WO2002059183A2 - Drag-reducing polymers and drag-reducing polymer suspensions and solutions - Google Patents
Drag-reducing polymers and drag-reducing polymer suspensions and solutions Download PDFInfo
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- WO2002059183A2 WO2002059183A2 PCT/US2001/044361 US0144361W WO02059183A2 WO 2002059183 A2 WO2002059183 A2 WO 2002059183A2 US 0144361 W US0144361 W US 0144361W WO 02059183 A2 WO02059183 A2 WO 02059183A2
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
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- 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
- C08J3/005—Processes for mixing polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/902—Monomer polymerized in bulk in presence of transition metal containing catalyst
Definitions
- the present invention relates to drag-reducing polymers and their method of manufacture. More specifically, this invention relates to a method for preparing ultra- high molecular weight, substantially non-crystalline hydrocarbon-soluble polymers through bulk polymerization.
- a drag-reducing agent is one that substantially reduces the friction loss that results from the turbulent flow of a fluid. Where fluids are transported over long distances, such as in oil and other hydrocarbon liquid pipelines, these friction losses result in inefficiencies that increase equipment and operations costs.
- Ultra-high molecular weight polymers are known to function well as drag-reducing agents, particularly in hydrocarbon liquids. In general, drag reduction depends in part upon the molecular weight of the polymer additive and its ability to dissolve in the hydrocarbon under turbulent flow. Effective drag-reducing polymers typically have molecular weights in excess of five million.
- Drag-reducing polymers are known in the art. Representative, but non- exhaustive, samples of such art are: U.S. Pat. No. 3,692,675, which teaches a method for reducing friction loss or drag for pumpable fluids through pipelines by adding a minor amount of a high molecular weight, non-crystalline polymer; and U.S. Pat. No. 3,884,252, which teaches the use of polymer crumb as a drag-reducing material. These materials are extremely viscoelastic, and, in general, have no known use other than as drag-reducing materials. However, the very properties that make these materials effective as drag-reducing additives make them difficult to handle because they have a severe tendency to cold flow and reagglomerate even at subambient temperatures. Under conditions of pressure, such as stacking or palleting, cold flow is even more intense and reagglomeration occurs very quickly.
- Pat. No. 3,736,288 teaches solutions of drag-reducing polymers in inert, normally liquid vehicles for addition to liquids flowing in conduits. A "staggered dissolution" effect is provided by varying the size of the polymer particles. Suspension or surface-active agents can also be used. While directed to ethylene oxide polymers, the method is useful for hydrocarbon-soluble polymers as well.
- U.S. Pat. No. 4,088,622 describes a method of making an improved, molded drag-reducing coating by incorporating antioxidants, lubricants, and plasticizers and wetting agents in the form of a coating which is bonded directly onto the surface of materials passing through a liquid medium.
- 4,340,076 teaches a process for dissolving ultra-high molecular weight hydrocarbon polymer and liquid hydrocarbons by chilling to cryogenic temperatures comminuting the polymer formed into discrete particles and contacting these materials at near cryogenic temperatures with the liquid hydrocarbons to more rapidly dissolve the polymer.
- U.S. Pat. No. 4,341,078 immobilizes toxic liquids within a container by injecting a slurry of cryogenically ground polymer particles while still at cryogenic temperatures into the toxic liquid.
- 4,420,440 teaches a method for collecting spilled hydrocarbons by dissolving sufficient polymer to form a nonflowing material of semisolid consistency by contacting said hydrocarbons with a slurry of cryogenically comminuted ground polymer particles while still at cryogenic temperatures.
- Some current drag-reduction systems inject a drag-reducing polymer solution containing a high percentage of dissolved, ultra-high molecular weight polymer into conduits containing the hydrocarbon.
- the drag-reducing polymer solution is normally extremely thick and difficult to handle at low temperatures.
- Solid polymers of these types can take days to dissolve in some cases, even though drag reduction is greatly enhanced once dissolution has finally occurred. Dissolution at low temperatures, i.e., below 70 F, may be so slow with some polymers that there is little practical drag-reduction benefit with those polymers.
- certain polymers may not be suitable for certain hydrocarbons. For instance, copolymers of ⁇ - olefins will not dissolve in heavy, aromatic crude oils and so are unsuitable in these applications as drag-reducing agents.
- Another way to introduce ultra-high molecular weight polymers into the flowing hydrocarbon stream is through a suspension. Powdered ultra-high molecular weight polymers are suspended in a liquid that will not dissolve or will only partially dissolve the ultra-high molecular weight polymer. This suspension is then introduced into the flowing hydrocarbon stream. The tendency of the ultra-high molecular weight polymers to reagglomerate makes manufacture of these suspensions difficult.
- a way of controlling the tendency of the ultra-high molecular weight polymers to reagglomerate is to partially surround the polymer particles with a partitioning agent, occasionally termed a coating material, to reduce the ability of these polymers to reagglomerate.
- partitioning agent describes a process whereby the polymer is ground and then coated with alumina to form a free-flowing powder.
- Some processes using a partitioning agent require that the partitioning agent completely surround the polymer core, which requires that at least 20% and often as much as 50% of the weight of the final composition be the partitioning agent.
- Other examples of partitioning agents used in the art include talc, tri-calcium phosphate, calcined clays, magnesium stearate, silica, polyanhydride polymers, sterically hindered alkyl phenol antioxidants, and graphite. Partitioning agents, however, add weight to the drag-reducing agent material, resulting in higher transport costs and additional handling equipment, without any drag-reducing benefit. Further, some partitioning agents are incompatible with the hydrocarbon fluid or may be an unwanted contaminant in the hydrocarbon fluid.
- One alternative to solution polymerization is bulk polymerization.
- Bulk-polymerized drag-reducing polymers should have five characteristics: 1) less than 5% unpolymerized material should remain in the bulk polymerized material; 2) it must be possible to grind them to a fine, stable powder; 3) they must form stable suspensions; 4) they must dissolve rapidly in various hydrocarbons at temperatures as low as 30°F; and 5) they must effectively reduce the frictional drag in hydrocarbon pipelines. Accordingly, a drag-reducing polymer, and drag-reducing polymer suspension and method of manufacturing the drag-reducing polymer suspension are disclosed herein that meet all five of these criteria.
- One embodiment of the present invention is drawn to an ultra-high molecular weight copolymer composed of a vinyl
- the ultra-high molecular weight copolymer has a molecular weight of greater than 1 million.
- method of manufacturing an ultra-high molecular weight copolymer is disclosed where the ultra-high molecular weight copolymer is
- an ultra-high molecular weight copolymer is manufactured by forming a monomer mixture composed of an ⁇ -olefin monomer having a carbon chain length of between 2 and 20 carbon atoms and a vinyl aromatic monomer. An initiator, catalyst and promoter are then added and the mixture allowed to react to form the ultra-high molecular weight copolymer.
- the ultra-high molecular weight copolymer has a molecular weight of greater than 1 million.
- a method for the preparation of a drag-reducing copolymer suspension is disclosed where an ultra-high molecular weight copolymer is prepared by co-polymerization of an ⁇ -olefin with a vinyl aromatic, wherein the ⁇ - olefin has a carbon chain length of between 2 and 20 carbon atoms.
- a drag-reducing polymer solution is disclosed, which is composed of an ultra-high molecular weight copolymer having a vinylaromatic monomer and an ⁇ -olefin monomer having a carbon chain lengths of between 2 and 20 carbon atoms, and a heavy hydrocarbon.
- the drag-reducing polymer suspension is easily transportable and does not require pressurized or special equipment for storage, transport, or injection.
- Another advantage is that the drag- reducing polymer is quickly dissolved in various flowing hydrocarbon streams.
- the copolymers of the present invention are soluble in heavy aromatic hydrocarbons at temperatures as low as 0°C (32°F).
- Another advantage of copolymers of the present invention is that they may either be transported in a stable suspension, or pre-dissolved in a small amount of heavy hydrocarbon.
- Still another advantage of the present invention is that reagglomeration of the drag-reducing polymers is greatly reduced, allowing for easier handling during manufacture.
- Another advantage of the present invention is that the drag-reducing polymer suspension is stable, allowing a longer shelf life and balancing of customer demand with manufacturing time. Another advantage is that costly solvent removal is minimized. A further advantage of the present invention is that the amount of inert ingredients in the final product is reduced.
- Figure 1 is a schematic of the apparatus for manufacturing the drag-reducing polymer suspension.
- drag-reducing polymers are produced via bulk polymerization to produce a substantially non-crystalline, hydrocarbon-soluble, ultra- high molecular weight drag-reducing polymer.
- the polymer is produced by the bulk
- the polymerization medium contains primarily catalyst, ⁇ -olefins monomers, and
- the reaction medium will normally contain at least 80% reactive monomers by weight, and normally these monomers are nearly completely reacted, resulting in polymer contents of normally at least 80% by weight of the total reaction medium, based on the total reactor content.
- the monomers comprise at least 90% by weight of the total reaction medium, resulting in final polymer contents of normally at least 90% by weight of the total reaction medium, and most preferably the monomers comprise at least 95% by weight of the total reaction medium, resulting in final polymer contents of normally at least 95% by weight of the total reaction medium.
- the bulk polymerizations of the present invention may be carried out using any ⁇ -olefin polymerization catalyst, but Ziegler-Natta catalysts are preferred.
- the Ziegler- Natta catalysts used can be any of those described in the art. Particularly useful materials are those described in U.S. Pat. Nos. 4,945,142, 4,358,572, 4,371,455, 4,415,714, 4,333,123, 4,493,903 and 4,493,904, which are hereby incorporated by reference. Applicable metallocene catalysts may also be used.
- catalysts are used typically at a concentration of 3500 moles monomer per mole transition metal halide in the catalyst, although ratios can vary from as low of 500/1 to as high as 10000/1 or more. Catalyst concentration affects rate of reaction and temperature as well as molecular weight. These catalysts often are more effective when used in the presence of a promoter, such as dibutyl ether, or an initiator, such as disobutyl aluminum chloride (DIB AC).
- a promoter such as dibutyl ether
- DIB AC disobutyl aluminum chloride
- Consistent conversions of more than 95 percent polymer by weight can be obtained by using these catalysts in bulk polymerizations.
- Polymers prepared according to the present invention are extremely effective relative to solution- polymerized materials now in commercial use which contain solvent.
- the reduction in solvent used to manufacture bulk-polymerized materials results in reduction or elimination of the solvent removal step.
- the polymers of the present invention are produced by co-polymerizing one or
- the ⁇ -olefin monomer component(s) should have a carbon chain length of between
- ⁇ -olefin monomers may be used as long as all ⁇ -olefin monomers have carbon chain lengths of between 2
- Non-exclusive examples of these ⁇ -olefin monomers include 1-
- the second monomer of the present invention is a vinyl aromatic.
- vinyl aromatics include styrene, alkyl-styrenes with an alkyl group having between 1 and 10 carbon atoms, such as methylstyrenes, such as 4-methylstyrene, 3-methylstyrene, alpha-methylstyrene, and beta-methylstyrene, and t-butylstyrene, vinyl toluenes, and naphthalene and its derivatives, such as 1-vinylnaphthalene and 2- vinylalkylnaphthalene, as well as mixtures of two or more of the listed vinyl aromatics.
- the amount of vinyl aromatic in the bulk polymerization mixture should be between 1% and 50% by weight of the total reaction medium, preferably between 2% and 25%.
- the vinyl aromatic is fully incorporated into the copolymer, i.e., the vinyl aromatic percentage in the copolymer is approximately equal to that of the original mixture.
- These polymers are copolymers as they are composed of more than one type of monomer.
- the ⁇ -olefin and vinylaromatic monomers are collectively referred to as co-
- aromatic copolymers are generally more soluble than polymers formed from only ⁇ - olef ⁇ n monomers in heavy aromatic crude oils particularly at temperatures below 20°C (68°F) and as low as 0°C (32°F). Further, these copolymers have excellent solubility in many hydrocarbons other than heavy aromatic crude oils. Some vinyl aromatics, particularly styrene also may be less costly than other monomers often used to make drag-reducing polymers. Vinyl aromatics also tend to decrease the crystallinity of the polymer, increasing its effectiveness as a drag reducer. For polymerization reactions which are incomplete, removal of unreacted monomers is advantageous, and can be carried out by vacuum drying and/or vacuum drying with precipitation according to well known techniques. However, it is preferred that a bulk reaction simply be carried out to substantial completion preferably to 99% completion or more and that the drying step to remove monomer and or solvent be avoided whenever possible.
- Polymerization reactions of this invention are exothermic reactions. It is preferred and sometimes even necessary to control the heat transfer and or temperature rise in bulk polymerizations in order to obtain ultra-high molecular weights (inherent viscosity) required for best drag reduction.
- the polymer should have a molecular weight in excess of 1 million and preferably in excess of 5 million. In order to keep the temperatures of the reaction mixture sufficiently low throughout the reaction period to make such ultra-high molecular weight polymer more or less uniform in the reaction container, it is preferred to design reaction enclosures as small as possible in the various dimensions.
- reaction vessels should be shaped such that maximum surface area is exposed to a cooling medium in order to facilitate heat transfer and to achieve ultra-high molecular weight.
- Polymeric bottles and bags may be used as effective polymerization reaction enclosures.
- the produced polymer is generally adherent to the walls of such reaction enclosures, and, therefore, it is more convenient that the polymeric reaction enclosures may be ground with the final product in forming the drag-reducing materials of the present invention. It is, of course, possible to carry out bulk polymerization in conventional reactors, belt polymerization systems, clam-shell reactors or reactions in single-layer polymer reactors (bottles or bags).
- barrier polymers which are capable of excluding air and water from the reaction mixture during the reaction. These barrier polymers are crystalline and are non-soluble in the hydrocarbons in which the drag- reducing non-crystalline polymers are soluble at ambient conditions, such as crude oil and refined fuels. These barrier polymers may be cross-linked.
- the reaction enclosures may contain five to seven layers, including a water impervious polyolefin such as polypropylene, polyethylene, polybutylene, a bonding polymer, and ethylene vinyl alcohol copolymer oxygen barrier, another bonding polymer, and externally coated with polyethylene, polypropylene or polybutylene.
- a water impervious polyolefin such as polypropylene, polyethylene, polybutylene, a bonding polymer, and ethylene vinyl alcohol copolymer oxygen barrier, another bonding polymer, and externally coated with polyethylene, polypropylene or polybutylene.
- ethylene terephthlate is an excellent oxygen barrier but a poor water barrier
- polyethylene, polypropylene, polybutylene and the like are excellent water barriers but do permit the passage of oxygen.
- a polymer designed to adhere to both is sandwiched between these materials.
- An example of the bonding polymer are the coextrudable adhesive polymers sold under the registered trademark "BYNEL" by the
- the ethylenevinyl alcohol copolymer also has better oxygen barrier properties when dry, and placing the ethylenevinyl alcohol copolymer layer interior to the water resistant exterior polyolefin materials enhances its oxygen barrier effectiveness.
- a function of the polyolefin layer adjacent the reaction mixture is to protect the catalyst from reacting with the functional groups on the ethylenevinyl alcohol copolymer.
- the catalyst and monomers are combined in a reaction vessel and agitated at ambient conditions for a period of time sufficient to increase viscosity of the reaction mixture sufficiently to suspend the catalyst and then placed into a cool environment to allow the reaction to proceed.
- the cool environment is normally maintained at a temperature from about -20°C to about 25°C (about - °F to about 80°F), allowing the reaction to proceed at a relatively constant pace, while removing heat and forming high molecular weight polymers. Conversions of more than 95% can be obtained with a 99% preferred. Depending on the monomers and catalyst used and reaction conditions, reaching such conversion levels may require longer reaction times, typically in the range of from about one hour to several days.
- the ultra-high molecular weight copolymer of the present invention may be ground at temperatures below the glass transition temperature of the polymer, and then mixed in a carrier fluid. Glass transition temperatures vary with the type of polymer, and typically range between -10°C to -100°C (14°F and -148°F). This temperature can vary depending upon the glass transition point of the particular copolymer, but normally such temperatures must be below the lowest glass transition point of a polymer which comprises a polymer blend.
- the ultra-high molecular weight, polymer is conveyed to coarse grinder 110.
- Coarse grinder 110 chops large chunks of copolymer into small polymer pieces, typically between VA to 114 centimeters (1/2" to 5/8") in diameter. While coarse chopper 110 may be operated at ambient temperatures, it is preferable to cool the polymer in coarse chopper 110 to between 5° to 15°C (41° to 59°F).
- the polymer in coarse chopper 110 may be cooled either internally or externally or both, with a liquid, gaseous, or solid refrigerant, or a combination thereof, but most commonly by spraying a liquid refrigerant into coarse-chopped 110, such as liquid nitrogen, liquid helium, liquid argon, or a mixture of two or more such refrigerants. It is more preferred to avoid the use of partitioning agent, as it is inert material in the final drag-reducing suspension that does not impart any drag-reducing benefits.
- Pre-cooler 120 may be an enclosed screw conveyor with nozzles for spraying a liquid refrigerant, such as liquid nitrogen, liquid helium, liquid argon, or mixtures thereof onto the small polymer pieces. While a gaseous refrigerant may also be used alone, the cooling efficiency is often too low. Pre-cooler 120 reduces the temperature of the small polymer pieces to a temperature below the glass transition temperature of the polymer.
- This temperature is preferably below -130°C (-202°F), and most preferably below -150°C (-238°F).
- These temperatures may be produced by any known methods, but use of liquid refrigerant such as that consisting essentially of liquid nitrogen, helium, argon, or a mixture of two or more such refrigerants sprayed directly onto the polymer is preferred as the resulting atmosphere reduces or eliminates hazards that exist when polymer particles are mixed with an oxygen-containing atmosphere.
- the rate of addition of the liquid refrigerant may be adjusted to maintain the polymer within the preferred temperature range.
- cryomill 130 After the small polymer pieces are cooled in pre-cooler 120, they are transported to cryomill 130. Again, this transport may be accomplished by any typical solids handling method, but often by an auger or a pneumatic transport system.
- a liquid refrigerant may be added to cryomill 130 in order to maintain the temperature of the polymer in cryomill 130 below the glass transition temperature of the ultra-high molecular weight, polymer. In one embodiment of the invention, this liquid refrigerant is added to the small polymer pieces at the entrance to cryomill 130.
- the temperature of the cryomill must be kept at a temperature below the glass transition temperature. It is preferable to maintain the temperature of the cryomill between -130°C to -155°C (- 202°F to -247°F).
- Cryomill 130 may be any of the types of cryomills known in the art, such as a hammer mill or an attrition mill, hi an attrition cryomill, the polymer pieces are ground between a rapidly rotating disk and a stationary disk to form small particles between 10 and 800 microns in diameter.
- the small particles formed in cryomill 130 are then transferred to separator 140.
- Most of the liquid refrigerant vaporizes in separator 140.
- Separator 140 acts to separate the primarily vaporized refrigerant atmosphere from the solid polymer particles, and the larger polymer particles from the small polymer particles.
- Separator 140 may be any known of separator suitable for separating particles of this size, including a rotating sieve, vibrating sieve, centrifugal sifter and a cyclone separator.
- Separator 140 vents a portion of the primarily vaporized refrigerant atmosphere from cryomill 130, and separates particles into a first fraction with less than about 400 microns in diameter from a second fraction of those with diameters of about 400 microns and above.
- the second fraction of those particles of about 400 microns and greater is discarded or preferably returned for recycle purposes to the pre-cooler for re-grinding.
- the first fraction of those particles of less than about 400 microns is then transported to mix tank 150.
- the 400 micron size for the particles is nominal and may vary or have a distribution of anywhere from about 300 to about 500 microns, depending on the separator, operating conditions, and desired end use.
- the small polymer particles (first fraction) are mixed with a suspending fluid in mix tank 150 to form a suspending fluid/polymer particles mixture.
- the suspending fluid is any liquid that is a non-solvent for the ultra-high molecular weight polymer. Water is most commonly used. For many other mixtures, lower carbon alcohols such as methanol, ethanol or their mixtures, with or without water, may also be used as the suspending fluid.
- Mix tank 150 acts to form a suspension of the polymer particles in the suspending fluid. Other components may be added, to the mix tank before, during, or after mixing the ground polymer particles with the suspending fluid in order to aid the formation of the suspension, and/or to maintain the suspension.
- glycols such as ethylene glycol or propylene glycol
- the amount of glycol added may range from 10% to 60% by weight of the suspending fluid, as needed.
- a suspension stabilizer may be used to aid in maintaining the suspension of the ultra-high molecular weight, non-tacky polymer particles.
- Typical suspension stabilizers include talc, tri- calcium phosphate, magnesium stearate, silica, polyanhydride polymers, sterically hindered alkyl phenol antioxidants, and graphite. The amount of the suspension stabilizer may be minimized or eliminated where possible to reduce the amount of material in the suspension that does not act as a drag-reducing agent.
- the amount of the suspension stabilizer added may range from 0% to 40% of the suspending fluid, by weight, but is preferably between 5% and 25%, most preferably between 8% and 12%.
- a wetting agent such as a surfactant may be added to aid in the dispersal of the polymer particles to form a uniform mixture.
- Non-ionic surfactants such as linear secondary alcohol ethoxylates, linear alcohol ethoxylates, alkylphenol exthoxylates and anionic surfactants such as alkyl benzene sulfonates and alcohol ethoxylate sulfates, e.g., sodium lauryl sulfate, are preferred.
- the amount of wetting agent added may range from 0.01% to 1% by weight, but is preferably between 0.01% and 0.1%.
- a suitable antifoaming agent may be used, typically a silicon oil based commercially available antifoam.
- antifoaming agents are antifoam agents, trademark of, and sold by, Dow Corning, Midland, Michigan; and Bubble Breaker products, trademark of, and sold by, Witco Chemical Company, Organics Division. Generally, no more than 1% of the suspending fluid by weight of the active antifoaming agent is used.
- Mix tank 150 may be blanketed with a non-oxidizing gas such as nitrogen, argon, neon, carbon dioxide, and carbon monoxide, or other similar gases, or the non-oxidizing gas may be sparged into mix tank 150 during polymer particle addition to reduce the hazard of fire or explosion resulting from the interaction between the small polymer particles.
- a non-oxidizing gas such as nitrogen, argon, neon, carbon dioxide, and carbon monoxide, or other similar gases, or the non-oxidizing gas may be sparged into mix tank 150 during polymer particle addition to reduce the hazard of fire or explosion resulting from the interaction between the small polymer particles.
- a thickening agent may be added to increase the viscosity of the mixture.
- Typical thickening agents are high molecular weight, water-soluble polymers, including polysaccharides, xanthurn gum, carboxymethyl cellulose, hydroxypropyl guar, and hydroxyethyl cellulose.
- the pH of the suspending fluid should be basic, preferably above 9 to inhibit the growth of microorganisms.
- the product resulting from the agitation in the mix tank is a stable suspension of a drag-reducing polymer in a carrier fluid suitable for use as a drag-reducing agent. This suspension may then be pumped or otherwise transported to storage for later use, or used immediately.
- the copolymers of the present invention may, instead of suspending them in a suspending fluid, be dissolved in a small amount of a heavy hydrocarbon.
- Desirable heavy hydrocarbons are often those transported through conduits, and include crude oil, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p- xylene, gasoline, diesel oil, jet fuel, low polynuclear aromatic mixtures and purified hydrocarbon distillates.
- gentle mixing should be used to avoid shear, which will result in a performance drop.
- the present invention is illustrated by the following examples.
- a catalyst was prepared by combining, in an inert environment under ambient temperature and pressure, 2.78 grams of TiCB.AA with 24.07 grams of purified petroleum distillate, together with 2.03 grams of dibutyl ether promoter according to the teachings of Mack U.S. Pat. No. 4,416,714. The solution was held for 30 minutes while stirring. The catalyst was then activated using 19.80 grams of an aluminum cocatalyst, a 25% solution of diisobutyl aluminum chloride (DIBAC) in heptane solvent ("25% DIBAC solution"). Again, the mixture was held for 30 minutes while stirring.
- DIBAC diisobutyl aluminum chloride
- a styrene-octene copolymer was prepared in an inert environment under standard temperature and pressure by mixing 47.1 grams of styrene with 453.0 grams of octene in a beaker. After stirring, 4.0 milhliters of a 25% DIBAC solution was added to the beaker. The mixture was held for 30 minutes without stirring. A 3.0 miUiliter portion of the catalyst mixture prepared in Example 1 was added to the beaker while stirring continuously. The entire mixture was allowed to react. The subsequent copolymer was subsequently tested and found to have a 95.3% conversion to polymer with an inherent viscosity of 28.1 deciliters/gram.
- Example 3 t-butylstyrene-hexene-dodecene Copolymer
- a catalyst was prepared in accordance with Example 1.
- the t-butylstyrene- hexene-dodecene terpolymer was produced in an inert environment under standard temperature and pressure by combining 134.0 grams of t-Butylstyrene, 56.0 grams of hexene, and 311.3 grams of dodecene in a beaker. After stirring, 4.0 milhliters of a 25% DIBAC solution was added to the beaker and the mixture held without stirring for 30 minutes. A 3.0 miUiliter portion of the catalyst prepared in accordance with Example 1 was added to the beaker while stirring continuously. The entire mixture was allowed to react. The subsequent polymer was tested and found to have a 91.6% conversion.
Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01997019A EP1358231B1 (en) | 2000-11-28 | 2001-11-27 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions |
AU2002248144A AU2002248144A1 (en) | 2000-11-28 | 2001-11-27 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions |
DE60135385T DE60135385D1 (en) | 2000-11-28 | 2001-11-27 | FLOW-PROPELLED POLYMERS AND SUSPENSIONS AND SOLUTIONS OF FLOW-ACCUMULATING POLYMERS |
MXPA03004740A MXPA03004740A (en) | 2000-11-28 | 2001-11-27 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions. |
CA2429939A CA2429939C (en) | 2000-11-28 | 2001-11-27 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions |
DK01997019T DK1358231T3 (en) | 2000-11-28 | 2001-11-27 | Resistance-reducing polymers and suspensions and solutions of resistance-reducing polymers |
NO20032399A NO20032399L (en) | 2000-11-28 | 2003-05-27 | Kite-reducing polymer and kite-reducing polymer suspensions and solutions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/724,049 | 2000-11-28 | ||
US09/724,049 US6576732B1 (en) | 2000-11-28 | 2000-11-28 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions |
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PCT/US2001/044361 WO2002059183A2 (en) | 2000-11-28 | 2001-11-27 | Drag-reducing polymers and drag-reducing polymer suspensions and solutions |
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US (1) | US6576732B1 (en) |
EP (1) | EP1358231B1 (en) |
AT (1) | ATE404596T1 (en) |
AU (1) | AU2002248144A1 (en) |
CA (1) | CA2429939C (en) |
DE (1) | DE60135385D1 (en) |
DK (1) | DK1358231T3 (en) |
ES (1) | ES2307672T3 (en) |
MX (1) | MXPA03004740A (en) |
NO (1) | NO20032399L (en) |
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US6894088B2 (en) | 2003-03-24 | 2005-05-17 | Baker Hughes Incorporated | Process for homogenizing polyolefin drag reducing agents |
US6946500B2 (en) | 2002-12-17 | 2005-09-20 | Baker Hughes Incorporated | Non-cryogenic process for grinding polyolefin drag reducing agents |
US7119132B2 (en) | 2002-12-17 | 2006-10-10 | Baker Hughes Incorporated | Continuous neat polymerization and ambient grinding methods of polyolefin drag reducing agents |
CN114456407A (en) * | 2020-11-09 | 2022-05-10 | 中国石油天然气集团有限公司 | Drag reducer and preparation method thereof |
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- 2001-11-27 MX MXPA03004740A patent/MXPA03004740A/en active IP Right Grant
- 2001-11-27 RU RU2003119448/04A patent/RU2003119448A/en not_active Application Discontinuation
- 2001-11-27 EP EP01997019A patent/EP1358231B1/en not_active Expired - Lifetime
- 2001-11-27 ES ES01997019T patent/ES2307672T3/en not_active Expired - Lifetime
- 2001-11-27 AT AT01997019T patent/ATE404596T1/en not_active IP Right Cessation
- 2001-11-27 CA CA2429939A patent/CA2429939C/en not_active Expired - Lifetime
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6946500B2 (en) | 2002-12-17 | 2005-09-20 | Baker Hughes Incorporated | Non-cryogenic process for grinding polyolefin drag reducing agents |
US7119132B2 (en) | 2002-12-17 | 2006-10-10 | Baker Hughes Incorporated | Continuous neat polymerization and ambient grinding methods of polyolefin drag reducing agents |
US6894088B2 (en) | 2003-03-24 | 2005-05-17 | Baker Hughes Incorporated | Process for homogenizing polyolefin drag reducing agents |
CN114456407A (en) * | 2020-11-09 | 2022-05-10 | 中国石油天然气集团有限公司 | Drag reducer and preparation method thereof |
CN114456407B (en) * | 2020-11-09 | 2024-03-01 | 中国石油天然气集团有限公司 | Drag reducer preparation method and drag reducer |
Also Published As
Publication number | Publication date |
---|---|
CA2429939C (en) | 2011-04-26 |
EP1358231B1 (en) | 2008-08-13 |
EP1358231A4 (en) | 2004-06-23 |
AU2002248144A1 (en) | 2002-08-06 |
NO20032399D0 (en) | 2003-05-27 |
DE60135385D1 (en) | 2008-09-25 |
ES2307672T3 (en) | 2008-12-01 |
WO2002059183A8 (en) | 2004-03-11 |
MXPA03004740A (en) | 2005-01-25 |
NO20032399L (en) | 2003-07-15 |
CA2429939A1 (en) | 2002-08-01 |
RU2003119448A (en) | 2004-12-27 |
US6576732B1 (en) | 2003-06-10 |
WO2002059183A3 (en) | 2002-09-19 |
EP1358231A2 (en) | 2003-11-05 |
DK1358231T3 (en) | 2008-11-24 |
ATE404596T1 (en) | 2008-08-15 |
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