Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
  • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B2009/125—Micropellets, microgranules, microparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/772—Articles characterised by their shape and not otherwise provided for
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the present invention relates to polyamide beads or granules and to a method of manufacturing these beads and also to their use as a proppant for natural or artificial underground cracks of the earth's crust used, in particular, for extracting hydrocarbons such as oil or natural gas.
• It relates more particularly to small-diameter beads having a uniform shape.
• Thermoplastic polymers such as polyamides are very important materials for the manufacture of numerous articles used in numerous fields. These articles are generally obtained by shaping starting from the molten polymer in spinning, extrusion or molding processes for example.
• the raw material used for producing these articles is in the form of polymer granules obtained by casting of the molten polymer exiting polymerization installations in rod form and cutting of these rods into granules of cylindrical shape.
• These granules generally of cylindrical shape have a length of a few millimeters.
• granules of a particular shape for example of substantially spherical shape.
• Such spherical granules will be referred to hereinbelow as beads, and have, in particular, a better flowability.
• thermoplastic beads For many years, one granulating process makes it possible to produce thermoplastic beads.
• This process and device for implementing it are known as an “underwater pelletizing” device or process and are described, for example, in patents U.S. Pat. No. 2,918,701 or U.S. Pat. No. 3,749,539.
• thermoplastic polymer beads require beads of small size or diameter, especially the use of polyamide beads as a proppant for natural or artificial underground cracks of the earth's crust in installations for extracting hydrocarbons as described in Patent US 2006/0151170 for example.
• One of the objectives of the present invention is to provide small-size polyamide beads and a method that uses an underwater pelletizing device that makes it possible to produce such beads without the drawbacks of the known installations and methods.
• the invention provides polyamide beads of spherical or ellipsoidal shape, the surface of which does not comprise concave portions, advantageously of uniform shape, characterized in that they have an average diameter less than or equal to 1.7 mm and a porosity of less than 0.1 ml/g, measured according to the mercury porosity measurement method using a MICROMERITICS AutoPore IV mercury porosimeter according to the standard ASTM Standards of catalysts D 4284-83.
• the average diameter D is understood to be the diameter determined by the measurement of the mass P of a random sample of 100 beads.
• the diameter D is given by the following formula (I):
• P represents the mass in grams of a sample of 100 beads or granules
• Mv represents the density of the material forming the beads.
• the density Mv is determined according to the following method:
• the volume of the pearls is estimated by water displacement according to the following protocol:
• a volumetric Erlenmeyer flask having a volume suitable for the size of the beads is filled with water up to the brim of the neck, which corresponds to a volume V 1 of water.
• the mass of the flask+water assembly is measured, and noted as M 1 .
• the water is drained from the flask.
• the flask is filled with a given mass m 1 of beads.
• the flask is again filled with water up to the brim of the neck.
• the mass of the flask+water+beads assembly is measured, it is noted as M 2 .
• the density of the bead is then calculated by the following formula II:
• V 0 represents the density of the water in g/cm 3 .
• the beads of the invention have a uniform shape that does not have any concave portions. This feature is understood to mean that the imaginary envelope of the bead does not comprise any concave portions.
• the surface of the bead may comprise small protuberances or small cavities that form irregularities on the surface of the bead such as the defects generated by gas bubbles for example.
• the beads of the invention are obtained from a polyamide resin or from a material comprising, as a polymeric matrix, a polyamide resin and fillers or additives.
• polyamide resins and materials suitable for the invention advantageously have high mechanical properties and a high chemical resistance, advantageously compatible for the use of the beads as proppants in hydrocarbon extraction wells.
• the polyamide resin used for manufacturing beads is chosen from polyamide thermoplastic polymers having a high melting point, advantageously those that have a melting point above 200° C., such as polyamides 6-6, polyamide 6, copolyamides 66/6, copolyamides 6/66, copolyamides comprising at least 80% by weight of polyamide 6 units, or at least 80% of polyamide 66 units, semiaromatic polyamides such as those sold under the tradenames AMODEL or NYLON HTN, polyamide T6, polyamide 4,6.
• polyamide thermoplastic polymers having a high melting point advantageously those that have a melting point above 200° C.
• polyamides 6-6 polyamide 6, copolyamides 66/6, copolyamides 6/66, copolyamides comprising at least 80% by weight of polyamide 6 units, or at least 80% of polyamide 66 units
• semiaromatic polyamides such as those sold under the tradenames AMODEL or NYLON HTN, polyamide T6, polyamide
• the materials used comprise a polyamide matrix and reinforcing and/or bulking fillers added to the thermoplastic polymers.
• concentration of these reinforcing and/or bulking fillers may vary to a large extent. This concentration is advantageously between 5% and 90% by weight relative to the mass of the final material.
• These reinforcing and/or bulking fillers may be chosen from the group comprising fibers such as glass fibers, aramid fibers, ceramic fibers, fibers made of thermosetting material, ceramic or glass beads, mineral fillers in powder form such as clays, kaolin, talc, silica, aluminum, molecular sieves, natural fillers or fibers such as jute fibers, ground coconut fibers or similar fibers.
• fibers such as glass fibers, aramid fibers, ceramic fibers, fibers made of thermosetting material, ceramic or glass beads, mineral fillers in powder form such as clays, kaolin, talc, silica, aluminum, molecular sieves, natural fillers or fibers such as jute fibers, ground coconut fibers or similar fibers.
• the materials may also contain additives that modify certain properties such as plasticizers, additives for stabilization to oxidation, heat and/or light stabilizers, pigments, dyes, mattifying agents, flame retardants, crosslinking agents or similar.
• the polyamide beads have an average diameter between 0.5 and 1.7 mm, advantageously between 0.8 mm and 1.5 mm, preferably between 0.9 and 1.3 mm.
• polyamide beads described above may be used in numerous applications such as processes for manufacturing molded or injection-molded articles.
• These beads may also be used as is as a means of filling, and preferably as means of shoring up underground fractures and cracks that are natural or that are generated artificially in wells for extracting oil and natural gas in particular.
• these polyamide beads are driven into the underground cracks by various techniques described, for example, in patents U.S. Pat. No. 3,659,651, U.S. Pat. No. 7,128,118, US 2006/0151170, US 2006/0065398.
• the polyamide beads of the invention are produced by a method for manufacturing beads that uses an underwater pelletizing device for cutting a molten polymer.
• the underwater pelletizing devices for the manufacture of substantially spherical granules from molten polymer have been known for a long time.
• US 2005/0035483 describes an underwater pelletizing method and device that makes it possible to reduce the problems generated by the supply of polymers having a high melting point and a high crystallization such as polyamides. This is because, with such polymers, the risks of crystallization of the polymer in the die holes are high.
• This document describes a solution that consists in equipping the die with means for heating the polymer at the die hole.
• This document describes the manufacture of spherical polyamide granules having a diameter greater than 3 mm corresponding to a weight of 100 granules that is between 2.5 and 4.3 g.
• the method of the invention consists in implementing conditions for operating and feeding of the underwater pelletizing device that make it possible to obtain beads having an average diameter of less than 1.7 mm with a minimal risk of blocking of the die holes that is compatible with an industrial production polyamide beads.
• the method of the invention consists in introducing the polyamide or a polyamide-based composition into a granulating device having an underwater pelletizer comprising a die provided with holes, the diameter of which is between 0.3 mm and 1.7 mm, the temperature of the cooling liquid is between 70° C. and 100° C.
• the polyamide or the composition is fed into the die holes under a pressure between 70 bar and 250 bar.
• the feed pressure of the polymer in the die holes is established at at least 80% of its nominal value indicated above in a very short time, less than 5 seconds, preferably less than 3 seconds. Moreover, this pressure is kept substantially stable throughout the granulating process.
• the feeding of the polyamide or of the composition is carried out by the use, in series, of a single-screw or twin-screw device and of a gear pump.
• a gear pump makes it possible to feed the molten polyamide into the die holes at a constant throughput which is advantageously between 3 and 15 kg per hole per hour, preferably between 5 and 12 kg per hole per hour.
• the gear pump is cited by way of example as a device suitable for rapidly establishing a polymer feed pressure on starting the feeding of the molten polymer into the die of the granulating process.
• the granulating devices having an underwater pelletizer generally and advantageously comprise a valve between the die and the outlet of the molten polymer feed device, in the present case the outlet of the gear pump.
• a valve between the die and the outlet of the molten polymer feed device, in the present case the outlet of the gear pump.
• the rotational speed of the knife or cutting device at the submerged surface of the die is determined in order to obtain beads of desired diameter, and is advantageously between 3000 and 6000 rpm.
• the polyamide beads thus produced are recovered by any known means, especially by centrifugation, settling or filtration.
• the beads thus recovered are then advantageously dried. They may also be subjected to treatments in order to modify some of their properties such as the improvement of the mechanical properties by a heat treatment or a radiation treatment in order to produce an increase in the molecular weight of the polymer and/or its degree of crosslinking.
• Another subject of the present invention is a device for implementing the manufacturing method as mentioned previously, comprising a granulating device having an underwater pelletizer comprising at least:
• the feed means preferably comprises a single-screw or twin-screw extruder combined with a gear pump.
• the feed means advantageously comprises a means for controlling the throughput of the polyamide in the die that makes it possible to obtain a throughput between 3 and 15 kg/h per hole, preferably between 5 and 12 kg/h per hole.
• the cutting means preferably comprises a rotating knife driven by a rotary drive at a rotational speed between 3000 and 6000 rpm.
• these beads are suitable to be used as means for propping open underground cracks in the devices and installations for extracting oil or gas.
• these beads have mechanical properties, especially compressive strength, and also chemical resistance properties that are suitable for this application.
• a polyamide of type 66 sold by RHODIA under the tradename STABAMID 27 AE1 has a viscosity index VI equal to 136 (measured at 25° C. in a Hubbelhode type viscosimeter from a solution containing 5 g/l of polymer dissolved in a mixture composed of 90% by weight of formic acid and 10% by weight of water) and a melting point of 263° C. (determined by the DSC method).
• This polymer is melted at a temperature of 308° C. using a twin-screw extruder having a diameter of 50 mm sold by Leistriz and is fed into a gear pump sold by Maag.
• This gear pump feeds an underwater pelletizing device sold by GALA under the tradename AS PAC 6 at a material pressure of 169 bar.
• the die of this underwater pelletizing device has 32 holes that are 0.8 mm in diameter.
• the die is heated at a temperature of 345° C.
• the device comprises a knife holder equipped with 16 blades that turn in the cutting chamber at a speed of 5000 rpm.
• water at 76° C. circulates with a flow rate of 22 m 3 /h. Under these conditions, the method makes it possible to produce, for a polymer throughput in the holes of the die equal to 170 kg/h with a throughput per hole of 5 kg/h, substantially spherical particles having a diameter equivalent to 1.4 mm.
• a copolyamide 66/6 comprising 40% by weight of kaolin as mineral fillers is melted at a temperature of 329° C. using a twin-screw extruder, having a diameter of 50 mm sold by Leistriz, which feeds a gear pump sold by Maag.
• This gear pump feeds an underwater pelletizing device identical to that from example 1 under a pressure of 91 bar, pressure observed 3 seconds after the feeding of the polymer into the die.
• the die of this underwater pelletizer has 72 holes of 1.2 mm and is heated at a temperature of 369° C.
• a knife holder equipped with 16 blades turns in the cutting chamber at a speed of 4500 rpm.
• water at 89° C. circulates at a flow rate of 11 m 3 /h. Under these conditions, for an extrusion throughput of 420 kg/h, substantially spherical particles are obtained having a diameter equivalent to 1.5 mm.
• a copolyamide 6/66 comprising 40% mineral filler constituted by kaolin is melted at a temperature of 333° C. using a twin-screw extruder identical to that from examples 1 and 2, which feeds a gear pump identical to that from examples 1 or 2.
• This gear pump feeds an underwater pelletizing device identical to that from example 1 or 2 under a feed pressure of 135 bar.
• the die of this underwater pelletizing device has holes of 1 mm in diameter and is heated at a temperature of 389° C.
• a knife holder equipped with 16 blades turns in the cutting chamber at a speed of 5000 rpm. In this same cutting chamber, water at 92° C. circulates at a flow rate of 20 m 3 /h. Under these conditions, for an extrusion throughput of 400 kg/h, particles are obtained having a diameter equivalent to 1.25 mm.

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• 2006
  • 2006-12-22 FR FR0611260A patent/FR2910368B1/fr not_active Expired - Fee Related
• 2007
  • 2007-12-20 CA CA002673086A patent/CA2673086A1/fr not_active Abandoned
  • 2007-12-20 EP EP07857983.6A patent/EP2121261B1/fr active Active
  • 2007-12-20 WO PCT/EP2007/064364 patent/WO2008077895A1/fr active Application Filing
  • 2007-12-20 CN CN2007800506045A patent/CN101600549B/zh active Active
  • 2007-12-20 BR BRPI0719450-1A patent/BRPI0719450B1/pt not_active IP Right Cessation
  • 2007-12-20 EA EA200970625A patent/EA014994B1/ru unknown
  • 2007-12-20 US US12/520,584 patent/US20100285998A1/en not_active Abandoned
  • 2007-12-21 TW TW096149617A patent/TWI428221B/zh not_active IP Right Cessation
• 2014
  • 2014-12-01 US US14/557,033 patent/US9676121B2/en active Active
• 2017
  • 2017-05-08 US US15/589,498 patent/US20170239844A1/en not_active Abandoned
• 2019
  • 2019-01-30 US US16/261,734 patent/US10940612B2/en active Active

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