WO2002043849A2

WO2002043849A2 - Drag-reducing polymer suspensions

Info

Publication number: WO2002043849A2
Application number: PCT/US2001/044419
Authority: WO
Inventors: Kenneth W. Smith; Stuart Milligan; Ray L. Johnston; Jana L. Krottinger
Original assignee: Conoco, Inc.
Priority date: 2000-11-28
Filing date: 2001-11-27
Publication date: 2002-06-06
Also published as: WO2002043849A3; WO2002043849A8; AU2002239357A1

Abstract

A drag-reducing suspension is described, along with a process for manufacturing the drag-reducing suspension. The drag-reducing suspension is easily transprotable, non-hazardous, easily handled, and provides a significant increase in drag-reducing capability over existing products. The drag-reducing suspension is manufactured by grinding an ultra-high molecular weight, non-tacky polymer in the absence of a partitioning agent.

Description

DRAG-REDUCING POLYMER SUSPENSIONS

The present invention relates to drag-reducing polymer suspensions and their method of manufacture. More specifically, this invention relates to a method for preparing ultra-high molecular weight, non-tacky, substantially non-crystalline hydrocarbon soluble polymers with decreased dissolution time in hydrocarbons flowing through conduits. 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. The general propensity of non-crosslinked elastomeric polymers (elastomers) to cold flow and agglomerate is well-known. Polymers of this sort cannot be pelletized or put into discrete form and then stored for any reasonable period of time without the materials flowing together to form large agglomerates. Because of such difficulties, elastomers are normally shipped and used as bales of rubber. However, such bales must be handled on expensive equipment and cannot be pre-blended. In addition, polymers such as the drag-reducing additives described are not susceptible to such balings, since cold flow is extremely severe. Further, dissolution time for such drag- reducing materials from a polymer state in the flowing hydrocarbons to a dissolved state is so lengthy as to severely reduce the effectiveness of this material as a drag- reducing substance.

Numerous attempts have been made to overcome the disadvantages inherent in cold-flowing polymers. Representative, but non-exhaustive, of such art is that described in U.S. Pat. No. 3,791,913, wherein elastomeric pellets are surface cured, i.e., vulcanized to a minor depth in order to maintain the unvulcanized interior of the polymer in a "sack" of cured material, and U.S. Pat. No. 4,147,677, describing a method of preparing a free-flowing, finely divided powder of neutralized sulfonated elastomer by admixing with fillers and oils. This reference does not teach a method for making free-flowing powders of non-elastomeric material. U.S. 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. U.S. Pat. No. 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. U.S. Pat. No. 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. Depending upon the temperature of the hydrocarbon and the concentration at which the drag-reducing polymer solution is injected, significant time elapses before dissolution and resulting drag reduction. 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. Also, such ultra-high molecular weight polymer solutions become very viscous as polymer content increases, in some cases limiting the practical application of these solutions to those containing no more than about 15 weight percent polymer. This makes complex equipment necessary for storing, dissolving, pumping, and injecting metered quantities of drag-reducing material into flowing hydrocarbons. Another way to introduce ultra-high molecular weight polymers into the flowing hydrocarbon stream is through a suspension. The 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 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. U.S. Pat. No. 4,584,244, which is hereby incorporated by reference, 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, 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.

Accordingly, a drag-reducing suspension and a method of producing a drag- reducing suspension are disclosed herein. One embodiment of the present invention is drawn to a method for the preparation of a drag-reducing polymer suspension wherein an ultra-high molecular weight, non-tacky polymer is ground at a temperature below the glass-transition temperature of the ultra-high molecular weight, non-tacky polymer to form ground polymer particles. The grinding is done without the presence of a partitioning agent. The ground polymer particles are then mixed with a suspending fluid to form the drag-reducing polymer suspension. In another embodiment of the present invention, drag-reducing polymer suspension is prepared by cooling an ultra- high molecular weight non-tacky polymer with nitrogen, helium argon, or dry ice. The ultra-high molecular weight non-tacky polymer is a poly(α-olefin) prepared from a monomer with a carbon chain length of 10 carbons or more, ultra-high molecular weight polybutadiene, a copolymer of styrene and butadiene, a copolymer of styrene and an α-olefin with a carbon chain length of 10 carbons or more, a copolymer of an

alkyl styrene and an α-olefin with a carbon chain length of 10 carbons or more or a ultra-high molecular weight linear low density polyethylene. The ultra-high molecular weight non-tacky polymer is then ground at a temperature below the glass transition temperature of the ultra-high molecular weight non-tacky polymer to form ground polymer particles. No partitioning agent is present during the grinding process. The ground polymer particles are then mixed with a suspending fluid, and a wetting agent, an antifoaming agent and a thickening agent are then added. Another embodiment of the present invention is drawn to a drag-reducing polymer suspension made from an ultra-high molecular weight, non-tacky polymer, and a suspending fluid. The suspension contains no suspension stabilizer or partitioning agent. One advantage of the present invention is that 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 the flowing hydrocarbon stream. Yet another advantage of the present invention is that the extra bulk and cost associated with the inert partitioning agent may be eliminated or reduced, allowing easier transport. 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. 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.

In the present invention, ultra-high molecular weight, non-tacky, polymers are ground at temperatures below the glass transition temperature of the polymer or polymer blends, and then mixed in a suspending fluid. These polymers are generally not highly-crystalline. An ultra-high molecular weight, non-tacky polymer is one that will not reagglomerate by cold flowing at temperatures above its glass transition temperature, and has a molecular weight of greater than 1 million, preferably more than 5 million. Glass transition temperatures vary with the type of polymer, and typically range between - 10°C and -100°C (14°F and - 148°F). This temperature can vary depending upon the glass transition point of the particular polymer or polymer blend, but normally such grinding temperatures must be below the lowest glass transition point of any polymer that comprises a polymer blend. Preferred ultra-high molecular weight, non-tacky polymers include: poly(α-

olefins) prepared from monomers with carbon chain lengths of ten carbons or more, ultra-high molecular weight polybutadienes, copolymers of styrene and butadiene, copolymers of styrene and α-olefins with carbon chain lengths of ten carbons or more,

copolymers of alkyl styrenes and α-olefins prepared from monomers with carbon chain

lengths of ten carbons or more, ultra-high molecular weight linear low density polyethylenes, and mixtures of two or more such polymers. Other polymers of a generally similar nature that are non-tacky above their glass transition temperature and are soluble in the liquid hydrocarbon that do not cold flow and reagglomerate will also function in the invention. As shown in Figure 1, the ultra-high molecular weight, non-tacky polymer is conveyed to coarse grinder 110. Coarse grinder 110 chops large chunks of polymer into small polymer pieces, typically between 1 to VA centimeters (3/8" 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°C to 15°C (41°F 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 liquid refrigerants, or by mixing the ultra-high molecular weight, non-tacky polymer with dry ice (solid carbon dioxide) with or without the above-mentioned liquid refrigerants. Partitioning agent should not be used in coarse chopper 110 so that the amount of inert material in the final suspension that does not perform as a drag reducer is reduced. The small pieces of polymer formed in coarse chopper 110 are then transported to pre-cooler 120. This transport may be accomplished by any number of typical solids handling methods, but is most often accomplished through the use of an auger or a pneumatic transport system. 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 a mixture of two or more such liquid refrigerants 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.

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 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, non-tacky 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° 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. In 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 smaller polymer particles. Separator 140 may be any known type of separator suitable for separating particles of this size, including a rotating sieve, vibrating sieve, centrifugal sifter and 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 400 microns and above. The second fraction of those particles of about 400 microns and greater is discarded or preferably returned for recycling 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 5 400 micron size for the particles is nominal and may vary or have a distribution 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 0 fluid is any liquid that is a non-solvent for the ultra-high molecular weight non-tacky polymer. Water is most commonly used. For many other mixtures, low carbon alcohols such as methanol, ethanol or their mixtures, with or without water, may also be used as the suspending fluid. Mix tank 150 may be any type of vessel designed to agitate the mixture to achieve uniform composition of the suspending fluid polymer 5 particles mixture, typically a stirred tank reactor. Mix tank 150 acts to form a suspension of the polymer particles in the suspending fluid. Other components may be added to mix tank 150 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. For instance, glycols, such as ethylene glycol or propylene glycol, may 0 be added for freeze protection or as a density balancing agent. The amount of glycol added may range from 10% to 60% 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 0.1% by weight of the suspending agent, but is preferably between 0.01% and 0.1 %. In order to prevent foaming of the suspending fluid/polymer particle mixture during agitation, a suitable antifoaming agent may be used, typically a silicon oil based commercially available antifoam. Generally, no more than 1% of the suspending fluid by weight of the active antifoaming agent is used. Representative but non-exhaustive examples of antifoaming agents are the trademark of, and sold by, Dow Corning, Midland, Michigan; and Bubble Breaker products, trademark of, and sold by, Witco Chemical Company, Organics Division. 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. After the suspending fluid/polymer particle mixture is agitated to form a uniform mixture, a thickening agent may be added to increase the viscosity of the mixture. The increase in viscosity retards separation of the suspension. Typical thickening agents are high molecular weight, water-soluble polymers, including polysaccharides, xanthum gum, carboxymethyl cellulose, hydroxypropyl guar, and hydroxyethyl cellulose. Where water is the suspending fluid, 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 suspending 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 liquid refrigerant, suspending fluid, suspension stabilizer, glycol, wetting agent, anti-foaming agent, and thickener, should be combined in effective amounts to accomplish the results desired and to avoid hazardous operating conditions. These amounts will vary depending on individual process conditions and can be determined by one of ordinary skill in the art. Also, where temperatures and pressures are indicated, those given are a guide to the most reasonable and best conditions presently known for those processes, but temperatures and pressures outside of those ranges can be used within the scope of this invention. The range of values expressed as between two values is intended to include the value stated in the range.

Claims

1. A method for the preparation of a drag-reducing polymer suspension comprising: a) grinding an ultra-high molecular weight, non-tacky polymer at a temperature below the glass transition temperature of the ultra-high molecular weight, non-tacky polymer in the absence of a partitioning agent to form ground polymer particles; and b) mixing the ground polymer particles with a suspending fluid to form the drag-reducing polymer suspension.

2. The method as described in claim 1, wherein the ultra-high molecular weight non-tacky polymer is selected from the group consisting of a poly(α- olefin) prepared from a monomer with a carbon chain length of 10 carbons or more, an ultra-high molecular weight polybutadiene, a copolymer of styrene and butadiene, a copolymer of styrene and an α-olefin with a carbon chain length of 10 carbons or more, a copolymer of an alkyl styrene and an α-olefin with a carbon chain length of 10 carbons or more, an ultra-high molecular weight linear low density polyethylene, and mixtures thereof.

3. The method as described in claim 1, further comprising prior to or simultaneous with step a): cooling the non-tacky thermoplastic polymer with one or more refrigerants selected from the group consisting of liquid nitrogen, liquid helium, liquid argon, dry ice, and mixtures thereof.

4. The method as described in claim 3, further comprising prior to step a) cooling the ultra-high molecular weight non-tacky polymer to a temperature below -130 ° C.

5. The method of claim 1, further comprising after step a) and before step b): separating ground polymer particles into a first fraction with a diameter of less than 400 microns from a second fraction with a diameter of 400 microns or greater; and regrinding the second fraction of the ground polymer particles with a diameter of 400 microns or greater.

6. The method of claim 1, wherein the suspending fluid comprises water.

7. The method of claim 1, wherein the suspending fluid further comprises a suspension stabilizer.

8. The method of claim 7, wherein the suspending fluid further comprises one or more components selected from the group consisting of a wetting agent, an antifoaming agent, and a thickening agent.

9. A method for the preparation of a drag-reducing polymer suspension comprising: a) cooling an ultra-high molecular weight non-tacky polymer with one or more refrigerants selected from the group consisting of nitrogen, helium argon, and dry ice wherein the ultra-high molecular weight non-tacky polymer is selected from the group consisting of a poly(α-olefin) prepared from a monomer with a carbon chain length of 10 carbons or more, an ultra-high molecular weight polybutadiene, a copolymer of styrene and butadiene, a copolymer of styrene and an α-olefin with a carbon chain length of 10 carbons or more, a copolymer of an alkyl styrene and an α- olefin with a carbon chain length of 10 carbons or more, an ultra-high molecular weight linear low density polyethylene, and mixtures thereof; b) grinding the ultra-high molecular weight non-tacky polymer at a temperature below the glass transition temperature of the ultra-high molecular weight non-tacky polymer in the absence of a partitioning agent to form ground polymer particles; c) mixing the ground polymer particles with a suspending fluid, wherein the suspending fluid further comprises one or more compounds selected from the group consisting of a wetting agent, an antifoaming agent, and a thickening agent.

10. A drag-reducing polymer suspension comprising: a) an ultra-high molecular weight, non-tacky polymer; and b) a suspending fluid; wherein the drag-reducing polymer suspension contains no suspension stabilizer or partitioning agent.

11. The method as described in claim 10, wherein the ultra-high molecular weight non-tacky thermoplastic polymer is selected from the group consisting of a poly(α-olefin) prepared from a monomer with a carbon chain length of 10 carbons or more, an ultra-high molecular weight polybutadiene, a copolymer of styrene and butadiene, a copolymer of styrene and an α-olefin with a carbon chain length of 10 carbons or more, a copolymer of an alkyl styrene and an α-olefin with a carbon chain length of 10 carbons or more, an ultra-high molecular weight linear low density polyethylene, and mixtures thereof.

12. The drag-reducing polymer suspension of claim 10 wherein suspending fluid comprises water.

13. The drag-reducing polymer suspension of claim 12, wherein the suspending fluid further comprises one or more compounds selected from the group consisting of a wetting agent, an antifoaming agent, and a thickening agent.

14. A drag-reducing polymer suspension comprising: a) an ultra-high molecular weight non-tacky polymer selected from the group consisting of a poly(α-olefin) prepared from a monomer with a carbon chain length of 10 carbons or more, an ultra-high molecular weight polybutadiene, a copolymer of styrene and butadiene, a copolymer of styrene and an α- olefin with a carbon chain length of 10 carbons or more, a copolymer of an alkyl styrene and an α-olefin with a carbon chain length of 10 carbons or more, an ultra-high molecular weight linear low density polyethylene and mixtures thereof; b) water; c) a suspension stabilizer; d) a wetting agent; e) an antifoaming agent; and f) a thickening agent.