CA2447798A1 - Drag reducing agent slurries having alfol alcohols and processes for forming them - Google Patents
Drag reducing agent slurries having alfol alcohols and processes for forming them Download PDFInfo
- Publication number
- CA2447798A1 CA2447798A1 CA 2447798 CA2447798A CA2447798A1 CA 2447798 A1 CA2447798 A1 CA 2447798A1 CA 2447798 CA2447798 CA 2447798 CA 2447798 A CA2447798 A CA 2447798A CA 2447798 A1 CA2447798 A1 CA 2447798A1
- Authority
- CA
- Canada
- Prior art keywords
- reducing agent
- drag reducing
- alcohol
- forming
- polyalphaolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0391—Affecting flow by the addition of material or energy
Abstract
A composition including a polyalphaolefin and at least one alfol alcohol tha t function as drag reducing agent slurries and a process for the preparation o f the drag reducing agent slurries are disclosed. The process includes contacting alpha olefin monomers with a catalyst in a reactant mixture to fo rm a polyalphaolefin. The polyalphaolefin is combined with at least one alfol alcohol to form a drag reducing agent slurry. A process for reducing drag in a conduit is also disclosed.
Description
DRAG REDUCING AGENT SLURRIES HAVING
ALFOL ALCOHOLS AND PROCESSES FOR
FORMING DRAG REDUCING AGENT SLURRIES HAVING
ALFOL ALCOHOLS
RELATED APPLICATION
This application claims the benefit of U. S. Non-Provisional Patent Application Serial No.
09/877,341, filed June 8, 2001.
BACKGROUND OF THE INVENTION
1. Field Of The Invention This invention relates to drag reducing agent slurries, and in particular, drag reducing agent slurries having alfol alcohols used in methods for improving flow of hydrocarbons through conduits, particularly pipelines. The invention also relates to methods for making drag reducing agent slurries.
2. Description Of Related Art Generally speaking, the flow of liquid in a conduit, such as a pipeline, results in frictional energy losses. As a result of this energy loss, the pressure of the liquid in the conduit decreases along the conduit in the direction of the flow. For a conduit of fixed diameter, this pressure drop increases with increasing flow rate. When the flow in the conduit is turbulent (Reynold's number greater than about 2100), certain high molecular weight polymers can be added to the liquid flowing through the conduit to reduce the frictional energy losses and alter the relationship between pressure drop and flow rate. These polymers are sometimes referred to as drag reducing agents ("DRAs"), and they interact with the turbulent flow processes and reduce frictional pressure losses such that the pressure drop for a given flow rate is less, or the flow rate for a given pressure drop is greater. Because DRAB reduce frictional energy losses, increase in the flow capability of pipelines, hoses and other conduits in which liquids flow can be achieved.
DRAs can also decrease the cost of pumping fluids, the cost of equipment used to pump fluids, and provide for the use of a smaller pipe diameter for a given flow capacity.
One type of drag reducing agent presently utilized is a slurry. Drag reducing agent slurries are those formed by polymerizing monomers, preferably alpha olefin monomers, to form polymers that are subsequently ground to a small size and suspended in a liquid vehicle, i.e.
suspending agent. Drag reducing agent slurries facilitate the rapid dispersion of the drag reducing agent through out the hydrocarbon being transported through a conduit. While various polymerization methods, reactants, partitioning agents, and slurries have been published in the patent literature, many of those methods include components of drag reducing agent slurries that increase the cost of production of the drag reducing agents slurry. Further, some components of drag reducing agent slurries cannot be removed from the hydrocarbon after they have been introduced into the conduit. In many, if not all instances, these slurry components remaining in the hydrocarbon foul the hydrocarbon in the conduit, thereby decreasing the number of uses of the hydrocarbon and/or the effectiveness of the use of the hydrocarbon.
Generally, water soluble alcohols, water, glycols, glycerin, and water/water-soluble alcohol mixtures (referred to herein as "water-alcohol mixtures") are known in the art as being suspending materials. All of these prior attempts have shortcomings. For example, the addition of water poses serious implications as it relates to water contamination, i.e., hazing, of motor fuel, e.g., gasoline, diesel, and kerosene, in pipelines. Other significant problems associated with the inclusion of water in the drag reducing agent slurries include additional wastewater generation, thereby requiring disposal, increased systems corrosion, increased biological activity in "free-water" fallout areas within the pipeline and terminal storage tanks.
In other prior drag reducing agent slurries, small amounts of polar and/or other water soluble alcohols have been linked with serious biological upsets and resulting operational problems due, in part, to food to microorganism balances, undesirable biological facilitation, excessive biological oxygen demand and chemical oxygen demand loading, and bio-mass bulking within various refineries' activated sludge processes. These refineries depend on activated sludge processes as the most practical and efficient means of treating wastewater received and generated within the refining processes prior to its reintroduction, or discharge outside of, the refineries. In fact, some refineries have set strictly enforced limits on drag reducing agents slurries containing water soluble alcohols, glycols, and glycerins received into their refineries from crude oil pipelines.
Additionally, the inclusion of water, glycols, glycerin, and water-alcohol mixtures as a part of, or as the entire, suspending agent, generally requires the inclusion of other components, thereby increasing the cost of formation of the drag reducing agent, increasing potential harm to refineries, and increasing cost ofrefining the hydrocarbon due to the cost of removal and disposal of these additives. For example, surfactants, e.g., nonylphenol ethyoxylate, alkaline metal stearates, e.g., magnesium stearate and calcium stearate used as partitioning agents to reduce the potential of the finely ground polymer solids from re-agglomerating and thus destabilizing the drag reducing agent slurry, and biocides are included in some prior drag reducing agent slurries.
Some refineries have prohibited the use of drag reducing agent slurries containing surfactants and metal stearates in their crude oil pipeline because, upon entering the refining facilities, the surfactants and alkaline metal stearates axe believed to be responsible for upset the refining process, including the refineries vital desalting processes.
Siloxane containing antifoams are also usually included in prior drag reducing agent slurries to reduce or eliminate the potential of foaming within the end user's pipeline system following the addition of drag reducing agent slurry. Siloxane containing antifoams are objectionable components because they axe believed to be responsible for causing deleterious effects~on various refining processes and facilitate fouling within the refining process.
Generally, all of these additional components are insoluble contaminants in the hydrocarbon stream in the pipeline. Such contaminants are undesirable and the art has continually sought a drag reducing agent slurry that excludes these undesirable components.
Another disadvantage of the prior drag reducing agent slurries is that the "shelf life" of these drag reducing agent slurries are extremely short and they require storage within strict temperature ranges. For example, one prior drag reducing agent slurry containing water and water-alcohol mixtures as the suspending agent requires its storage to be within expensive temperature controlled housing/containment, or container/building, to help insure its usability and stability, (i.e. between 35-85° F). Without proper temperature control in such a storage facility this prior drag reducing agent slurry becomes frozen at or near the freezing point of water, or microbiologically decomposes and destabilizes/ferments in an unacceptably short time as ambient temperatures move above 90°F. As known to persons skilled in the art, a large portion of crude oil is produced in extremely hot regions of the world, e.g., Saudi Arabia, Venezuela, Texas, Mexico, and Gulf of Mexico, and extremely cold regions of the world, e.g., Alaska, Siberia, and Canada. Accordingly, these prior drag reducing agent slurries are not suitable for use in these environments without additional storage facilities.
Another shortcoming of prior drag reducing agent slurries is that the polymer load per gallon, i.e., the amount of active polymer that can be suspended in a gallon of suspending agent without the polymer particles re-agglomerating, is limited. Applicants are unaware of any drag reducing agent slurry that contains greater than about 2.0 pounds of this polymer per gallon of suspending material. Addition of polymer in amounts greater than about 2.0 pounds of polymer per gallon results in an extremely viscous and unstable drag reducing agent slurry. The ability to increase the polymer solids as a ratio to the total weight of the slurry offers improved treating performance, better logistical benefits and lower logistical and capital costs.
Still another shortcoming of prior drag reducing agent slurries is that the drag reducing agent slurry is not capable of being "re-suspended" should the polymer "separate" from its suspending material. As prior drag reducing agent slurries age, the polymer has a tendency to separate by settling to the bottom or rising to the top of the tank, or other container, containing the drag reducing agent slurry. When this occurs, the polymer further re-agglomerates and cannot be "re-suspended." As such, the drag reducing agent slurry is of no value and new, or "fresh" drag reducing agent slurry is required.
Additionally, none of the prior attempts provide the surprisingly unexpected results of using the suspending materials of the present invention. For instance, the suspending materials of the present invention provide a drag reducing agent slurry that has an increased shelf life, a minimal impact on pipeline and refinery operations, and permit formation of a drag reducing agent slurries having more active polymer per gallon than any other prior drag reducing agent slurries.
Accordingly, prior to the development of the present invention, there has been no drag reducing agent slurry, process for forming a drag reducing agent slurry, or process for reducing drag in a conduit, which: does not negatively impact wastewater treatment facilities; permits longer term storage without biological degradation and temperature destabilization; does not insult motor fuels and other refined products; reduces instances of re-agglomeration; and provides a more stable drag reducing agent slurry during production, transportation, storage, and use. Therefore, the art has sought a drag reducing agent slurry, process for forming a drag reducing agent slurry, and process for reducing drag in a conduit, which: does not negatively impact wastewater treatment facilities; permits longer term storage without biological degradation and temperature destabilization; does not insult motor fuels and other refined products; reduces instances of re-agglomeration; and provides a more stable drag reducing agent slurry during production, transportation, storage, and use.
While various components of drag reducing slurries have been used in connection with certain drag reducing agents, the inventors are not aware of any patents or publications showing alfol alcohols being used as a component of drag reducing agent slurries. For example, U.S.
Patents Nos. 6,172,151; 5,244,937; 5,449,732; 5,504,131; 5,504,132; and 5,539,044 disclose certain components of drag reducing agent slurries, but do not disclose or suggest the alfol alcohols as a component of drag reducing agent slurries.
SUMMARY OF INVENTION
In accordance with the invention, the foregoing advantages have been achieved through the present process for forming a drag reducing agent slurry comprising:
forming a drag reducing agent; and mixing the drag reducing agent with at least one alfol alcohol.
A further feature of the process for forming a drag reducing agent slurry is that the alfol alcohol rnay be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for forming a drag reducing agent slurry comprising: contacting alpha olefin monomer with a catalyst in a reactant mixture; polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the process for forming a drag reducing agent slurry is that the catalyst may be a transition metal catalyst. Another feature of the process for forming a drag reducing agent slurry is that the transition metal catalyst may be a Ziegler-Natta catalyst. An additional feature of the process for forming a drag reducing agent slurry is that the Ziegler-Natta catalyst may be titanium trichloride. Still another feature of the process for forming a drag reducing agent slurry is that the reactant mixture may include at least one co-catalyst. A further feature of the process for forming a drag reducing agent slurry is that the at least one co-catalyst may be selected from the group consisting of alkylaluminoxanes, halohydrocarbons, diethylaluminum chloride, and dibutylaluminum chloride. Another feature of the process for forming a drag reducing agent slurry is that the alpha olefin monomers may comprise homopolymers, terpolymers or copolymers. An additional feature of the process for forming a drag reducing agent slurry is that the alpha olefin monomers may comprise co-polymers of 1-hexene and 1-dodecene alpha olefins or co-polymers of 1-octene and 1-tetradodecene alpha olefins. Still another feature of the process for forming a drag reducing agent slurry is that the polyalphaolefin may be an ultra-high molecular weight polyalphaolefin having an inherent viscosity of at least about 10 deciliters per gram and may be amorphous with substantially no crystalline particles. A further feature of the process for forming a drag reducing agent slurry is that the process may further comprise the step of cryogrinding the polyalphaolefin prior to mixing the polyalphaolefin with the at least one alfol alcohol. Still another feature of the process for forming a drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected fromthe group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol formed by mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, I-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefm and at least one alfol alcohol formed by contacting alpha olefin monomers with a catalyst in a reactant mixture;
ALFOL ALCOHOLS AND PROCESSES FOR
FORMING DRAG REDUCING AGENT SLURRIES HAVING
ALFOL ALCOHOLS
RELATED APPLICATION
This application claims the benefit of U. S. Non-Provisional Patent Application Serial No.
09/877,341, filed June 8, 2001.
BACKGROUND OF THE INVENTION
1. Field Of The Invention This invention relates to drag reducing agent slurries, and in particular, drag reducing agent slurries having alfol alcohols used in methods for improving flow of hydrocarbons through conduits, particularly pipelines. The invention also relates to methods for making drag reducing agent slurries.
2. Description Of Related Art Generally speaking, the flow of liquid in a conduit, such as a pipeline, results in frictional energy losses. As a result of this energy loss, the pressure of the liquid in the conduit decreases along the conduit in the direction of the flow. For a conduit of fixed diameter, this pressure drop increases with increasing flow rate. When the flow in the conduit is turbulent (Reynold's number greater than about 2100), certain high molecular weight polymers can be added to the liquid flowing through the conduit to reduce the frictional energy losses and alter the relationship between pressure drop and flow rate. These polymers are sometimes referred to as drag reducing agents ("DRAs"), and they interact with the turbulent flow processes and reduce frictional pressure losses such that the pressure drop for a given flow rate is less, or the flow rate for a given pressure drop is greater. Because DRAB reduce frictional energy losses, increase in the flow capability of pipelines, hoses and other conduits in which liquids flow can be achieved.
DRAs can also decrease the cost of pumping fluids, the cost of equipment used to pump fluids, and provide for the use of a smaller pipe diameter for a given flow capacity.
One type of drag reducing agent presently utilized is a slurry. Drag reducing agent slurries are those formed by polymerizing monomers, preferably alpha olefin monomers, to form polymers that are subsequently ground to a small size and suspended in a liquid vehicle, i.e.
suspending agent. Drag reducing agent slurries facilitate the rapid dispersion of the drag reducing agent through out the hydrocarbon being transported through a conduit. While various polymerization methods, reactants, partitioning agents, and slurries have been published in the patent literature, many of those methods include components of drag reducing agent slurries that increase the cost of production of the drag reducing agents slurry. Further, some components of drag reducing agent slurries cannot be removed from the hydrocarbon after they have been introduced into the conduit. In many, if not all instances, these slurry components remaining in the hydrocarbon foul the hydrocarbon in the conduit, thereby decreasing the number of uses of the hydrocarbon and/or the effectiveness of the use of the hydrocarbon.
Generally, water soluble alcohols, water, glycols, glycerin, and water/water-soluble alcohol mixtures (referred to herein as "water-alcohol mixtures") are known in the art as being suspending materials. All of these prior attempts have shortcomings. For example, the addition of water poses serious implications as it relates to water contamination, i.e., hazing, of motor fuel, e.g., gasoline, diesel, and kerosene, in pipelines. Other significant problems associated with the inclusion of water in the drag reducing agent slurries include additional wastewater generation, thereby requiring disposal, increased systems corrosion, increased biological activity in "free-water" fallout areas within the pipeline and terminal storage tanks.
In other prior drag reducing agent slurries, small amounts of polar and/or other water soluble alcohols have been linked with serious biological upsets and resulting operational problems due, in part, to food to microorganism balances, undesirable biological facilitation, excessive biological oxygen demand and chemical oxygen demand loading, and bio-mass bulking within various refineries' activated sludge processes. These refineries depend on activated sludge processes as the most practical and efficient means of treating wastewater received and generated within the refining processes prior to its reintroduction, or discharge outside of, the refineries. In fact, some refineries have set strictly enforced limits on drag reducing agents slurries containing water soluble alcohols, glycols, and glycerins received into their refineries from crude oil pipelines.
Additionally, the inclusion of water, glycols, glycerin, and water-alcohol mixtures as a part of, or as the entire, suspending agent, generally requires the inclusion of other components, thereby increasing the cost of formation of the drag reducing agent, increasing potential harm to refineries, and increasing cost ofrefining the hydrocarbon due to the cost of removal and disposal of these additives. For example, surfactants, e.g., nonylphenol ethyoxylate, alkaline metal stearates, e.g., magnesium stearate and calcium stearate used as partitioning agents to reduce the potential of the finely ground polymer solids from re-agglomerating and thus destabilizing the drag reducing agent slurry, and biocides are included in some prior drag reducing agent slurries.
Some refineries have prohibited the use of drag reducing agent slurries containing surfactants and metal stearates in their crude oil pipeline because, upon entering the refining facilities, the surfactants and alkaline metal stearates axe believed to be responsible for upset the refining process, including the refineries vital desalting processes.
Siloxane containing antifoams are also usually included in prior drag reducing agent slurries to reduce or eliminate the potential of foaming within the end user's pipeline system following the addition of drag reducing agent slurry. Siloxane containing antifoams are objectionable components because they axe believed to be responsible for causing deleterious effects~on various refining processes and facilitate fouling within the refining process.
Generally, all of these additional components are insoluble contaminants in the hydrocarbon stream in the pipeline. Such contaminants are undesirable and the art has continually sought a drag reducing agent slurry that excludes these undesirable components.
Another disadvantage of the prior drag reducing agent slurries is that the "shelf life" of these drag reducing agent slurries are extremely short and they require storage within strict temperature ranges. For example, one prior drag reducing agent slurry containing water and water-alcohol mixtures as the suspending agent requires its storage to be within expensive temperature controlled housing/containment, or container/building, to help insure its usability and stability, (i.e. between 35-85° F). Without proper temperature control in such a storage facility this prior drag reducing agent slurry becomes frozen at or near the freezing point of water, or microbiologically decomposes and destabilizes/ferments in an unacceptably short time as ambient temperatures move above 90°F. As known to persons skilled in the art, a large portion of crude oil is produced in extremely hot regions of the world, e.g., Saudi Arabia, Venezuela, Texas, Mexico, and Gulf of Mexico, and extremely cold regions of the world, e.g., Alaska, Siberia, and Canada. Accordingly, these prior drag reducing agent slurries are not suitable for use in these environments without additional storage facilities.
Another shortcoming of prior drag reducing agent slurries is that the polymer load per gallon, i.e., the amount of active polymer that can be suspended in a gallon of suspending agent without the polymer particles re-agglomerating, is limited. Applicants are unaware of any drag reducing agent slurry that contains greater than about 2.0 pounds of this polymer per gallon of suspending material. Addition of polymer in amounts greater than about 2.0 pounds of polymer per gallon results in an extremely viscous and unstable drag reducing agent slurry. The ability to increase the polymer solids as a ratio to the total weight of the slurry offers improved treating performance, better logistical benefits and lower logistical and capital costs.
Still another shortcoming of prior drag reducing agent slurries is that the drag reducing agent slurry is not capable of being "re-suspended" should the polymer "separate" from its suspending material. As prior drag reducing agent slurries age, the polymer has a tendency to separate by settling to the bottom or rising to the top of the tank, or other container, containing the drag reducing agent slurry. When this occurs, the polymer further re-agglomerates and cannot be "re-suspended." As such, the drag reducing agent slurry is of no value and new, or "fresh" drag reducing agent slurry is required.
Additionally, none of the prior attempts provide the surprisingly unexpected results of using the suspending materials of the present invention. For instance, the suspending materials of the present invention provide a drag reducing agent slurry that has an increased shelf life, a minimal impact on pipeline and refinery operations, and permit formation of a drag reducing agent slurries having more active polymer per gallon than any other prior drag reducing agent slurries.
Accordingly, prior to the development of the present invention, there has been no drag reducing agent slurry, process for forming a drag reducing agent slurry, or process for reducing drag in a conduit, which: does not negatively impact wastewater treatment facilities; permits longer term storage without biological degradation and temperature destabilization; does not insult motor fuels and other refined products; reduces instances of re-agglomeration; and provides a more stable drag reducing agent slurry during production, transportation, storage, and use. Therefore, the art has sought a drag reducing agent slurry, process for forming a drag reducing agent slurry, and process for reducing drag in a conduit, which: does not negatively impact wastewater treatment facilities; permits longer term storage without biological degradation and temperature destabilization; does not insult motor fuels and other refined products; reduces instances of re-agglomeration; and provides a more stable drag reducing agent slurry during production, transportation, storage, and use.
While various components of drag reducing slurries have been used in connection with certain drag reducing agents, the inventors are not aware of any patents or publications showing alfol alcohols being used as a component of drag reducing agent slurries. For example, U.S.
Patents Nos. 6,172,151; 5,244,937; 5,449,732; 5,504,131; 5,504,132; and 5,539,044 disclose certain components of drag reducing agent slurries, but do not disclose or suggest the alfol alcohols as a component of drag reducing agent slurries.
SUMMARY OF INVENTION
In accordance with the invention, the foregoing advantages have been achieved through the present process for forming a drag reducing agent slurry comprising:
forming a drag reducing agent; and mixing the drag reducing agent with at least one alfol alcohol.
A further feature of the process for forming a drag reducing agent slurry is that the alfol alcohol rnay be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for forming a drag reducing agent slurry comprising: contacting alpha olefin monomer with a catalyst in a reactant mixture; polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the process for forming a drag reducing agent slurry is that the catalyst may be a transition metal catalyst. Another feature of the process for forming a drag reducing agent slurry is that the transition metal catalyst may be a Ziegler-Natta catalyst. An additional feature of the process for forming a drag reducing agent slurry is that the Ziegler-Natta catalyst may be titanium trichloride. Still another feature of the process for forming a drag reducing agent slurry is that the reactant mixture may include at least one co-catalyst. A further feature of the process for forming a drag reducing agent slurry is that the at least one co-catalyst may be selected from the group consisting of alkylaluminoxanes, halohydrocarbons, diethylaluminum chloride, and dibutylaluminum chloride. Another feature of the process for forming a drag reducing agent slurry is that the alpha olefin monomers may comprise homopolymers, terpolymers or copolymers. An additional feature of the process for forming a drag reducing agent slurry is that the alpha olefin monomers may comprise co-polymers of 1-hexene and 1-dodecene alpha olefins or co-polymers of 1-octene and 1-tetradodecene alpha olefins. Still another feature of the process for forming a drag reducing agent slurry is that the polyalphaolefin may be an ultra-high molecular weight polyalphaolefin having an inherent viscosity of at least about 10 deciliters per gram and may be amorphous with substantially no crystalline particles. A further feature of the process for forming a drag reducing agent slurry is that the process may further comprise the step of cryogrinding the polyalphaolefin prior to mixing the polyalphaolefin with the at least one alfol alcohol. Still another feature of the process for forming a drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected fromthe group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol formed by mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, I-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present drag reducing agent slurry comprising a polyalphaolefm and at least one alfol alcohol formed by contacting alpha olefin monomers with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin;
and mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for reducing drag in a conduit, comprising:
forming a drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol; and introducing the drag reducing agent slurry into the conduit.
A further feature of the process for reducing drag in a conduit is that the alfol alcohol may be selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for reducing drag in a conduit, comprising:
forming a drag reducing agent comprising a polyalphaolefin, wherein the drag reducing agent is formed by contacting alpha olefin monomers with a catalyst in a reactant mixture; polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; mixing the polyalphaolefm with at least one alfol alcohol to form a drag reducing agent slurry; and introducing the drag reducing agent slurry into the conduit.
A further feature of the process for reducing drag in a conduit is that the alfol alcohol may be selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
The drag reducing agent slurry, process for forming a drag reducing agent slurry, and process for reducing drag in a conduit have the advantages of not negatively impacting wastewater treatment facilities; permitting longer term storage without biological degradation and temperature destabilization; not insulting motor fuels and other refined products; reducing instances of re-agglomeration; and providing amore stable drag reducing agent slurry during production, transportation, storage, and use.
and mixing the polyalphaolefin with at least one alfol alcohol.
A further feature of the drag reducing agent slurry is that the alfol alcohol may be selected from the group consisting of 1-pentanol, l-hexanol, l-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for reducing drag in a conduit, comprising:
forming a drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol; and introducing the drag reducing agent slurry into the conduit.
A further feature of the process for reducing drag in a conduit is that the alfol alcohol may be selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
In accordance with the invention, the foregoing advantages have also been achieved through the present process for reducing drag in a conduit, comprising:
forming a drag reducing agent comprising a polyalphaolefin, wherein the drag reducing agent is formed by contacting alpha olefin monomers with a catalyst in a reactant mixture; polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; mixing the polyalphaolefm with at least one alfol alcohol to form a drag reducing agent slurry; and introducing the drag reducing agent slurry into the conduit.
A further feature of the process for reducing drag in a conduit is that the alfol alcohol may be selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol.
The drag reducing agent slurry, process for forming a drag reducing agent slurry, and process for reducing drag in a conduit have the advantages of not negatively impacting wastewater treatment facilities; permitting longer term storage without biological degradation and temperature destabilization; not insulting motor fuels and other refined products; reducing instances of re-agglomeration; and providing amore stable drag reducing agent slurry during production, transportation, storage, and use.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description refers to certain details and specific aspects of the invention, including specific embodiments and examples of the invention. Also, for purposes of better understanding the invention, certain terms will now be explained and defined. It is to be understood that the invention is not limited or restricted to the specif c examples and embodiments described below, which are included to assist a person skilled in the art in practicing the invention. On the contrary, it is intended to cover all alternatives, modifications, and equivalents, as may be included within the spirit and scope of the invention as defined by the appended claims.
The term "drag reducing agent" (DRA) as used herein refers to a composition that includes at least the formed polyalphaolefm polymer. The term "polyalphaolefin" refers to the polymer material formed by the polymerization of alpha olefin monomers, and is broadly construed to include not only the polymer in its final form, but also any intermediate polymers being formed, sometimes referred to as "oligomers." Preferably, the polyalphaolefin polymer is amorphous, i.e., the polyalphaolefin has no crystalline structures, or habits, existing in a single phase with substantially no solid particles, and has an ultra-high molecular weight and inherent viscosity of 10 dL/g or greater.
"Ultra-high molecular weight," means a molecular weight corresponding to an inherent viscosity of at least about 10 dL/g. Because of the extremely high molecular weight of the DR.A
polymer, it is difficult to reliably and accurately measure the actual molecular weight, but inherent viscosity provides a useful approximation of molecular weight.
"Inherent viscosity" is measured using a Cannon-Ubbelohde four bulb shear dilution viscometer (0.05 g polyrner/100 ml hexane at 25°C). Inherent viscosities are calculated for each of the last three bulbs. The viscosities are then plotted as a function of shear rate. The plot is then used to determine the inherent viscosity at a shear rate of 300 sec-1. It is contemplated that an inherent viscosity of dL/g corresponds roughly to a molecular weight of at least about 10 or 15 million. Preferably, the ultra-high molecular weight polyalphaolefins have molecular weights even higher, e.g., greater than 25 million. The polyalphaolefins formed preferably have a narrow molecular weight distribution. Because different assumptions about the properties of the polyalphaolefm can yield different estimates of molecular weights, the inventors prefer using inherent viscosity to characterize the molecular weights of their drag reducing agents.
The following detailed description refers to certain details and specific aspects of the invention, including specific embodiments and examples of the invention. Also, for purposes of better understanding the invention, certain terms will now be explained and defined. It is to be understood that the invention is not limited or restricted to the specif c examples and embodiments described below, which are included to assist a person skilled in the art in practicing the invention. On the contrary, it is intended to cover all alternatives, modifications, and equivalents, as may be included within the spirit and scope of the invention as defined by the appended claims.
The term "drag reducing agent" (DRA) as used herein refers to a composition that includes at least the formed polyalphaolefm polymer. The term "polyalphaolefin" refers to the polymer material formed by the polymerization of alpha olefin monomers, and is broadly construed to include not only the polymer in its final form, but also any intermediate polymers being formed, sometimes referred to as "oligomers." Preferably, the polyalphaolefin polymer is amorphous, i.e., the polyalphaolefin has no crystalline structures, or habits, existing in a single phase with substantially no solid particles, and has an ultra-high molecular weight and inherent viscosity of 10 dL/g or greater.
"Ultra-high molecular weight," means a molecular weight corresponding to an inherent viscosity of at least about 10 dL/g. Because of the extremely high molecular weight of the DR.A
polymer, it is difficult to reliably and accurately measure the actual molecular weight, but inherent viscosity provides a useful approximation of molecular weight.
"Inherent viscosity" is measured using a Cannon-Ubbelohde four bulb shear dilution viscometer (0.05 g polyrner/100 ml hexane at 25°C). Inherent viscosities are calculated for each of the last three bulbs. The viscosities are then plotted as a function of shear rate. The plot is then used to determine the inherent viscosity at a shear rate of 300 sec-1. It is contemplated that an inherent viscosity of dL/g corresponds roughly to a molecular weight of at least about 10 or 15 million. Preferably, the ultra-high molecular weight polyalphaolefins have molecular weights even higher, e.g., greater than 25 million. The polyalphaolefins formed preferably have a narrow molecular weight distribution. Because different assumptions about the properties of the polyalphaolefm can yield different estimates of molecular weights, the inventors prefer using inherent viscosity to characterize the molecular weights of their drag reducing agents.
While the polyalphaolefin polymer may be formed using any method known to persons skilled in the art (e.g., using the methods disclosed in U.S. Patents Nos.
3,692,676; 4,289,679;
4,358,572; 4,433,123; 4,493,903; 4,493,904; 5,244,937; 5,449,732; 5,504,131;
5,504,132; and 5,539,044, all of which are hereby incorporated by reference), the polyalphaolefm polymer is preferably made in accordance with the methods described in U.S. Patent Nos.
5,869,570 and 6,015,779, both of which are hereby incorporated by reference. Generally, the polyalphaolefin polymer is formed by contacting alpha olefin monomers, e.g., alpha olefins monomers having 2 to 20 carbon atoms, with a catalyst in a reactant mixture. Homopolymers, copolymers and terpolymers may be used. Preferred alpha olefins include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene;
conjugated or unconjugated dimes such as butadiene and l, 4-hexadiene; aromatic vinyls such as styrene; and cyclic olefins such as cyclobutene. Most preferably, the alpha olefin monomers are co-polymers of 1-hexene and 1-dodecene present in a 1:1 mole ratio; or co-polymers of 1-octene and 1-tetradecene present in a 1:1 mole ratio.
In one preferred embodiment, disclosed in U.S. Patent No. 6,015,779, alpha olefin monomers are contacted with a catalyst and a co-catalyst system having at least one co-catalyst.
While it is contemplated that any catalyst known to persons skilled in the art may be utilized, e.g., metallocene or Ziegler-Natta catalysts, preferred catalysts include transition metal catalysts such as those catalysts containing titanium trichloride, titanium tetrachloride or metallocene or combinations thereof. Preferably, the transition metal catalysts are non-metallocene. Titanium trichloride, which is most preferred, has been used for years in making drag reducing agents, and is preferably used in an amount ranging from at least about 100 to 1500 parts per million (ppm) based on the weight of all the components, i.e., the alpha olefins, co-catalysts, and catalysts supplied to the reactor.
Co-catalysts have also been used for years to form drag reducing agents. It is contemplated that any co-catalyst known to persons skilled in the art may be included with the catalyst; however, preferred co-catalysts includes one or more co-catalyst selected from the group consisting of alkylaluminoxanes, halohydrocarbons, diethylaluminum chloride ("DEAC") and dibutylaluminum chloride ("DIBAC"). As mentioned above, the process of forming the drag reducing agent may include no co-catalyst, one co-catalyst, or a plurality of co-catalysts.
3,692,676; 4,289,679;
4,358,572; 4,433,123; 4,493,903; 4,493,904; 5,244,937; 5,449,732; 5,504,131;
5,504,132; and 5,539,044, all of which are hereby incorporated by reference), the polyalphaolefm polymer is preferably made in accordance with the methods described in U.S. Patent Nos.
5,869,570 and 6,015,779, both of which are hereby incorporated by reference. Generally, the polyalphaolefin polymer is formed by contacting alpha olefin monomers, e.g., alpha olefins monomers having 2 to 20 carbon atoms, with a catalyst in a reactant mixture. Homopolymers, copolymers and terpolymers may be used. Preferred alpha olefins include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene;
conjugated or unconjugated dimes such as butadiene and l, 4-hexadiene; aromatic vinyls such as styrene; and cyclic olefins such as cyclobutene. Most preferably, the alpha olefin monomers are co-polymers of 1-hexene and 1-dodecene present in a 1:1 mole ratio; or co-polymers of 1-octene and 1-tetradecene present in a 1:1 mole ratio.
In one preferred embodiment, disclosed in U.S. Patent No. 6,015,779, alpha olefin monomers are contacted with a catalyst and a co-catalyst system having at least one co-catalyst.
While it is contemplated that any catalyst known to persons skilled in the art may be utilized, e.g., metallocene or Ziegler-Natta catalysts, preferred catalysts include transition metal catalysts such as those catalysts containing titanium trichloride, titanium tetrachloride or metallocene or combinations thereof. Preferably, the transition metal catalysts are non-metallocene. Titanium trichloride, which is most preferred, has been used for years in making drag reducing agents, and is preferably used in an amount ranging from at least about 100 to 1500 parts per million (ppm) based on the weight of all the components, i.e., the alpha olefins, co-catalysts, and catalysts supplied to the reactor.
Co-catalysts have also been used for years to form drag reducing agents. It is contemplated that any co-catalyst known to persons skilled in the art may be included with the catalyst; however, preferred co-catalysts includes one or more co-catalyst selected from the group consisting of alkylaluminoxanes, halohydrocarbons, diethylaluminum chloride ("DEAC") and dibutylaluminum chloride ("DIBAC"). As mentioned above, the process of forming the drag reducing agent may include no co-catalyst, one co-catalyst, or a plurality of co-catalysts.
The alpha olefin monomers may be polymerized at an initial temperature at about or less than 25°C, and preferably, at about or less than 10°C, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefm. Preferably, the alpha olefin monomers are polymerized at an initial temperature of about -5°C.
In some instances, the polyalphaolefin is cryoground as disclosed in U. S.
Patent Nos. U.5.
PatentsNos. 5,504,131; 5,504,132; and 5,539,044. Additionally, partitioning agents, also known as coating agents, may be, and preferably are, mixed with the polyalphaolefin.
Partitioning agents are compositions that help prohibit polyalphaolefin polymer particles from sticking together in large clumps, thereby facilitating the dispersion of the polyalphaolefin in the hydrocarbon in the conduit. The partitioning agents may be added during polymerization and/or during grinding of the polyalphaolefin into fine polymer particles.
Partitioning agents are generally known to persons skilled in the art and may be included in the reactant mixture or, alternatively, mixed with the polyalphaolefin after polymerization. Preferred partitioning agents axe alpha olefin monomer partitioning agent having 30 to at least about 65 carbons. In an especially preferred embodiment, alpha olefin monomer partitioning agent, i.e., alpha olefin monomers having about 30 to about 65 carbon atoms, is mixed with the polymer prior to adding the suspending material to the polymerlpartitioning agent particles.
Drag reducing agent slurries are formed by mixing the drag reducing agent with at least one slurry component or suspending material. Numerous slurry components are known to persons skilled in the art. Examples of suitable slurry components are disclosed in U.S. Patent Nos. 5,244,937; 5,449,732; 5,504,131; 5,504,132; 5,539,044, alI of which are hereby incorporated by reference. An additional slurry component, or suspending material, is at least one alfol alcohol.
In a preferred embodiment, after the polyalphaolefin is formed it is combined, or mixed, preferably under agitation, with at least one alfol alcohol to form a drag reducing agent slurry.
Alfol alcohols are straight-chained alcohols that are substantially insoluble, or immiscible, in water. Substantially insoluble, or immiscible, in water is herein defined as having a solubility in water of less than 0.2% by weight of alcohol to water. Additionally, preferably, the alfol alcohol is substantially pure or neat, i.e, contains less than 0.25% of any additional liquid, gas, or solid. Preferred, alfol alcohols of the present invention include 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol and are commercially available. In the preferred embodiment, 1-hexanol is included in the drag reducing agent slurry.
The alfol alcohol may be present in the drag reducing agent slurry at a concentration in the range from about 40.0% to about 85.0% based upon the weight of alfol alcohol to drag reducing agent slurry. Preferably, the at least one alfol alcohol is mixed with the polyalphaolefin to form a drag reducing agent slurry at a concentration ranging from about 45%
to about 55%
based upon the weight of alfol alcohol to drag reducing agent slurry.
It has been observed that the inclusion of 1-hexanol as the suspending material provides the added benefit in that should the drag reducing agent slurry separate, i.e., the polyalphaolefin is not no longer uniformly dispersed through out the suspending material such as due to long term settling of the polyalphaolefin with no mixing energy applied, the polyalphaolefin can be re-constituted back to its original suspended state by simply re-applying mixing energy, i.e., applying an'agitator.
Another surprising and advantageous result of including 1-hexanol as the suspending material is that 1-hexanol, and presumably other alfol alcohols, demonstrates unique particle wetting characteristics on the polymer/partitioning agent particles. This preferential oil soluble surface wetting of discrete polymer/partitioning agent particles facilitates the prevention of re-agglomeration of the polymer/partitioning agent particles which would produce an unusable drag reducing agent slurry. Further, and unexpectedly, the wetted polymer/partitioning agent particles demonstrate an improvement in the ability of the polyrner/partitioning agent particles to dissolve in petroleum streams and become functional, and thus provide drag reducing, much faster after introduction into the hydrocarbon stream.
Still another surprising and advantageous result of including 1-hexanol as the suspending material is that 1-hexanol, and presumably other alfol alcohols, permit increased percentages of polymer per gallon of suspending material. As noted previously, the highest known ratio of polymer to suspending agent is approximately 2.0 pounds of polymer per gallon of suspending agent. Using a polymer formed in accordance with the process disclosed in U.S.
Patent No.
6,015,779 and combined with C3o+ alpha olefin monomer partitioning agent (purchased from Chevron-Phillips), polymer/partitioning agent particles were formed by cryogrinding and were combined with 1-hexanol (45 g polymer/partitioning agent to 65 grams of 1-hexanol). A stable drag reducing agent slurry was formed having a ratio of polymer to suspending agent of 2.5 pounds per gallon, and in one specific example, 2.8 pounds per gallon. These results represent a 2S% and, in at least one case, a 28% increase over prior drag reducing agent slurries that translates into an increase of drag reduction capability with less volume of drag reducing agent slurry.
Additionally, the drag reducing agent slurries of the present invention provided a longer shelf life than prior drag reducing agent slurries. Several samples of drag reducing agent slurries were prepared using the polymer formed using the process disclosed in U.S.
Patent No.
6,015,779. After the polymer was formed, it was combined with C3°+
alpha olefin monomer partitioning agent and cryoground. The cryoground polymer/partitioning agent particles were then combined with the suspending agents listed in TABLE I at a concentration of 4S grams of polymer/partitioning agent particles to 6S grams of suspending material.
Therefore, the only difference between each example is that different suspending materials were selected.
Each drag reducing agent slurry sample was then allowed to set for 30 days at 7S° C
without any agitation. After 30 days, each sample was analyzed to determine whether the sample had re-agglomerated, and thus, had become unusable. The results are shown in TABLE I.
TABLE I
Suspending Material Slurry State after 30 days at 7S° C
(No agitation) Ethanol Separation/Severe re-agglomeration Ethanol-Water Mixture Separation/Severe re-agglomeration (SO vol./SO vol.) Butanol (Neat) Separation/Severe re-agglomeration Butanol-Water Mixture Separation/Severe re-agglomeration (SO vol./S0 vol.) Methanol (Neat) Separation/Severe re-agglomeration Methanol-Water Mixture Separation/Severe re-agglomeration (SO vol./SO vol.) Isopropanol (Neat) Separation/Re-agglomeration Isopropanol-Water Mixture SeparationlSevere re-agglomeration (50 vo1.150 vol.) 1-Hexanol (Neat) Slight Separation/No re-agglomeration As shown in TABLE I, only the drag reducing agent slurries containing 1-hexanol (Neat) showed no re-agglomeration after 30 days. While this sample showed slight separation, because there was no re-agglomeration, this sample was capable of being re-suspended, and thus, was still usable after 30 days. The other drag reducing agent slurries, all of which are prior drag reducing agent slurries, all separated and re-agglomerated. In fact, in all but one of the samples, the drag reducing agents severely re-agglomerated. As a result, none of these samples were suitable as drag reducing agent slurries after 30 days at 75° C.
Drag reducing agent slurries comprising a drag reducing agent and at least one alfol alcohol may be used to reduce drag in a conduit by adding the drag reducing agent slurry to a conduit containing a hydrocarbon. Additionally, the drag reducing agent slurry comprising at least one alfol alcohol may also be further processed by any method known to those skilled in the art to be utilized to reduce drag in a conduit.
It is to be understood that the invention is not limited to the exact details of construction, operation, exact materials, or embodiments shown and described, as obvious modifications and equivalents will be apparent to one skilled in the art. Accordingly, the invention is therefore to be limited only by the scope of the appended claims.
In some instances, the polyalphaolefin is cryoground as disclosed in U. S.
Patent Nos. U.5.
PatentsNos. 5,504,131; 5,504,132; and 5,539,044. Additionally, partitioning agents, also known as coating agents, may be, and preferably are, mixed with the polyalphaolefin.
Partitioning agents are compositions that help prohibit polyalphaolefin polymer particles from sticking together in large clumps, thereby facilitating the dispersion of the polyalphaolefin in the hydrocarbon in the conduit. The partitioning agents may be added during polymerization and/or during grinding of the polyalphaolefin into fine polymer particles.
Partitioning agents are generally known to persons skilled in the art and may be included in the reactant mixture or, alternatively, mixed with the polyalphaolefin after polymerization. Preferred partitioning agents axe alpha olefin monomer partitioning agent having 30 to at least about 65 carbons. In an especially preferred embodiment, alpha olefin monomer partitioning agent, i.e., alpha olefin monomers having about 30 to about 65 carbon atoms, is mixed with the polymer prior to adding the suspending material to the polymerlpartitioning agent particles.
Drag reducing agent slurries are formed by mixing the drag reducing agent with at least one slurry component or suspending material. Numerous slurry components are known to persons skilled in the art. Examples of suitable slurry components are disclosed in U.S. Patent Nos. 5,244,937; 5,449,732; 5,504,131; 5,504,132; 5,539,044, alI of which are hereby incorporated by reference. An additional slurry component, or suspending material, is at least one alfol alcohol.
In a preferred embodiment, after the polyalphaolefin is formed it is combined, or mixed, preferably under agitation, with at least one alfol alcohol to form a drag reducing agent slurry.
Alfol alcohols are straight-chained alcohols that are substantially insoluble, or immiscible, in water. Substantially insoluble, or immiscible, in water is herein defined as having a solubility in water of less than 0.2% by weight of alcohol to water. Additionally, preferably, the alfol alcohol is substantially pure or neat, i.e, contains less than 0.25% of any additional liquid, gas, or solid. Preferred, alfol alcohols of the present invention include 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol, and 1-decanol and are commercially available. In the preferred embodiment, 1-hexanol is included in the drag reducing agent slurry.
The alfol alcohol may be present in the drag reducing agent slurry at a concentration in the range from about 40.0% to about 85.0% based upon the weight of alfol alcohol to drag reducing agent slurry. Preferably, the at least one alfol alcohol is mixed with the polyalphaolefin to form a drag reducing agent slurry at a concentration ranging from about 45%
to about 55%
based upon the weight of alfol alcohol to drag reducing agent slurry.
It has been observed that the inclusion of 1-hexanol as the suspending material provides the added benefit in that should the drag reducing agent slurry separate, i.e., the polyalphaolefin is not no longer uniformly dispersed through out the suspending material such as due to long term settling of the polyalphaolefin with no mixing energy applied, the polyalphaolefin can be re-constituted back to its original suspended state by simply re-applying mixing energy, i.e., applying an'agitator.
Another surprising and advantageous result of including 1-hexanol as the suspending material is that 1-hexanol, and presumably other alfol alcohols, demonstrates unique particle wetting characteristics on the polymer/partitioning agent particles. This preferential oil soluble surface wetting of discrete polymer/partitioning agent particles facilitates the prevention of re-agglomeration of the polymer/partitioning agent particles which would produce an unusable drag reducing agent slurry. Further, and unexpectedly, the wetted polymer/partitioning agent particles demonstrate an improvement in the ability of the polyrner/partitioning agent particles to dissolve in petroleum streams and become functional, and thus provide drag reducing, much faster after introduction into the hydrocarbon stream.
Still another surprising and advantageous result of including 1-hexanol as the suspending material is that 1-hexanol, and presumably other alfol alcohols, permit increased percentages of polymer per gallon of suspending material. As noted previously, the highest known ratio of polymer to suspending agent is approximately 2.0 pounds of polymer per gallon of suspending agent. Using a polymer formed in accordance with the process disclosed in U.S.
Patent No.
6,015,779 and combined with C3o+ alpha olefin monomer partitioning agent (purchased from Chevron-Phillips), polymer/partitioning agent particles were formed by cryogrinding and were combined with 1-hexanol (45 g polymer/partitioning agent to 65 grams of 1-hexanol). A stable drag reducing agent slurry was formed having a ratio of polymer to suspending agent of 2.5 pounds per gallon, and in one specific example, 2.8 pounds per gallon. These results represent a 2S% and, in at least one case, a 28% increase over prior drag reducing agent slurries that translates into an increase of drag reduction capability with less volume of drag reducing agent slurry.
Additionally, the drag reducing agent slurries of the present invention provided a longer shelf life than prior drag reducing agent slurries. Several samples of drag reducing agent slurries were prepared using the polymer formed using the process disclosed in U.S.
Patent No.
6,015,779. After the polymer was formed, it was combined with C3°+
alpha olefin monomer partitioning agent and cryoground. The cryoground polymer/partitioning agent particles were then combined with the suspending agents listed in TABLE I at a concentration of 4S grams of polymer/partitioning agent particles to 6S grams of suspending material.
Therefore, the only difference between each example is that different suspending materials were selected.
Each drag reducing agent slurry sample was then allowed to set for 30 days at 7S° C
without any agitation. After 30 days, each sample was analyzed to determine whether the sample had re-agglomerated, and thus, had become unusable. The results are shown in TABLE I.
TABLE I
Suspending Material Slurry State after 30 days at 7S° C
(No agitation) Ethanol Separation/Severe re-agglomeration Ethanol-Water Mixture Separation/Severe re-agglomeration (SO vol./SO vol.) Butanol (Neat) Separation/Severe re-agglomeration Butanol-Water Mixture Separation/Severe re-agglomeration (SO vol./S0 vol.) Methanol (Neat) Separation/Severe re-agglomeration Methanol-Water Mixture Separation/Severe re-agglomeration (SO vol./SO vol.) Isopropanol (Neat) Separation/Re-agglomeration Isopropanol-Water Mixture SeparationlSevere re-agglomeration (50 vo1.150 vol.) 1-Hexanol (Neat) Slight Separation/No re-agglomeration As shown in TABLE I, only the drag reducing agent slurries containing 1-hexanol (Neat) showed no re-agglomeration after 30 days. While this sample showed slight separation, because there was no re-agglomeration, this sample was capable of being re-suspended, and thus, was still usable after 30 days. The other drag reducing agent slurries, all of which are prior drag reducing agent slurries, all separated and re-agglomerated. In fact, in all but one of the samples, the drag reducing agents severely re-agglomerated. As a result, none of these samples were suitable as drag reducing agent slurries after 30 days at 75° C.
Drag reducing agent slurries comprising a drag reducing agent and at least one alfol alcohol may be used to reduce drag in a conduit by adding the drag reducing agent slurry to a conduit containing a hydrocarbon. Additionally, the drag reducing agent slurry comprising at least one alfol alcohol may also be further processed by any method known to those skilled in the art to be utilized to reduce drag in a conduit.
It is to be understood that the invention is not limited to the exact details of construction, operation, exact materials, or embodiments shown and described, as obvious modifications and equivalents will be apparent to one skilled in the art. Accordingly, the invention is therefore to be limited only by the scope of the appended claims.
Claims (23)
1. A process for forming a drag reducing agent slurry comprising:
forming a polyalphaolefin; and mixing the polyalphaolefin with at least one alfol alcohol.
forming a polyalphaolefin; and mixing the polyalphaolefin with at least one alfol alcohol.
2. The process for forming a drag reducing agent slurry of claim 1, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
3. A process for forming a drag reducing agent slurry comprising:
contacting alpha olefin monomer with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin;
mixing the polyalphaolefin with at least one alfol alcohol.
contacting alpha olefin monomer with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin;
mixing the polyalphaolefin with at least one alfol alcohol.
4. The process for forming a drag reducing agent slurry of claim 3, wherein the catalyst is a transition metal catalyst.
5. The process for forming a drag reducing agent slurry of claim 3, wherein the transition metal catalyst is a Ziegler-Natta catalyst.
6. The process for forming a drag reducing agent slurry of claim 3, wherein the Ziegler-Natta catalyst is titanium trichloride.
7. The process for forming a drag reducing agent slurry of claim 3, wherein the reactant mixture includes at least one co-catalyst.
8. The process for forming a drag reducing agent slurry of claim 7, wherein the at least one co-catalyst is selected from the group consisting of alkylaluminoxanes, halohydrocarbons, diethylaluminum chloride, and dibutylaluminum chloride.
9. The process for forming a drag reducing agent slurry of claim 3, wherein the alpha olefin monomers comprise homopolymers, terpolymers or copolymers.
10. The process for forming a drag reducing agent slurry of claim 3, wherein the alpha olefin monomers comprise co-polymers of 1-hexene and 1-dodecene alpha olefins or co-polymers of 1-octene and 1-tetradodecene alpha olefins.
11. The process for forming a drag reducing agent slurry of claim 3, wherein the polyalphaolefin is an ultra-high molecular weight polyalphaolefin having an inherent viscosity of at least about 10 deciliters per gram and is amorphous with substantially no crystalline particles.
12. The process for forming a drag reducing agent slurry of claim 3, further comprising the step of cryogrinding the polyalphaolefin prior to mixing the polyalphaolefin with at least one alfol alcohol.
13. The process for forming a drag reducing agent slurry of claim 3, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
14. A drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol.
15. The process for forming a drag reducing agent slurry of claim 14, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
16. A drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol formed by mixing the polyalphaolefin with at least one alfol alcohol.
17. The process for forming a drag reducing agent slurry of claim 16, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
18. A drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol formed by contacting alpha olefin monomers with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; and mixing the polyalphaolefin with at least one alfol alcohol.
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin; and mixing the polyalphaolefin with at least one alfol alcohol.
19. The process for forming a drag reducing agent slurry of claim 18, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
20. A process for reducing drag in a conduit, comprising:
forming a drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol; and introducing the drag reducing agent slurry into the conduit.
forming a drag reducing agent slurry comprising a polyalphaolefin and at least one alfol alcohol; and introducing the drag reducing agent slurry into the conduit.
21. The process for forming a drag reducing agent slurry of claim 20, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
22. A process for reducing drag in a conduit, comprising:
forming a drag reducing agent comprising a polyalphaolefin, wherein the drag reducing agent is formed by contacting alpha olefin monomers with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin;
mixing the polyalphaolefin with at least one alfol alcohol to form a drag reducing agent slurry; and introducing the drag reducing agent slurry into the conduit.
forming a drag reducing agent comprising a polyalphaolefin, wherein the drag reducing agent is formed by contacting alpha olefin monomers with a catalyst in a reactant mixture;
polymerizing the alpha olefin monomers, wherein during the polymerization, at least a portion of the alpha olefin monomers polymerize in the reactant mixture to provide a polyalphaolefin;
mixing the polyalphaolefin with at least one alfol alcohol to form a drag reducing agent slurry; and introducing the drag reducing agent slurry into the conduit.
23. The process for forming a drag reducing agent slurry of claim 22, wherein the at least one alfol alcohol is selected from the group consisting of 1-pentanol, 1-hexanol, 1-heptanol, n-octyl alcohol, n-nonyl alcohol and 1-decanol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/877,341 | 2001-06-08 | ||
| US09/877,341 US7012046B2 (en) | 2001-06-08 | 2001-06-08 | Drag reducing agent slurries having alfol alcohols and processes for forming drag reducing agent slurries having alfol alcohols |
| PCT/US2002/017670 WO2002101282A2 (en) | 2001-06-08 | 2002-06-07 | Drag reducing agent slurries having alfol alcohols and processes for forming drag reducing agent slurries having alfol alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2447798A1 true CA2447798A1 (en) | 2002-12-19 |
Family
ID=25369783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2447798 Abandoned CA2447798A1 (en) | 2001-06-08 | 2002-06-07 | Drag reducing agent slurries having alfol alcohols and processes for forming them |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7012046B2 (en) |
| EP (1) | EP1392995B1 (en) |
| CN (1) | CN1267675C (en) |
| AT (1) | ATE420318T1 (en) |
| AU (1) | AU2002329180A1 (en) |
| CA (1) | CA2447798A1 (en) |
| DE (1) | DE60230745D1 (en) |
| DK (1) | DK1392995T3 (en) |
| NO (1) | NO20035404D0 (en) |
| RU (1) | RU2297574C2 (en) |
| WO (1) | WO2002101282A2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6815011B2 (en) * | 2000-11-27 | 2004-11-09 | Energy & Environmental International, L.C. | Alpha olefin monomer partitioning agents for drag reducing agents and methods of forming drag reducing agents using alpha olefin monomer partitioning agents |
| US6989357B2 (en) * | 2001-06-08 | 2006-01-24 | Eaton Gerald B | Alcohol absorbed polyalphaolefin drag reducing agents |
| US6649670B1 (en) | 2002-12-17 | 2003-11-18 | Baker Hughes Incorporated | Continuous neat polymerization and ambient grinding methods of polyolefin drag reducing agents |
| US6946500B2 (en) * | 2002-12-17 | 2005-09-20 | Baker Hughes Incorporated | Non-cryogenic process for grinding polyolefin drag reducing agents |
| US6894088B2 (en) * | 2003-03-24 | 2005-05-17 | Baker Hughes Incorporated | Process for homogenizing polyolefin drag reducing agents |
| CN1309777C (en) * | 2003-12-09 | 2007-04-11 | 中国石油天然气股份有限公司 | Method for preparing powder of frictional reducing polymer of alpha olefin in high grade and appts. thereof |
| US7271205B2 (en) * | 2005-09-20 | 2007-09-18 | Baker Hughes Incorporated | Non-cryogenic process for granulating polymer drag reducing agents |
| RU2463320C1 (en) * | 2011-07-27 | 2012-10-10 | Государственное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" | Method of producing suspension-type anti-turbulence additive for oil and oil products |
| CN105179943B (en) * | 2015-09-11 | 2017-12-22 | 中国石油大学胜利学院 | The polyalphaolefin stable suspension of PVA modified urea-formaldehyde resin microcapsule coateds |
| US9969826B2 (en) | 2015-11-19 | 2018-05-15 | Saudi Arabian Oil Company | Catalyst composition and a process for making ultra high molecular weight poly (alpha-olefin) drag reducing agents |
| RU2612834C1 (en) * | 2015-11-24 | 2017-03-13 | Общество с ограниченной ответственностью "КЕМТЕК" | Non-aqueous suspension of agent reducing hydrodynamic drag of hydrocarbon liquids |
| RU2627355C1 (en) * | 2016-11-15 | 2017-08-07 | Общество с ограниченной ответственностью "МИРРИКО" | Turbulent viscosity reducing additive with anticorrosion properties |
Family Cites Families (119)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151399A (en) | 1990-10-18 | 1992-09-29 | Shell Oil Company | Olefin polymerization catalyst |
| US3542044A (en) | 1966-09-22 | 1970-11-24 | John J Padden | Friction reducing compositions for oil-based fracturing fluids |
| US3645822A (en) | 1969-01-31 | 1972-02-29 | Dow Chemical Co | Method for providing multilayer films having improved slip properties |
| US4057680A (en) | 1969-11-26 | 1977-11-08 | Showa Denko Kabushiki Kaisha | Method of polymerizing α-olefins |
| US3692676A (en) | 1969-12-22 | 1972-09-19 | Continental Oil Co | Method of friction loss reduction in oleaginous fluids flowing through conduits |
| US3669948A (en) | 1970-09-04 | 1972-06-13 | Chisso Corp | Method for producing poly{60 -olefins |
| US3730275A (en) | 1971-02-16 | 1973-05-01 | Continental Oil Co | Method using low friction loss liquid composition having resistance to shear degradation |
| US3791913A (en) | 1971-05-17 | 1974-02-12 | Exxon Research Engineering Co | Free flowing elastomer pellets and process for their preparation |
| US3736288A (en) | 1971-07-09 | 1973-05-29 | Union Carbide Corp | Drag reducing formulations |
| US3767561A (en) | 1971-07-21 | 1973-10-23 | Exxon Research Engineering Co | Alpha-olefin polymers as dewaxing aids |
| US5521242A (en) * | 1971-09-30 | 1996-05-28 | The United States Of America As Represented By The Secretary Of The Navy | High concentration slurry-formulation and application |
| BE792607A (en) | 1971-12-20 | 1973-06-12 | Shell Int Research | TITANCHLORIDE-CONTAINING COMPOSITIONS SUITABLE FOR POLYMERIZATION |
| NL7206290A (en) | 1972-05-10 | 1973-11-13 | ||
| US3843589A (en) | 1973-02-05 | 1974-10-22 | Union Carbide Corp | Stable pumpable slurries of ethylene oxide polymers |
| DE2329641C3 (en) | 1973-06-09 | 1978-09-28 | Hoechst Ag, 6000 Frankfurt | Process for the polymerization of ct-olefins |
| US3884252A (en) | 1973-06-20 | 1975-05-20 | Shell Oil Co | Friction reduction |
| US4190069A (en) | 1975-06-06 | 1980-02-26 | General Electric Company | Process for transmitting a hydrocarbon fluid through a pipeline |
| US4142991A (en) | 1975-12-22 | 1979-03-06 | Stauffer Chemical Company | Substantially agglomeration-free catalyst component |
| US4147677A (en) | 1977-11-29 | 1979-04-03 | Exxon Research & Engineering Co. | Dry blending of neutralized sulfonated elastomeric powders |
| US4212312A (en) | 1978-08-28 | 1980-07-15 | Shell Oil Company | Fragmented polymers as friction reducers in pipeline transportation of products |
| DE2847986A1 (en) | 1978-11-04 | 1980-05-22 | Huels Chemische Werke Ag | METHOD FOR PRODUCING POWDER-SHAPED, THERMOPLASTIC COPOLYMERS FROM AETHYLENE AND BUTEN- (1) |
| US4263926A (en) | 1978-12-04 | 1981-04-28 | Shell Oil Company | Injection system for solid friction reducing polymers |
| US4335964A (en) | 1978-12-04 | 1982-06-22 | Shell Oil Company | Injection system for solid friction reducing polymers |
| US4415714A (en) | 1979-01-02 | 1983-11-15 | Conoco Inc. | Catalyst and method for preparation of drag reducing substances |
| US4433123A (en) | 1979-01-29 | 1984-02-21 | Conoco Inc. | Polymerization process for drag reducing substances |
| US4282114A (en) | 1979-02-08 | 1981-08-04 | Mitsui Toatsu Chemicals, Inc. | Catalyst for polymerizing α-olefins |
| US4395358A (en) | 1979-02-12 | 1983-07-26 | Exxon Research & Engineering Co. | Titanium trichloride catalyst complex and process for the production thereof |
| US4262104A (en) | 1979-02-12 | 1981-04-14 | Exxon Research & Engineering Co. | Titanium trichloride catalyst complex and process for the production thereof |
| US4340076A (en) | 1979-02-27 | 1982-07-20 | General Technology Applications, Inc. | Dissolving polymers in compatible liquids and uses thereof |
| EP0019312B1 (en) | 1979-04-30 | 1983-08-17 | Shell Internationale Researchmaatschappij B.V. | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| CA1141093A (en) | 1979-05-17 | 1983-02-08 | Brian L. Goodall | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| US4289679A (en) | 1979-12-14 | 1981-09-15 | Conoco, Inc. | Method for producing solutions of drag reducing substances |
| US4267292A (en) | 1979-12-26 | 1981-05-12 | The Standard Oil Company | Addition of chlorine compound to Ziegler polymerization process |
| US4333488A (en) | 1980-09-08 | 1982-06-08 | Conoco Inc. | Method of transporting viscous hydrocarbons |
| US4358572A (en) | 1981-05-07 | 1982-11-09 | Conoco Inc. | Method for the preparation of non-crystalline polymers of high molecular weight |
| US4493903A (en) | 1981-05-12 | 1985-01-15 | Conoco Inc. | Polymerization process for drag reducing substances |
| US4493904A (en) | 1981-06-29 | 1985-01-15 | Conoco Inc. | Catalyst and method for preparation of drag reducing substances |
| JPS5853905A (en) | 1981-09-29 | 1983-03-30 | Toa Nenryo Kogyo Kk | Catalytic component for polymerizing olefin |
| US4384089A (en) | 1981-10-15 | 1983-05-17 | Atlantic Richfield Company | Low temperature polymerization process |
| US4371455A (en) | 1981-12-21 | 1983-02-01 | Conoco, Inc. | Supported catalyst for olefin polymerization |
| US4426317A (en) | 1982-11-24 | 1984-01-17 | Cities Service Company | Process for making olefin polymerization catalyst |
| US4478951A (en) | 1983-01-03 | 1984-10-23 | Exxon Research & Engineering Co. | Titanium trichloride catalyst component and the process for the production thereof |
| US4522982A (en) | 1983-06-06 | 1985-06-11 | Exxon Research & Engineering Co. | Isotactic-stereoblock polymers of alpha-olefins and process for producing the same |
| US4959436A (en) | 1983-06-15 | 1990-09-25 | Exxon Research And Engineering Co. | Narrow MWD alpha-olefin copolymers |
| JPS6094408A (en) | 1983-10-28 | 1985-05-27 | Sumitomo Chem Co Ltd | Treatment of polymer slurry |
| US4656204A (en) | 1983-11-02 | 1987-04-07 | Exxon Research And Engineering Company | Process for use of drag reduction agent in a hydrocarbon liquid |
| US4539374A (en) | 1984-03-21 | 1985-09-03 | E. I. Du Pont De Nemours And Company | Polyolefin with improved processing properties |
| DE3501858A1 (en) | 1985-01-22 | 1986-07-24 | Neste Oy, Espoo | CATALYST COMPONENTS, CATALYST AND METHOD FOR THE POLYMERIZATION OF OLEFINS |
| US4642410A (en) | 1985-03-14 | 1987-02-10 | Uniroyal Chemical Company, Inc. | Catalytic poly alpha-olefin process |
| US4584244A (en) | 1985-05-28 | 1986-04-22 | Conoco Inc. | Preparation of cold flow resistant polymer powders |
| US4693321A (en) | 1985-11-18 | 1987-09-15 | Conoco Inc. | Method using encapsulated flow improvers to reduce turbulence |
| US4845178A (en) | 1985-11-21 | 1989-07-04 | Pony Industries, Inc. | Polymerization process |
| US4758354A (en) | 1985-12-12 | 1988-07-19 | General Technology Applications, Inc. | Separation process |
| US4720397A (en) | 1985-12-12 | 1988-01-19 | General Technology Applications, Inc. | Rapid dissolving polymer compositions and uses therefor |
| US4659685A (en) | 1986-03-17 | 1987-04-21 | The Dow Chemical Company | Heterogeneous organometallic catalysts containing a supported titanium compound and at least one other supported organometallic compound |
| FR2597487B1 (en) | 1986-04-17 | 1989-09-29 | Bp Chimie Sa | AMORPHOUS COPOLYMERS OF HIGH MOLECULAR MASS OF ETHYLENE AND ALPHA-OLEFINS. |
| USH316H (en) | 1986-05-02 | 1987-08-04 | Exxon Research And Engineering Co. | Hydrocarbon drag reduction with interpolymer complexes containing novel sulfo-octene |
| US5241025A (en) | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| US4756326A (en) | 1987-07-13 | 1988-07-12 | Conoco Inc. | Polymeric drag reducer performance by injection through a land-length die |
| US4771800A (en) | 1987-07-13 | 1988-09-20 | Conoco Inc. | Dissolution performance by injection through a die-type nozzle |
| US4804794A (en) | 1987-07-13 | 1989-02-14 | Exxon Chemical Patents Inc. | Viscosity modifier polymers |
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| JPH072798B2 (en) | 1987-10-28 | 1995-01-18 | 住友化学工業株式会社 | Solid catalyst component for olefin polymerization |
| US4771799A (en) | 1987-10-29 | 1988-09-20 | Conoco Inc. | Method for improving the performance of highly viscous concentrates of high molecular weight drag reducing polymers |
| US4968853A (en) | 1987-12-29 | 1990-11-06 | The Lubrizol Corporation | Alpha-olefin polymers |
| US5320994A (en) | 1988-06-23 | 1994-06-14 | Norsolor | Process for preparing a catalyst for the polymerization of olefins |
| FR2633298B1 (en) | 1988-06-23 | 1991-01-18 | Norsolor Sa | CATALYTIC COMPONENT FOR POLYMERIZATION OF OLEFINS AND PROCESS FOR PREPARING THE SAME |
| US4881566A (en) | 1988-10-11 | 1989-11-21 | Conoco Inc. | Method for reducing pressure drop in the transportation of drag reducer |
| US5276116A (en) | 1988-11-14 | 1994-01-04 | Conoco Inc. | Composition and method for friction loss reduction |
| US4952738A (en) | 1988-11-14 | 1990-08-28 | Conoco Inc. | Composition and method for friction loss reduction |
| US4945142A (en) | 1988-11-14 | 1990-07-31 | Conoco Inc. | Composition and process for friction loss reduction |
| US5639842A (en) * | 1988-12-26 | 1997-06-17 | Mitsui Petrochemical Industries, Ltd. | Ethylene random copolymers |
| DE69025964T2 (en) | 1989-01-21 | 1996-08-08 | Mitsubishi Petrochemical Co | Process for the production of ethylene copolymers |
| JP2752695B2 (en) | 1989-05-25 | 1998-05-18 | 出光興産株式会社 | Method for drying aluminoxane and method for producing polymer |
| GB8925945D0 (en) | 1989-11-16 | 1990-01-04 | Shell Int Research | Olefin polymerization catalysts |
| US5104839A (en) | 1990-05-29 | 1992-04-14 | Phillips Petroleum Company | Method for producing olefin polymer blends utilizing a chromium-zirconium dual catalyst system |
| US5080121A (en) | 1990-08-06 | 1992-01-14 | Council Of Scientific & Industrial Research | Process for the preparation of a new polymer useful for drag reduction in hydrocarbon fluids in exceptionally dilute polymer solutions |
| US5244937A (en) | 1990-09-04 | 1993-09-14 | Conoco Inc. | Stable nonagglomerating aqueous suspensions of oil soluble polymeric friction reducers |
| US5162277A (en) | 1990-10-18 | 1992-11-10 | Shell Oil Company | Olefin polymerization catalyst |
| US5243001A (en) | 1990-11-12 | 1993-09-07 | Hoechst Aktiengesellschaft | Process for the preparation of a high molecular weight olefin polymer |
| FI86989C (en) * | 1990-12-19 | 1992-11-10 | Neste Oy | Process for producing a polymerization catalyst component for olefins, a polymerization catalyst component prepared by the process, and its use |
| FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
| DE59209897D1 (en) | 1991-05-27 | 2001-04-26 | Targor Gmbh | Process for the production of polyolefins with a broad molar mass distribution |
| IT1251465B (en) | 1991-07-12 | 1995-05-15 | Enichem Polimeri | SUPPORTED CATALYST FOR THE (CO) POLYMERIZATION OF ETHYLENE. |
| US5710224A (en) * | 1991-07-23 | 1998-01-20 | Phillips Petroleum Company | Method for producing polymer of ethylene |
| IT1250706B (en) | 1991-07-25 | 1995-04-21 | Enichem Polimeri | CATALYST FOR THE POLYMERIZATION OF OLEFINE |
| TW300901B (en) | 1991-08-26 | 1997-03-21 | Hoechst Ag | |
| CA2077744C (en) | 1991-09-30 | 2003-04-15 | Edwar Shoukri Shamshoum | Homogeneous-heterogeneous catalyst system for polyolefins |
| DE59210001D1 (en) | 1991-10-15 | 2005-02-17 | Basell Polyolefine Gmbh | Process for the preparation of an olefin polymer using metallocenes with specifically substituted indenyl ligands |
| US5359015A (en) | 1991-11-07 | 1994-10-25 | Exxon Chemical Patents Inc. | Metallocene catalysts and their production and use |
| EP0544308B1 (en) | 1991-11-28 | 1998-02-18 | Showa Denko Kabushikikaisha | Novel metallocene and process for producing polyolefin using the same |
| TW318184B (en) | 1991-11-30 | 1997-10-21 | Hoechst Ag | |
| JPH05178927A (en) | 1991-12-27 | 1993-07-20 | Tosoh Corp | Catalyst for polymerization of olefin and production of olefin polymer |
| US5165441A (en) | 1991-12-30 | 1992-11-24 | Conoco Inc. | Process and apparatus for blending drag reducer in solvent |
| US5198399A (en) | 1992-01-17 | 1993-03-30 | Quantum Chemical Corporation | Polymerization catalyst and method |
| IT1254223B (en) | 1992-02-26 | 1995-09-14 | Enichem Polimeri | CATALYST FOR THE POLYMERIZATION OF OLEFINE |
| US5434115A (en) * | 1992-05-22 | 1995-07-18 | Tosoh Corporation | Process for producing olefin polymer |
| US5238892A (en) | 1992-06-15 | 1993-08-24 | Exxon Chemical Patents Inc. | Supported catalyst for 1-olefin(s) (co)polymerization |
| US5276220A (en) | 1992-06-18 | 1994-01-04 | Ethyl Corporation | Actinide catalyzed chain growth process |
| CA2110654C (en) * | 1992-12-17 | 2006-03-21 | Albert Rossi | Dilute process for the polymerization of ethylene/alpha-olefin copolymer using metallocene catalyst systems |
| EP0698619B1 (en) * | 1993-03-31 | 2001-11-07 | Idemitsu Kosan Company Limited | Catalyst for producing vinyl polymer and process for producing vinylaromatic polymer |
| ZA943399B (en) * | 1993-05-20 | 1995-11-17 | Bp Chem Int Ltd | Polymerisation process |
| US5449732A (en) * | 1993-06-18 | 1995-09-12 | Conoco Inc. | Solvent free oil soluble drag reducing polymer suspension |
| US5376697B1 (en) | 1993-06-21 | 1998-06-02 | Conoco Inc | Drag reducers for flowing hydrocarbons |
| BE1007698A3 (en) * | 1993-11-04 | 1995-10-03 | Solvay | Catalyst system used for the polymerization of alpha-olefin polymerization and method for this. |
| US5416179A (en) * | 1994-03-16 | 1995-05-16 | Phillips Petroleum Company | Catalyst compositions and olefin polymerization |
| US5442019A (en) * | 1994-03-25 | 1995-08-15 | Exxon Chemical Company | Process for transitioning between incompatible polymerization catalysts |
| US5436212A (en) * | 1994-04-15 | 1995-07-25 | Phillips Petroleum Company | Organoaluminoxy product, preparation, and use |
| US5539044A (en) * | 1994-09-02 | 1996-07-23 | Conoco In. | Slurry drag reducer |
| US5712365A (en) * | 1995-03-27 | 1998-01-27 | Tosoh Corporation | Process for producing ethylene alpha-olefin copolymer |
| US5733953A (en) * | 1995-06-29 | 1998-03-31 | Baker Hughes Incorporated | Low viscosity, high concentration drag reducing agent and method therefor |
| US5728855A (en) * | 1995-10-19 | 1998-03-17 | Akzo Nobel Nv | Modified polyalkylaluminoxane composition formed using reagent containing carbon-oxygen double bond |
| US6015779A (en) * | 1996-03-19 | 2000-01-18 | Energy & Environmental International, L.C. | Methods for forming amorphous ultra-high molecular weight polyalphaolefin drag reducing agents |
| US5869570A (en) * | 1996-03-19 | 1999-02-09 | Energy & Environmental International, L.C. | Composition of and process for forming polyalphaolefin drag reducing agents |
| US5644007A (en) * | 1996-04-26 | 1997-07-01 | Minnesota Mining And Manufacturing Company | Continuous process for the production of poly(1-alkenes) |
| US6172151B1 (en) * | 1996-10-15 | 2001-01-09 | Conoco Inc. | Nonaqueous drag reducing suspensions |
| US5932670A (en) * | 1998-03-30 | 1999-08-03 | Phillips Petroleum Company | Polymerization catalysts and processes therefor |
| US6178980B1 (en) * | 1998-08-26 | 2001-01-30 | Texaco Inc. | Method for reducing the pipeline drag of heavy oil and compositions useful therein |
| US6399676B1 (en) * | 2000-11-28 | 2002-06-04 | Conoco, Inc. | Drag-reducing polymer suspensions |
-
2001
- 2001-06-08 US US09/877,341 patent/US7012046B2/en not_active Expired - Lifetime
-
2002
- 2002-06-07 DK DK02765780T patent/DK1392995T3/en active
- 2002-06-07 EP EP20020765780 patent/EP1392995B1/en not_active Expired - Lifetime
- 2002-06-07 CA CA 2447798 patent/CA2447798A1/en not_active Abandoned
- 2002-06-07 RU RU2003133281A patent/RU2297574C2/en not_active IP Right Cessation
- 2002-06-07 AU AU2002329180A patent/AU2002329180A1/en not_active Abandoned
- 2002-06-07 CN CNB02811311XA patent/CN1267675C/en not_active Expired - Fee Related
- 2002-06-07 AT AT02765780T patent/ATE420318T1/en not_active IP Right Cessation
- 2002-06-07 WO PCT/US2002/017670 patent/WO2002101282A2/en not_active Application Discontinuation
- 2002-06-07 DE DE60230745T patent/DE60230745D1/en not_active Expired - Fee Related
-
2003
- 2003-12-05 NO NO20035404A patent/NO20035404D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US7012046B2 (en) | 2006-03-14 |
| CN1267675C (en) | 2006-08-02 |
| AU2002329180A1 (en) | 2002-12-23 |
| CN1513098A (en) | 2004-07-14 |
| RU2003133281A (en) | 2005-05-10 |
| US20020198116A1 (en) | 2002-12-26 |
| DE60230745D1 (en) | 2009-02-26 |
| EP1392995A2 (en) | 2004-03-03 |
| WO2002101282A2 (en) | 2002-12-19 |
| NO20035404D0 (en) | 2003-12-05 |
| WO2002101282A3 (en) | 2003-08-07 |
| DK1392995T3 (en) | 2009-04-20 |
| ATE420318T1 (en) | 2009-01-15 |
| EP1392995B1 (en) | 2009-01-07 |
| RU2297574C2 (en) | 2007-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2232165C2 (en) | Method of preparing amorphous high-molecular weight poly-alpha-olefin agents reducing resistance of flow | |
| AU726390B2 (en) | Process for forming polyalphaolefin drag reducing agents and composition containing same | |
| US7012046B2 (en) | Drag reducing agent slurries having alfol alcohols and processes for forming drag reducing agent slurries having alfol alcohols | |
| CA2608026C (en) | Bi- or multi-modal particle size distribution to improve drag reduction polymer dissolution | |
| CA2561566A1 (en) | Alcohol absorbed polyalphaolefin drag reducing agents | |
| CA2444015C (en) | Ultra high molecular weight polyolefin useful as flow improvers in cold fluids | |
| EP1366093B1 (en) | Alpha olefin monomer partitioning agents for drag reducing agents and methods of forming drag reducing agents using alpha olefin monomer partitioning agents | |
| RU2238282C1 (en) | Method for preparing agent for reducing hydrodynamic resistance of hydrocarbon liquid | |
| CA2608280A1 (en) | Manipulation of topological characteristics of bulk polymerized poly(alpha-olefins) via reaction variables and conditions to enhance dissolution of drag reducing polymers | |
| EP1466123A1 (en) | Process for transporting a multiphase system through a pipeline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |