAL rtOPIWMÍD
<img file="MX359509B_D0011.tif" />
water contaminants found within a well, especially a well to produce oil and / or gas.
It would be desirable to have a bottom-hole system in place to remove dissolved contaminants, especially dissolved forms of heavy metals and NORM, deep in an oil or gas well that is effective but does not materially increase costs or change costs. wellhead procedures.
These and other objects of the invention that will become apparent from the description herein can be accomplished by a solid proppant associated with a contaminant removing component that will remove, sequester, chelate, or otherwise clean at least one contaminant, especially forms dissolved or otherwise ionic heavy metals and naturally occurring radioactive materials (NORMS), from groundwater or hydrocarbon deposits within a fractured stratum while also underpinning open cracks in that fractured stratum. Preferably, the contaminant removal component is associated with the solid proppant as a chemically distinct solid that is introduced together with the
IMPI
INSTITUTO MEXICANO DE LA F1OHEDAD INDUSTRIAL solid proppant as an insoluble solid secured to the outer surface of the solid proppant with a coating formulation that binds the solids together, as a solid lodged within the pores of the solid proppant or as a compound or chemical portion that mixes in or integrates with a coating or solid proppant structure.
Dual function proppants according to the invention provide good conductivity in an oil or gas production well while also removing at least some of the contaminated water and hydrocarbons at the bottom of the hole. Such water cleaning functions increase the proppant value by reducing the costs and / or treatment times needed to further clean the aqueous materials that are discharged from an oil or gas production well.
DETAILED DESCRIPTION OF THE INVENTION
The proppant of the present invention includes a proppant formulation containing a contaminant removal component associated with proppant particles. The association type encompasses various physical combinations of proppant particles and the
IMPI
INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL component for the removal of contaminants, such as (a) unified proppant particles in which the component for the elimination of contaminants has been integrated into the structure of the proppant particles as a compound or chemical portion, a liquid adsorbed or finely divided solids arranged in pores within the proppant particles, or adhered to the exterior of the proppant particles with a water-insoluble binder coating; or (b) a physical combination or mixture of proppant particles and non-proppant particles.
The best choice will depend largely on the well, the fractured stratum and the nature of the contaminants to be removed from the produced fluids.
It will be understood that the contaminant removal component described herein for use with a solid proppant can also be used in the same way with other solids that are employed in well operations. Examples of such other solids include gravel packs and sand filters of those used at the well terminations. The gravel pack operation includes a sand transport in the space between the screen and the carcass, and in the drilling tunnels. The sand is sized to prevent
IMPI
MUICANO INSTITUTE OF INDUSTRIAL PROPERTY that fine or fine particles of the specific formation pass through the package (normally 20-40 mesh or 30-50 mesh or 40-60 mesh). The sand is deposited in the annular space behind the screen and then packed to create a filter to stop fine particulate matter or fines from migrating to the hole in the well. The screen openings are also sized to act as a final filter for any of the fines that migrate through the sand bed. The pollutant removal particles of the present invention can easily be physically mixed with a gravel pack or filter or adhered to sand particles by means of a binder coating on the gravel or filter sand pack. The removal of additional contaminants such as water and hydrocarbons emitted from the fractured layer will be carried out.
The contaminant removal component (s) can remove contaminants by any chemical, physical, or biological method that is effective in removing the contaminant from the groundwater associated with a fractured well. The contaminant removal component in the propping formulation of the invention will generally have a
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY functional affinity for impurities in the water / hydrocarbon phase that passes through the fracture. Exemplary methods include ion attraction, ion exchange, sequestration, amalgamation, chelation, physical entrapment, absorption, adsorption, magnetic attraction, and adhesion. The specific removal method that is most advantageous for a specific well depends on the nature and identities of water contaminants that are produced from a specific well. Preferred types of contaminating components include ion exchange removal resins, zeolites and chemical compounds.
Ion exchange resins
Synthetic ion exchange resins consist essentially of a network of crosslinked polymer to which ionized or ionizable groups are attached. In the case of cation exchange resins, these groups are acidic groups (eg, -SO3H, -PO3H2, -CO2M, and phenolic hydroxyl) while in anion exchange resins the groups are basic (eg. eg, quaternary ammonium, aliphatic or aromatic amine groups). In ion exchange resin synthesis, ionizable and contaminant removal functional groups can be attached to
IMPI
<img file="MX359509B_D0012.tif" />
monomers or intermediates used in the preparation of the crosslinked polymer, or these can be subsequently introduced into a preformed polymer.
Cation exchange resins are prepared by sulfonation of styrene divinylbenzene copolymers as described in US Patent No.
2,366,007. Many strongly basic ion exchange resins are prepared by treating crosslinked polystyrene with chloromethyl ether in the presence of a Friedel-Crafts catalyst. The chloromethylated product is then treated with a tertiary amine, e.g. eg, trimethylamine, to give a resin containing strongly basic quaternary ammonium groups. Crosslinked polystyrene is generally a copolymer with up to about
10% divinylbenzene.
Ion exchange resins suitable for the present invention are generally classified as strong acid cation exchange resins, weak acid cation exchange resins, acid base anion exchange resins, and weak base anion exchange resins.
IMPI
<img file="MX359509B_D0013.tif" />
Ion exchange resins can be physically mixed with solid proppants generally within the range of weight ratios of from about 1000: 1 to about 1: 1000 of exchange resin to the proppant. The specific weight ratio will depend on the relative densities of these materials, the carrying capacity of the resin and the contaminants found at the bottom of the well. In general, ion exchange resins within the range of about 10-60 mesh (250-2000 pm) are suitable for physical mixtures with solid proppants. Otherwise, the exchange resin solids may be disposed within the pore openings or bonded to the solid proppant with an outer coating, adhesive, or binder that resists dissolution under downhole conditions. Ion exchange resins within the range of about 10-400 mesh (38-2000 pm) are generally suitable for such combinations, even smaller sizes can be used to meet the small pore requirements within the proppant particles.
Ion exchange resins are prone to depletion as they are used to collect
<img file="MX359509B_D0014.tif" />
IMPI pollutants. These resins can be regenerated in situ by injecting an acidic solution into the fractured layer containing the exchange resin. After an adequate recharge period, discharge water that is loaded with discharge flushed contaminants is recovered as well production resumes. See US Patent No. 7,896,080, the disclosure of which is incorporated herein by reference.
Molecular sieves and Zeolites
The composition of zeolites is similar to clay or clay minerals. More specifically, they are both alumino-silicates. These differ, however, in their crystal structure. Many clays have a layered crystal structure (similar to a deck of cards) and undergo shrinkage and swelling when water is absorbed and removed between the layers. In contrast, zeolites have a rigid three-dimensional (honeycomb-like) crystal structure consisting of a network of interconnected tunnels and cages. Water moves freely in and out of these pores but the zeolite framework remains rigid. Another special aspect of this structure is that the pore and channel sizes are almost uniform, allowing the crystal to act as a molecular sieve. Porous zeolite is a host
<img file="MX359509B_D0015.tif" />
for water molecules and potassium and calcium ions, as well as a variety of other positively charged ions, but only those of appropriate molecular size are allowed to fit in the pores creating the sieving property.
An important property of zeolite is the ability to exchange cations.
This is the exchange of one charged ion for another in the crystal.
A measure of this property is the cation exchange capacity. Zeolites have high cation exchange capabilities, which arise during zeolite formation from the substitution of an aluminum ion for a silicon ion in a portion of tetrahedral units that make up the zeolite crystal. See the
US patents
Nos. 2,653,089; 5,911,876; 7,326,346;
7,884,043 and US Published Patent Application No.
2004/010267 and 2005/018193. Other molecular sieves and adsorbents that have been synthesized appear to work well with NORMS-type contaminants. See Patent
US No. 7,332,089 and 7,537,702. The descriptions of each of these references are incorporated herein by reference.
IMPIfé
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY **
Molecular sieves and zeolites suitable for use in the present invention include pretreated or untreated natural and synthetic molecular sieves with pore size and exchange characteristics suitable for the contaminant to be removed, e.g. ex. , heavy metals. Examples of such zeolites include aluminosilicates such as clinoptilolite, clinoptilolite modified according to US Patent No. 7074257, vermiculite, montmorillonite, bentonite, chabazite, heulandite, stilbite, natrolite, analcime, philipsite, permatite, hydrotalcite, zeolites A, X and Y; antimony silicates; silicotitanates; and sodium titanates.
Chemical substances
Porous proppant particles can be impregnated with one or more chemical compounds that have an affinity for binding with the contaminants chosen for removal. Examples of chemical compounds with an affinity for different contaminants include sulfonic acids, carboxylic acids, phenolics, amino acids, glycollamines, polyamines, quaternary amines, polyhydroxy compounds, combinations of these.
This functionality should be primarily available on the surface of the coated particles to improve contact with the
IMPI
MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL ionic pollutant species and solution removal.
Other components for the removal of contaminants
In addition to the above, the water and hydrocarbon contaminants found in a fractured layer may include activated carbon, adsorbent solids, non-molecular sieves with an affinity for heavy metals, and reactive materials that will form insoluble complexes or amalgams with the chosen metal ionic contaminant species. .
Solid props
Solid proppants can be virtually any small or porous solid with adequate crush resistance and lack of chemical reactivity. Suitable examples include sand, ceramic particles (such as aluminum oxide, silicon dioxide, titanium dioxide, zinc oxide, zirconium dioxide, cerium dioxide, manganese dioxide, iron oxide, calcium oxide, or bauxite) that It may or may not incorporate the contaminant removal component as an integral component of the ceramic matrix or framework, or other granular materials as well. Shoring materials that have been widely used include:
IMPI
<img file="MX359509B_D0016.tif" />
(1) sintered ceramic particles, typically aluminum oxide, silica, or bauxite, often with clay-type binders or other additives to increase the compressive strength of the particles, especially sintered bauxite; (2) relatively coarse natural sand, the particles of which are almost spherical, generally called frac sand; (3) resin coated particles of these materials and (4) composite particles or composite particles containing a solid or porous solid core in which the contaminant removal agent is an integrated part of the solid core or is dispersed within the pores of the porous solid core. The proppants to be coated will preferably have an average particle size within the range of from about 50 μιη to about 3000 μπι, and more preferably within the range from about 100 μιη to about 2 000 μιη.
The proppant must have a distribution of particles ranging in size from about 4 meshes to about 100 meshes (US Standard Sieve Numbers), that is, the particles pass through a sieve opening of about 4760 microns ( mesh 4) and are held at τ
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX359509B_D0017.tif" />
a sieve opening of approximately 150 microns (100 mesh). Preferred proppants have a particle size distribution in which 90% is within the 8 mesh to 100 mesh range, and more typically in the 16 mesh to 70 mesh range. Particularly preferred proppants have a particle size distribution with at least 90% by weight of the particles having a size within a desired range, such as the 20 mesh to 40 mesh range, i.e. between about 850 and approximately 425 microns.
Covering
A coating can be used to provide exposed surface portions of the aforementioned types that have an affinity for removing contaminants, or the coating can be used as an insoluble binder to secure or adhere a component for removing particulate contaminants to the external surface of the proppant solid. The coatings can be cured, partially cured, or uncured and are intended to secure the contaminant removal component to the solid proppant. Which of these ways is more desirable for a particular well will depend on the
IMPI
<img file="MX359509B_D0018.tif" />
coating, its dissolution characteristics in the downhole environment and the nature of the cleaning component.
The coatings used to bind the contaminant removal agent and the solid proppant can utilize virtually any coating formulation but will preferably utilize previously used coating formulations to help consolidate or improve the proppant strength within the fractured layer and resist washing. Thermoset and thermoplastic resins are common.
Hot melt adhesives have been proposed for use based on a theory of operation that the coating on the proppant would have latent tack, i.e. the tack of the coating will not develop until the proppant is placed in the carrier formation of hydrocarbons. Within the hole-bottom environment, underground heat causes the adhesive to become tacky so that aggregation occurs when the coating softens to cause the tacky adhesive thermoplastic to produce stable agglomerates within the fractured underground formation.
<img file="MX359509B_D0019.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL FHOBÍDAD
Covered proppants come in three types: precured, partially cured, and curable. Pre-cured resin-coated proppants contain a resin-coated substrate that has been highly crosslinked. The resin coating of the precured props provides crush resistance to the substrate. Since the resin coating is already cured prior to its introduction into the well, even under high pressure and temperature conditions, the non-agglomerating proppant is capable of generating considerable resistance to particle-to-particle bonding. Such pre-cured resin-coated proppants are normally maintained in the fracture by the stress surrounding them. The resin coating of a partially cured proppant has undergone a partial reaction during the manufacturing process but retains a significant level of curability. The resin coating of a curable proppant is not significantly crosslinked or cured prior to injection into the oil or gas well. The partially cured and curable coatings are designed to crosslink under stress and temperature conditions in the wellbore formation. This causes the proppant particles to bond between
<img file="MX359509B_D0020.tif" />
IMPI itself forming a three-dimensional matrix and preventing the return of proppant flow.
Suitable coatings include 0.1-10% by weight of a cured, partially cured, or curable organic polymer, prepolymer and oligomer of the Resole or Novolac type. Specific chemical compositions of such organic coatings can be chosen from a wide selection, including epoxy, phenolic, polyurethane, polycarbodiimide, furan resins, and combinations of these with each other. The phenolic resins of the aforementioned Novolac and Resole polymers can be phenol moieties or bis-phenol moieties. Novolac resins are preferred. Specific thermoplastics include polyethylene, styrene-acrylonitrile-butadiene, polystyrene, polyvinyl chloride, fluoroplastics, polysulfide, polypropylene, styrene acrylonitrile, nylon, and phenylene oxide. Specific thermosetting resins include epoxy, phenolic, e.g. ex. , Resol (a true thermosetting resin) or Novolac (thermoplastic resin that becomes thermosetting with a hardening agent), polyester resin, polyurethanes and derivatives thereof, and an epoxy-modified Novolac resin. The phenolic resin contains any of the following: a phenolic Novolac polymer; a polymer
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL P »OMEDAD
Phenolic resol; a combination of a phenolic Novolac polymer and a phenolic Resol polymer; a cured phenolic / furan resin combination or a furan resin to form a pre-cured resin.
A preferred proppant coating for use in the present invention includes a substantially homogeneous mixture containing: (a) an isocyanate reagent, (b) a polyol reagent that may or may not have the reactive amine functionality, (c) as an option, an amine reagent that is different from the polyol reagent, and (d) as an option, an amine based latent curing agent. A typical proppant resin is a phenolic Novolac resin coating composition combined with hexamethylenediaminetetramine (HEXA), formaldehyde, paraformaldehyde, oxazolidines, phenol-aldehyde resol polymers and / or other known curing agents as a crosslinking agent to achieve a proppant precured or curable.
The coating process of the present invention applies one or more layers of considerably cured polyurethane around a solid proppant core. The coating cures and reticulates to the point that it can resist dissolution under a rigorous combination of
IMPI
MEXICAN INSTITUTE OF THE "AGE INDUSTRY!
high heat, agitation, abrasion and the water at the bottom of a well. Preferably, the considerably cured coating exhibits sufficient resistance to a 10-day autoclave test or 10-day conductivity test such that the coating resists loss by dissolution in hot water (LOI loss) of less than 25% by weight, more preferably less than 15% by weight, and even more preferably a loss of less than 5% by weight. The considerably cured coating of the invention thus resists dissolution in the fractured stratum while also exhibiting sufficient resistance to flow return and sufficiently high resistance to grinding to maintain fracture conductivity.
A preferred test method is described in ISO 13503-5: 2006 (E) Procedures for measuring the long term conductivity of proppants, the disclosure of which is incorporated herein by reference. ISO 135035: 2006 provides standard test procedures for evaluating proppants used in hydraulic fracturing and gravel pack operations. ISO 135035: 2006 provides a consistent methodology for tests performed on hydraulic fracturing and / or
<img file="MX359509B_D0021.tif" />
IMPI
INSTTTU ΓΟ MEXICANO DE LA HUyiEDAD INDUSTRIAL
<img file="MX359509B_D0022.tif" />
proppants of gravel packages. The proppants mentioned hereinafter in this part of ISO 13503-5: 2006 refer to sand, ceramic media, resin-coated proppants, gravel pack media, and other materials used for hydraulic fracturing and pack pack operations. gravel. ISO 135035: 2006 is not relevant for use in obtaining absolute proppant packing conductivity values under downhole conditions, but serves as a consistent method by which such downhole conditions can be simulated and performed proppant properties compared to laboratory settings.
The isocyanate component comprises an isocyanate with at least 2 reactive isocyanate groups. Other isocyanate containing compounds can be used, if desired. Examples of suitable isocyanates with at least 2 isocyanate groups, an aliphatic isocyanate, or an aromatic one with at least 2 isocyanate groups (eg, a diisocyanate, triisocyanate, or tetraisocyanate), or an oligomer or a polymer thereof can preferably be used. . These isocyanates with at least 2 isocyanate groups can also be carbocyclic
YOU
IMPIAS,
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY -heterocyclic and / or contain one or more heterocyclic groups.
Isocyanate with at least isocyanate groups is
<img file="MX359509B_D0023.tif" />
preferably a compound of the formula (III) or a compound of the formula (IV):
<img file="MX359509B_D0024.tif" />
(IV)
In formulas (III) and (IV), A is each, independently, an aryl, heteroaryl, cycloalkyl, or heterocycloalkyl . Preferably A is each independently an aryl or cycloalkyl. More preferably A is each, independently, an aryl which is preferably phenyl, naphthyl or
IMPI
<img file="MX359509B_D0025.tif" />
anthracenyl, and more preferably phenyl. Still more preferably A is a phenyl.
The aforementioned heteroaryl is preferably a heteroaryl with 5 or 6 ring atoms, of which 1, 2 or 3 ring atoms are each, independently, an oxygen, sulfur or nitrogen atom and the other ring atoms they are carbon atoms. More preferably heteroaryl is selected from pyridinyl, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl, or furazanil.
The aforementioned cycloalkyl is preferably a C cycloalkyl<sub>3</sub>-i<sub>0</sub>, more preferably a C5-7 cycloalkyl.
The aforementioned heterocycloalkyl is preferably a heterocycloalkyl with 3 to 10 ring atoms (more preferably with 5 to 7 ring atoms), of which one or more (eg, 1, 2 or 3) atoms in the ring are each, independently, an oxygen, sulfur or nitrogen atom and the other atoms in the ring are carbon atoms. More preferably the heterocycloalkyl is selected from
<img file="MX359509B_D0026.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX359509B_D0027.tif" />
tetrahydrofuranyl, piperidinyl, piperazinyl, aziridinyl, acetidinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydrothienyl, octahydroquinolinyl, octahydroisoquinolinyl, oxazolidinyl isoxazolidinyl.
Still more preferably, the heterocycloalkyl is selected from tetrahydrofuranyl, piperidinyl, piperazinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazolidinyl, tetrahydro thienyl, oxazolidinyl isoxazolidinyl.
In formulas (III) and (IV), each R<sup>1</sup> it is, independently, a covalent bond or Ci_4alkylene (eg methylene, ethylene, propylene or butylene).
In formulas (III) and (IV), each R<sup>2</sup> is each, independently, a halogen (eg, F, Cl, Br, or I), an alkyl of Ci_<sub>4</sub> (eg, methyl, ethyl, propyl, or butyl) or C1-4 alkoxy (eg, methoxy, ethoxy, propoxy, or butoxy). Preferably, each R<sup>2</sup> it is independently C1-4alkyl. More preferably each R<sup>2</sup> it is methyl.
In formula (IV), R<sup>3</sup> is a covalent bond, a C1-4 alkylene (eg, methylene, ethylene, propylene, or butylene) or a group - (CH<sub>2</sub>) R31-O- (CH<sub>2</sub>) R32-, where R31 and
IMPI
<img file="MX359509B_D0028.tif" />
R32 are each, independently, 0, 1, 2 or 3. Preferably R<sup>3</sup> is a group -CH<sub>2</sub>- or a group -0-.
In formula (III), p is equal to 2, 3 or 4, preferably 2 or 3, more preferably 2.
In formulas (III) and (IV), each q is, independently, an integer from 0 to 3, preferably 0, 1 or 2. When q is equal to 0, the corresponding group A has no substituent R<sup>2</sup>, but it has hydrogen atoms instead of R<sup>2</sup>.
In formula (IV), each rys are independently 0, 1, 2, 3 or 4, where the sum of rys is equal to 2, 3 or 4. Preferably, each rys are independently 0, 1 or 2, where the sum of r and s equals 2. More preferably, r equals 1 and s equals 1.
Examples of isocyanate with at least 2 isocyanate groups are: toluol-2,4-diisocyanate; toluol-2,6-diisocyanate; 1,5-naphthalindiisocyanate; cumol-2,4-diisocyanate; 4-methoxy-l, 3-phenyldiisocyanate; 4-chlorine-
1,3-phenyldiisocyanate; diphenylmethane-4,4-diisocyanate; diphenylmethane-2,4-diisocyanate; diphenylmethane-2,2IMPI
MEXICAN INSTITUTE OF PROPERTY 1NDUSTWA1 diisocyanate; 4-bromo-l, 3-phenyldiisocyanate; 4-ethoxy-
1,3-phenyl-diisocyanate; 2,4'-diisocyanate diphenyl ether;
5,6-dimethyl-l, 3-phenyl-diisocyanate; 2,4-dimethyl-l, 3-phenyldiisocyanate; 4,4-diisocyanate-diphenyl ether; 4,6dimethyl-1,3-phenyldiisocyanate; 9,10-anthracendiisocyanate; 2,4,6-toluol triisocyanate; 2,4,4'triisocyanododiphenyl ether; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,10decamethylene diisocyanate; 1,3-cyclohexylene diisocyanate; 4,4'-methylene-bis- (cyclohexyl isocyanate); xylol diisocyanate; l-isocyanate-3-methyl-isocyanate3,5,5-trimethylcyclohexane (isophorone diisocyanate); 13-bis (isocyanate-l-methylethyl) benzole (m-TMXDI); 1,4bis (isocyanate-l-methylethyl) benzole (p-TMXDl); oligomers or polymers of the aforementioned isocyanate compounds; or mixtures of two or more of the aforementioned isocyanate compounds or oligomers or polymers thereof.
Particularly preferred isocyanates with at least 2 isocyanate groups are toluol diisocyanate, diphenylmethane diisocyanate, a oligomer based on toluol diisocyanate, or an oligomer based on diphenylmethane diisocyanate.
<img file="MX359509B_D0029.tif" />
IMPI
A polyol component can be added to the coating formulation. The polyol component may or may not have reactive amine functionality. An especially preferred polyurethane coating is a phenolic polyurethane made with a phenolic polyol according to a patent application which was filed with no. German Patent Office DE 10 2010 051 817.4 on November 19, 2010 and entitled Proppant Coating Technology, the disclosure of which is incorporated herein by reference and summarized below in the context of the process of the present invention.
Another preferred polyol component for the present process contains a phenol resin comprising a condensation product of a phenol and an aldehyde, such as formaldehyde. The phenol resin is preferably a Resol or Novolac phenol resin and more preferably a benzyl ether resin.
The resol type phenol resin can be obtained, for example, by condensing phenol or one or more compounds of the following formula (I), with aldehydes, preferably formaldehyde, under basic conditions.
MEXICAN INSTITUTE OF THE MLOFIEDAÜ industrial
<img file="MX359509B_D0030.tif" />
(I)
In formula (I):
R is in each case, independently, a hydrogen atom, a halogen atom, Ci-i alkyl<sub>6 </sub>(preferably C1-12 alkyl, more preferably Ci- alkyl<sub>6</sub>, and even more preferably methyl, ethyl, propyl or butyl) or -OH;
p is an integer from 0 to 4, preferably 0, 1, 2 or 3, or more preferably 1 or 2. Those skilled in the art will understand that when p is 0, the compound of formula (I) is phenol.
The Novolac-type phenol resin for the present invention contains the condensation product of phenol or of one or more compounds of formula (I) defined above, with aldehydes, preferably formaldehyde, under acidic conditions.
IMPI
<img file="MX359509B_D0031.tif" />
In another preferred embodiment, the phenol resin is a benzyl ether resin of the general formula (II):
<img file="MX359509B_D0032.tif" />
In formula (II):
A, B and D are each, independently, a hydrogen atom, a halogen atom, a hydrocarbon residue of Ci_i<sub>6</sub>, - (Ci-i6 alkylene) -OH, -OH, a -0- (Ci_i hydrocarbon residue<sub>6</sub>), phenyl, - (Ci-6 alkylene) -phenyl, or - (Οχ-δ alkylene) -phenylene-OH;
The halogen atom is F, Cl, Br or I;
The hydrocarbon residue of Ci-i6 is preferably Ci-6 alkyl, C alkenyl<sub>2</sub>-6, C-alkynyl<sub>2</sub>-6, more preferably C1-12 alkyl, C2-12 alkenyl or C alkynyl<sub>2</sub>-i<sub>2</sub>, even more preferably alkyl of
Ci_6, C alkenyl<sub>2</sub>-6 or C-alkynyl<sub>2</sub>-6, and even more preferably C1-4 alkyl, C alkenyl<sub>2</sub>-4 o
IMPI
<img file="MX359509B_D0033.tif" />
C alkynyl<sub>2</sub>-<sub>4</sub>, and still more preferably C1-C12 alkyl, and still more preferably Ci-β alkyl, and still more preferably methyl, ethyl, propyl or butyl, and more preferably methyl;
<td>The residue</td><td>- (alkylene</td><td>of Οχ-χβ) —OH</td><td>is</td>
<td>preferably</td><td>- (alkylene of</td><td>Ci_i<sub>2</sub>) -OH,</td><td>plus</td>
<td>preferably</td><td>(C1-6 alkylene)</td><td>-OH, and still</td><td>plus</td>
<td>preferably</td><td>- (alkylene of</td><td>Ci_<sub>4</sub>) -OH, and</td><td>plus</td>
preferably a methyl group (-CH<sub>2</sub>-OH);
The residue -0- (Ci_i hydrocarbon<sub>6</sub>) is preferably Ci_6 alkoxy, more preferably C1-12 alkoxy, and still more preferably C1-6 alkoxy, and still more preferably C1-4 alkoxy, and still more preferably -O-CH3, -O-CH2CH3, - O- (CH<sub>2</sub>) 2CH<sub>3 </sub>or -0- (CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub>;
The residue - (Ci-6 alkylene) -phenyl is preferably - (C1-4 alkylene) -phenyl, and more preferably -CH<sub>2</sub>-phenyl;
The residue - (alkylene of Ci-<sub>6</sub>) -phenylene-OH is preferably - (C1-4alkylene) -phenylene-OH, and more preferably -CH<sub>2</sub>-phenylene-OH;
IMPI
<img file="MX359509B_D0034.tif" />
R is a hydrogen atom of a hydrocarbon residue of Ci_<sub>6</sub> (eg, Ci_alkyl<sub>6</sub> linear or branched). R is particularly preferred as a hydrogen atom. This is the case, for example, when formaldehyde is used as the aldehyde component in a condensation reaction with phenols to produce the benzyl ether resin of formula (II);
m<sup>1</sup> ym<sup>2</sup> they are each, independently, 0 or 1.
n is an integer from 0 to 100, preferably an integer from 1 to 50, more preferably from 2 to 10, and even more preferably from 2 to 5; and where the sum of n, m<sup>1</sup> ym<sup>2</sup> is at least 2.
In yet another embodiment, the polyol component is a phenol resin with cardol and / or cardanol based monomer units. Cardol and cardanol are produced from cashew nut oil which is obtained from the seeds of the cashew nut tree. Cashew nut oil consists of approximately 90% anacardic acid and approximately 10% cardol. By heat treatment in an acidic environment, a mixture of cardol and cardanol is obtained by decarboxylating the
IMPI
MEXICAN INSTITUTE
DELA MOPfEDAD
INDUTnUAL
<img file="MX359509B_D0035.tif" />
anacardic acid. Cardol and cardanol have the structures shown below:
<img file="MX359509B_D0036.tif" />
^5<sup>Η</sup>31_η n = 0.2,4.6
Oh
<img file="MX359509B_D0037.tif" />
°15<sup>Η</sup>3ί, η
0=0.2/1.6
Cardanol
Cartfol
As shown in the illustration above, the hydrocarbon residue (-Ci<sub>5</sub>H3i_<sub>n</sub>) in cardol and / or in cardanol can have one (n-2), two (n-4) or three (n = 6) double bonds. Cardol specifically refers to the compound CAS-No. 57486-25-6 and cardanol specifically to compound CAS-No. 37330-39-5.
Cardol and cardanol can each be used alone or in any particular mixing ratio in the phenol resin. You can also use decarboxylated cashew nut oil.
Cardol and / or cardanol may be condensed in the phenol resins described above, for example in phenol resins of the Resol or Novolac type. For this purpose, cardol and / or cardanol may be condensed
<img file="MX359509B_D0038.tif" />
IMPI
p. For example, with phenol or with one or more of the above defined compounds of formula (I), and also with aldehydes, preferably formaldehyde.
The amount of cardol and / or cardanol that condenses on the phenol resin is not particularly restricted and is preferably from about 1% by weight to about 99% by weight, more preferably from about 5% by weight to about 60% by weight , and even more preferably about 10% by weight to about 30% by weight, relative to 100% by weight of the amount of phenolic starter products used in the phenol resin.
In another embodiment, the polyol component is a phenol resin obtained by condensation of cardol and / or cardanol with aldehydes, preferably formaldehyde.
A phenol resin containing cardol and / or cardanol based monomer units as already described, or which can be obtained by condensation of cardol and / or cardanol with aldehydes, has a particularly low viscosity and can thus preferably be used with low or no addition of reactive diluents. Furthermore, this
<img file="MX359509B_D0039.tif" />
IMPI type of long chain substituted phenol resin is comparatively hydrophobic, which results in a favorable useful life of the coated proppants obtained by the method according to the present invention. Furthermore, such a phenol resin is also advantageous because cardol and cardanol are renewable raw materials.
In addition to the phenol resin, the polyol component may still contain other hydroxyl group-containing compounds. The other hydroxyl group-containing compounds can be selected from the hydroxyl-containing compounds which are known to be useful for preparing polyurethanes, e.g. eg, hydroxy-functional polyethers, hydroxy-functional polyesters, alcohols or glycols. A preferred hydroxyl group-containing compound is, for example, castor oil. Compounds containing hydroxyl groups such as alcohols or glycols, in particular cardol and / or cardanol, can be used as reactive diluents.
The amount of other hydroxyl group-containing compounds depends on the desired properties of the proppant coating and can be suitably selected by the person skilled in the art. The
<img file="MX359509B_D0040.tif" />
IMPI typical amounts of hydroxyl group-containing compounds are in the range of from about 10% by weight to about 80% by weight, preferably from about 20% by weight to about 70% by weight, relative to 100% by weight of the polyol component .
The process of the present invention is particularly useful when proppants are coated with a condensation reaction product that has been made with an excess of isocyanate component over polyol component. In step (a) therefore, 1 part by weight of the polyol component is used in an amount within the range of from about 100% by weight to about 10,000% by weight, preferably about 105% by weight to about 5,000% in weight, more preferably about 120% by weight to about 3000% by weight, and still more preferably about 130% by weight up to about 1000% by weight, of the isocyanate base value.
The isocyanate base value defines the amount of the isocyanate component that is equivalent to 100 parts by weight of the polyol component. The NCO content (%) of
<img file="MX359509B_D0041.tif" />
IMPI isocyanate component is defined herein in accordance with DIN ISO 53185. To determine the OH content (%) of the polyol component, first the so-called OH number is determined in mg KOH / g according to DIN ISO 53240 and this value It is divided by 33, in order to determine the OH content.
Furthermore, in step (a) one or more additives can be mixed with the apuntálente, the polyol component and the isocyanate component. These additives are not particularly restricted and can be selected from the known additives in the specific field of coated proppants. Provided that one of these additives has hydroxyl groups, it should be considered as a different hydroxyl group-containing compound, as already described in connection with the polyol component. If one of the additives has isocyanate groups, it should be considered as a different isocyanate group-containing compound. Additives with hydroxyl groups and isocyanate groups can be considered simultaneously as different hydroxyl group containing compounds and as different isocyanate group containing compounds.
Bonding functionality provided by the cleaning property may require an additive that is
IMPI
MEXICAN INSTITUTE AND INDUSTRIAL PROPERTY
<img file="MX359509B_D0042.tif" />
(a) reactive with the isocyanate or (b) reactive with the polyol, or (c) reactive with the curing agent to be used. Thus, additives (or combinations of additives) such as ethanolamines, amino acids, phenolsulfonic acids, salicylates and quaternary ammonium compounds can be introduced into the proppant as an additive in the coating process whereby the component for removal with water cleaning functionality it is incorporated directly into the proppant lining.
It may also be possible to incorporate the component for removal as an additive that already has the ability to clean water / hydrocarbon, where the coating on the proppant works to stick the additive to the proppant surface, allowing double action of the proppant and action water / hydrocarbon cleaner. Examples of this type would be a finely powdered form of commercial water treatment resins, such as anion exchange resins, cation exchange resins, and / or chelating ion exchange resins.
Otherwise, a physical mixture of coated or uncoated proppant particles and beads of
IMPI
MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL ion exchange resin can be used in the fracturing process as a means to introduce the combination of proppants and the required water / hydrocarbon cleaning activity. This physical mixture could be consolidated in the fracture to immobilize the ion exchange resin beads, thereby creating a cleaning capacity for the passage of fluids through the package within the fracture.
A preferred propping product could be a mixture of solid proppants of different composition and / or propping properties. For example, some proppants would be formulated to remove one type of contaminant while other solid proppants in the mix would be directed at different contaminants. The ratio of a solid mixture of coated proppants could vary widely within the range from about 1: 1000 to 1000: 1.
The coating formulation of the present invention may also include an amine reactive component that is different from the polyol reagent. Preferably, the reactive amine component is an amine terminated compound. This component improves the crosslinking density within the coating and,
<img file="MX359509B_D0043.tif" />
<img file="MX359509B_D0044.tif" />
Depending on the component selection, it can provide additional benefit characteristics for the cured coating. Particularly preferred reactive amine components for use in the present invention include amine-terminated compounds such as diamines, triamines, amine-terminated glycols such as amine-terminated polyalkylene glycols commercially available under the name JEFFAMINE from Huntsman Performance Products in The Woodlands , Texas.
Suitable diamines include primary, secondary, and higher polyamines and amine terminated compounds. Suitable compounds include, but are not limited to, ethylene diamine; propylenediamine; butandiamine; hexamethylenediamine; 1,2-diaminopropane;
1.4- diaminobutane; 1,3-diaminopentane; 1,6-diaminohexane;
2,5-diamino-2,5-dimethylhexane; 2,2,4-and / or 2,4,4-trimethyl-
1.6-diaminohexane; 1,11-diaminoundecane; 1,12 diaminododecane; 1,3- and / or 1,4-cyclohexane diamine; 1 amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane; 2,4- and / or
2.6- hexahydrotoluilen diamine; 2,4 'and / or 4,4'-diaminodicyclohexyl methane and 3,3'-dialkyl-4,4'-diaminodicyclohexyl methane as 3,3'-dimethyl-4,4-diaminodicyclohexyl methane and 3,3'-diethyl- 4,4'diaminodicyclohexyl methane; aromatic polyamines like
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX359509B_D0045.tif" />
2,4- and / or 2,6-diaminotoluene and 2,6-diaminotoluene and 2,4 'and / or 4,4'-diaminodiphenyl methane; and polyoxyalkylene polyamines (also referred to herein as amine-terminated polyethers).
Mixtures of polyamines can also be used in the preparation of aspartic esters, which are secondary amines obtained from a primary polyamine and a dialkyl maleic or fumaric acid ester, for use in the invention. Representative examples of useful maleic acid esters include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, mixtures thereof, and homologues thereof.
Suitable triamines and higher multifunctional polyamines for use in the present coating include diethylene triamine, triethylenetetramine, and higher homologs from this series.
JEFFAMINE diamines include D, ED and EDR series products. D stands for a diamine, ED stands for a diamine with the predominantly polyethylene glycol (PEG) backbone, and EDR designates a highly reactive PEG-based diamine.
<img file="MX359509B_D0046.tif" />
IMPI
INDUSTRY*·
The JEFFAMINE products of finished polypropylene glycols following representative structure:
the in
<img file="MX359509B_D0047.tif" />
series D are amine with the
<td>JEFFAWIINE®</td><td>X</td><td>MW</td>
<td> 0-230</td><td> *2.5</td><td> 230</td>
<td> 0-400</td><td> *6,1</td><td> 430</td>
<td>D-2000</td><td> *33</td><td> 2,000</td>
<td>0-4000 (XTJ-510)</td><td> *68</td><td> 4,000</td>
JEFFAMINE EDR-148 (XTJ-504) and JEFFAMINE EDR-176 (XTJ-590) amines are much more reactive than the other JEFFAMINE diamines and triamines. These are represented by the following structure:
<img file="MX359509B_D0048.tif" />
<td>JEFFAMNE®</td><td>and</td><td>X * 2</td><td>MW »</td>
<td>HK-511</td><td>2Λ</td><td> -1.2</td><td> 220</td>
<td>ED-600 IXTJ-500)</td><td> *9.0</td><td> *3.6</td><td> 600</td>
<td>ED-8O0 (XTJ-501)</td><td> -125</td><td> -6.0</td><td> 900</td>
<td>ED-2003 (XTJ-502)</td><td> *39</td><td> -6.0</td><td> 2,000</td>
The JEFFAMINE series products
T are triamines prepared by reacting propylene oxide (PO) with a triol initiator followed by amination of the
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY terminal hydroxyl groups. These are exemplified by the following structure:
<img file="MX359509B_D0049.tif" />
or
440
3000
5000
5-6 $5
CjH *
H
H
T-403
T-3000 (XTJ-509)
T-5000
The series products
SD and ST consist of secondary amine versions of core products
JEFFAMINE. SD stands for secondary diamine and ST stands for secondary triamine. The amine end groups are reacted with a ketone (eg, acetone) and reduced to create hindered secondary amine end groups represented by the following end structure:
<img file="MX359509B_D0050.tif" />
<img file="MX359509B_D0051.tif" />
A reactive hydrogen in each terminal group provides more selective reactivity and makes these secondary di- and triamines useful for the synthesis of intermediates and intrinsically slower reactivity compared to JEFFAMINE primary amines.
<td>JEFFAMINE®</td><td>Base product</td><td>P.M*</td>
<td>SD-231 (XTJ-584)</td><td>D-230</td><td> 315</td>
<td>SD-401 (XTJ-585)</td><td>D-400</td><td> 515</td>
<td>SD-2Q01 (XTJ-576)</td><td>D-2000</td><td> 2050</td>
<td>ST-404 (XTJ-586)</td><td>T-403</td><td> 565</td>
See also
US patents
Nos. 6,093,496;
6,306,964; 5,721,315;
7,012,043;
and publication of
US Patent Application No. 2007/0208156 the disclosure of which is incorporated herein by reference.
An amine-based latent curing agent may, as an option, be added to the coating formulation with the isocyanate component, the polyol component, the amine reactive polyol component, or added simultaneously as any of these components or pre-coated on the proppant. Amine-based latent curing agents suitable for use with the
IMPI
<img file="MX359509B_D0052.tif" />
Present invention include triethylene diamine; bis (2-dimethylaminoethyl) ether; tetramethylethylenediamine; pentamethyldiethylenetriamine; and other tertiary amine products of alkyleneamines. In addition, other catalysts that promote the reaction of isocyanates with hydroxyls and amines that are known in the industry can be used in the present invention.
The amine-based latent curing agents can be added in an amount within the range of from about 0.1 to about 10% by weight based on the total weight of the coating resin.
The proppant coating compositions of the invention may also include various additives.
For example, the coatings of the invention may also include pigments, dyes, colorants, and fillers in an amount to provide visible coloration in the coatings. Other materials traditionally included in coating compositions can also be compositions of the invention.
added to
These additional materials include, but are not limited to, reaction builders or catalysts, crosslinking agents,
IMPI
<img file="MX359509B_D0053.tif" />
optical brighteners, propylene carbonates, coloring agents, fluorescent agents, whitening agents, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, mica, talc, nano-sized fillers and other traditional additives.
All of these materials are well known in the art and are added for their usual purpose in typical amounts. For example, the additives are preferably present in an amount of about 15 weight percent or less. In one embodiment, the additive is present in an amount of about 5 percent or less by weight of the coating composition.
Other additives may include, for example, solvents, softeners, surface active agents, molecular sieves for removal of water from the reaction, diluents and / or bonding agents. Silanes are a particularly preferred type of bonding agent that improves the affinity of the coating resin for the proppant surface. The silanes can be mixed as additives in step (a), but they can also be chemically converted with reactive constituents of the polyol component or of the isocyanate component. Functional silanes like
IMPI
<img file="MX359509B_D0054.tif" />
Amino silanes, epoxy-, aryl vinyl silanes are commercially available and, as already described, can be used as additives or can be converted with the reactive constituents of the polyol component or the isocyanate component.
In particular.
amino-silanes and epoxy-silanes can be easily converted with the isocyanate component.
The method for the production of coated proppants according to the present invention can be implemented without the use of solvents. Consequently, the mixture obtained in step (a) in one embodiment of the method is solvent-free, or is practically solvent-free. The mixture is practically solvent-free, if it contains less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, and still more preferably less than 3% by weight, and more preferably less than 1 % by weight of solvent, in relation to the total mass of components of the mixture.
In step (a) the proppant is preferably heated to an elevated temperature and then contacted with the coating components. The proppant is preferably heated to a
IMPI
<img file="MX359509B_D0055.tif" />
temperature within the range of about 50 ° C to about 150 ° C to accelerate crosslinking reactions in the applied coating.
The mixer used for the coating process is not particularly restricted and can be selected from among known mixers in the specific field. For example, a mill mixer or agitation mixer can be used. For example, a drum mixer, a plate mixer, a tube mixer, a channel mixer or a conical mixer can be used. The easiest way is mixing on a rotating drum although a continuous or helical mixer can also be used.
Mixing can be carried out continuously or discontinuously. In suitable mixers it is possible, for example, to add adhesion agents, isocyanate, amine and optional ingredients continuously to the heated proppant. For example, the isocyanate components, amine reagents, and optional additives can be mixed with the solid proppants in a continuous mixer (such as a helical mixer) in one or more steps to make one or more layers of cured coating.
<img file="MX359509B_D0056.tif" />
<img file="MX359509B_D0057.tif" />
Preferably, the proppant, the isocyanate component, the amine reagent and optional additives are mixed homogeneously. Thus, the isocyanate component and the amine reagent are evenly distributed on the surface of the proppants. The coating ingredients are preferably kept in motion throughout the entire mixing process. It is also possible to arrange multiple mixers in series, or to coat the proppants in multiple runs in one mixer.
The temperature of the coating process is not particularly restricted outside of the practical aspects of component safety and integrity. Preferably, the coating step is performed at a temperature of between about 10 ° C and about 200 ° C, or more preferably at a temperature of about 10 ° C to about 150 ° C.
The coating material can be applied in more than one layer. In this case, the coating process is repeated as needed (eg, 1-5 times, 2-4 times, or 2-3 times) to obtain the desired coating thickness and / or synthetically apply the cleaning activity of water / hydrocarbon within
INSTITUTO MEXICANO DE LA RROPIEUAD INDUSTRIAL layers in the coated proppant. In this way, the
<td>thickness of</td><td>proppant coating can be</td>
<td>tight and</td><td>used either as an interval</td>
relatively narrow of proppant size or with proppants of other sizes, such as those with more or fewer numbers of polyurethane coating layers according to the present invention, to form a proppant mixture having more than one size distribution range. A preferred range for coated proppant is typically within the range of about 20-70 mesh.
The amount of coating resin, i.e. polyurethane resin applied to the proppant, preferably between approximately
0.5 of is approximately
10% by weight, more preferably between about and about 5% by weight, resin relative to the proppant mass as 100% by weight.
Coated proppants can also be treated with surface active aids, such as talcum powder or stearate, to improve fluidity.
If desired, coated props can be baked or heated for a period of time
<img file="MX359509B_D0058.tif" />
IMPI NSTrnjYo Mexican
OF INDUSTRIAL PROPERTY
<img file="MX359509B_D0059.tif" />
enough
<img file="MX359509B_D0060.tif" />
react
<img file="MX359509B_D0061.tif" />
isocyanate, less practically
<img file="MX359509B_D0062.tif" />
<img file="MX359509B_D0063.tif" />
groups
<img file="MX359509B_D0064.tif" />
amine stay
<img file="MX359509B_D0065.tif" />
reagents
<img file="MX359509B_D0066.tif" />
<img file="MX359509B_D0067.tif" />
<img file="MX359509B_D0068.tif" />
coated proppant.
This could
<img file="MX359509B_D0069.tif" />
later
<img file="MX359509B_D0070.tif" />
coating can occur even
<img file="MX359509B_D0071.tif" />
<img file="MX359509B_D0072.tif" />
uses additional contact time with a catalyst after a first coat or between coats. Typically, the post-coating curing step is performed as a baking step at a temperature within the range of from about 100 ° -200 ° C for a time of about 0.5-12 hours, preferably, the temperature is about 125 ° -175 ° C for 0.25-2 hours. Even more preferably, the coated proppant is cured for a time and under conditions sufficient to produce a coated proppant that exhibits a loss of coating of less than 25% by weight, preferably less than 15% by weight, and even more preferably less than 5%. Weight% when analyzed according to ISO 13503-5: 2006 (E).
With the method according to the present invention proppants can be coated at temperatures between about 10 ° C and about 200 ° C, preferably in a solvent-free form, and
IMPI
MEXICAN INSTITUTE?
OF INDUSTRIAL PROPERTY combined with a component for the elimination of contaminants such as a NORMS or a heavy metal or zeolitic ion exchange material, to effect the fracturing of the stratum and a measure of elimination of contaminants from the water and hydrocarbons produced while also reducing the proppant flow return.
Use of proppant formulation to remove contaminants
Furthermore, the invention includes the use of the proppant formulation for the removal of contaminants together with a fracturing liquid for the production of petroleum or natural gas. The fracturing liquid is not particularly restricted and can be selected from among the fractionating liquids known in the specific field. Suitable fracturing fluids are described, for example, in WC Lyons, GJ Plisga, Standard Handbook Of Petroleum And Natural Gas Engineering, Gulf Professional Publishing (2005). The fracturing liquid may be, for example, polymer gelled water, a polymer gelled water-in-oil emulsion, a polymer gelled water in oil emulsion, or gelled / non-gelled hydrocarbon. In a preferred embodiment, the
IMPI
<img file="MX359509B_D0073.tif" />
fracturing fluid comprises the following constituents in the indicated proportions: 1000 1 of water, 20 kg of potassium chloride, 0.120 kg of sodium acetate, 3.6 kg guar gum (polymer soluble in water), sodium hydroxide (as required) to adjust a pH value from 9 to 11, 0.120 kg of sodium thiosulfate and 0.180 kg of ammonium persulfate.
Furthermore, the invention relates to a method for the production of oil or natural gas which consists of the injection of the coated proppant into the fractured layer with the fracturing liquid, that is, the injection of a fracturing liquid containing the coated proppant , to a rock layer that carries oil or natural gas, and / or its introduction in a fracture in the rock layer that carries oil or natural gas. This method is not particularly restricted and can be implemented in a manner known in the specific field.
When the water / hydrocarbon cleaning method is made more efficient for use in a physical proppant mix and one or more commercial ion exchange resins or zeolites, these mixes can be produced at the coating process manufacturing site
IMPI • Mexican NSTITUTO
FROM the industrial PROPERTY of the proppant or it can be carried out in the hole during the fracturing process.
Once those skilled in the art are taught the invention, many variations and modifications are possible without departing from the inventive concepts described in. the present. The invention is therefore not restricted except in the spirit of the appended claims.
IMPI
INSTITUTO MEXICANO OELAHUXTCDAO INOUSTIUAL
Contents72
73 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73
52 members in 9 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 13224726 | United States of America | – | |
| 201113224726 | United States of America | A | |
| 2012053277 | United States of America | W | |
| 13224726 | – | – | – |
| PCTUS2012053277 | – | – | – |
| US201113224726 | – | – | – |
| WO2012US53277 | – | – | – |
Members52
| Document | Office | Kind | |
|---|---|---|---|
| US2012279703A1 | United States of America | A1 | |
| US2012283153A1 | United States of America | A1 | |
| WO2012151260A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2013016158A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2013056204A1 | United States of America | A1 | |
| WO2013033492A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2013065800A1 | United States of America | A1 | |
| CN103608427A | China | A | |
| CA2889928A1 | Canada | A1 | |
| WO2014052459A1 | World Intellectual Property Organization (WIPO) | A1 | |
| CN103764945A | China | A | |
| US2014162911A1 | United States of America | A1 | |
| CN103889706A | China | A | |
| US8763700B2 | United States of America | B2 | |
| MX2013012807A | Mexico | A | |
| MX2014002156A | Mexico | A | |
| MX2014000826A | Mexico | A | |
| US2014309149A1 | United States of America | A1 | |
| CA2921658A1 | Canada | A1 | |
| WO2015031415A2 | World Intellectual Property Organization (WIPO) | A2 | |
| US8993489B2 | United States of America | B2 | |
| US9040467B2 | United States of America | B2 | |
| RU2013153483A | Russian Federation | A | |
| CN104797681A | China | A | |
| US2015203745A1 | United States of America | A1 | |
| RU2014101935A | Russian Federation | A | |
| US2015259592A1 | United States of America | A1 | |
| MX2015003673A | Mexico | A | |
| RU2014112514A | Russian Federation | A | |
| WO2015031415A3 | World Intellectual Property Organization (WIPO) | A3 | |
| AR097446A1 | Argentina | A1 | |
| US9290690B2 | United States of America | B2 | |
| MX2016002427A | Mexico | A | |
| US2016194556A1 | United States of America | A1 | |
| CN105793385A | China | A | |
| RU2015115291A | Russian Federation | A | |
| BR112013028315A2 | Brazil | A2 | |
| BR112014001451A2 | Brazil | A2 | |
| BR112014004541A2 | Brazil | A2 | |
| US9624421B2 | United States of America | B2 | |
| HK1222670A | Hong Kong, China | A | |
| HK1222670A1 | Hong Kong, China | A1 | |
| US9725645B2 | United States of America | B2 | |
| US2017283686A1 | United States of America | A1 | |
| CN103608427B | China | B | |
| MX356907B | Mexico | B | |
| MX359509BThis record | Mexico | B | |
| US10087360B2 | United States of America | B2 | |
| US2019249078A1 | United States of America | A1 | |
| US10544358B2 | United States of America | B2 | |
| US2022169916A1 | United States of America | A1 | |
| CA2921658C | Canada | C |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 359509
- Publication, DOCDB
- 359509
- Publication, EPODOC
- MX359509
- Application
- 2014002156
- Application, DOCDB
- 2014002156
- Application, EPODOC
- MX20140002156
Titles
- Spanish
- APUNTALANTES DE FUNCIÓN DOBLE.
Classification
- CPC, 8
- C09K8/80
- C09K8/536
- E21B43/04
- E21B43/267
- C09K8/64
- C09K8/68
- C09K8/805
- C09K8/90
- IPC, 1
- E21B43 02