US20140336345A1 - System and method for catalyst preparation - Google Patents
System and method for catalyst preparation Download PDFInfo
- Publication number
- US20140336345A1 US20140336345A1 US14/340,205 US201414340205A US2014336345A1 US 20140336345 A1 US20140336345 A1 US 20140336345A1 US 201414340205 A US201414340205 A US 201414340205A US 2014336345 A1 US2014336345 A1 US 2014336345A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- precontactor
- polymerization catalyst
- complex
- polymerization
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/06—Solidifying liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultra-violet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- 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
- C08F110/02—Ethene
-
- 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
- C08F4/00—Polymerisation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0801—Controlling the process
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F2420/00—Metallocene catalysts
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/07—High density, i.e. > 0.95 g/cm3
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/08—Low density, i.e. < 0.91 g/cm3
Definitions
- the present disclosure relates generally to catalyst preparation, and more particularly, to preparation of metallocene catalysts.
- Catalysts can be employed to facilitate the formation of products through chemical reactions. It is often desirable to prepare the catalyst in a certain way to achieve desired properties of the catalyst and/or the products. For example, in certain polymerization manufacturing facilities, the catalyst is prepared off-site by a vendor and is then shipped to the polymerization reaction facility. At the vendor facility, the catalyst may be dissolved in a solvent to form a catalyst solution, which may be used by the polymerization manufacturing facility directly or with some additional processing or handling. However, the concentration of the catalyst in the solvent may be limited by the solubility of the catalyst in the solvent. In other words, attempting to dissolve greater amounts of the catalyst in the solution may cause precipitation of the catalyst out of solution, which may be undesirable.
- the solubility of the catalyst in the solvent may be affected by temperature.
- the solubility of the catalyst may decrease at low temperatures.
- the concentration of the catalyst in the solvent may be less than desirable, thereby resulting in feeding the catalyst solution at high flow rates.
- issues with catalyst concentration in the solvent may necessitate increased sizes of storage tanks, transfer lines, pumps, and other equipment associated with handling the catalyst solution to facilitate managing the high flow rates of the catalyst solution. This may add to both capital and operating expenditures of the polymerization manufacturing facility. Further, it is now recognized that the costs and other considerations associated with transporting catalyst solution may be greater than those associated with the transportation of only the catalyst.
- FIG. 1 is a block diagram of an embodiment of a polyolefin manufacturing system with a catalyst preparation system in accordance with present embodiments;
- FIG. 2 is a schematic flow diagram of an embodiment of a catalyst preparation system that may be employed in the polyolefin manufacturing system of FIG. 1 , in accordance with present embodiments;
- FIG. 3 is a schematic flow diagram of an embodiment of a catalyst preparation system with more than one catalyst tank that may be employed in the polyolefin manufacturing system of FIG. 1 , in accordance with present embodiments;
- FIG. 4 is a schematic flow diagram of an embodiment of a catalyst preparation system with more than one catalyst mix/run tank that may be employed in the polyolefin manufacturing system of FIG. 1 , in accordance with present embodiments;
- FIG. 5 is a schematic flow diagram of an embodiment of a catalyst preparation system with separate mix and run catalyst tanks that may be employed in the polyolefin manufacturing system of FIG. 1 , in accordance with present embodiments;
- FIG. 6 is a flow chart depicting a method for preparing catalyst in accordance with present embodiments.
- the present disclosure is directed to techniques for catalyst solution preparation. More specifically, the present disclosure is directed to techniques for catalyst solution preparation by an on-site catalyst preparation system.
- the term “on-site” refers to being on the same location and/or integral with a polymerization manufacturing facility and any adjacent associated manufacturing facilities.
- the polymerization manufacturing facility may produce various polymers in a variety of different reactors, such as, but not limited to, fluidized bed reactors, gas-phase reactors, loop slurry reactors, or any combination thereof.
- Such reactor systems may be modeled using a continuous ideal stirred tank reactor (CISTR) model.
- CISTR continuous ideal stirred tank reactor
- Reactors of a polymerization manufacturing facility may receive a monomer, a diluent, and a catalyst complex prepared by a catalyst preparation system in accordance with present embodiments to produce polymers.
- a polymerization catalyst tank of the catalyst preparation system mixes a polymerization catalyst and a solvent using an agitator to generate a polymerization catalyst solution.
- a heating system coupled to polymerization catalyst tank may help maintain a temperature of the polymerization catalyst solution above a threshold. For example, the threshold may be determined to help prevent precipitation of the polymerization catalyst out of the polymerization catalyst solution.
- a precontactor of the catalyst preparation system may then receive a cocatalyst, an activator, and the polymerization catalyst solution from the polymerization catalyst tank to generate the catalyst complex.
- the precontactor may also include a heating system.
- a transfer line may be used to transfer the catalyst complex from the precontactor to the reactors of the polymerization manufacturing facility.
- the polymerization catalyst may be shipped to the polymerization manufacturing facility from the vendor in solid form (e.g., a dry powder), thereby simplifying and reducing costs associated with the transportation of the polymerization catalyst.
- the solvent used to dissolve polymerization catalyst may be selected to be particularly compatible and/or desirable for use in the reactors of the polymerization manufacturing facility.
- the solvent may be a material already being fed to the reactor, such as a comonomer.
- the concentration of the polymerization catalyst may be greater than that of catalyst solutions shipped to the polymerization manufacturing facility by vendors.
- the storage tanks and other equipment associated with the polymerization catalyst solution may be smaller and less expensive than equipment associated with vendor-supplied catalyst solutions.
- the frequency of preparing batches of catalyst solution may be reduced.
- use of high-concentration catalyst solution may improve the control of the polymerization reaction. For example, the ratio of high-molecular weight polymer to low-molecular weight polymer may be facilitated by using high-concentration catalyst solution.
- FIG. 1 depicts an embodiment of a manufacturing system 10 that employs catalysts to produce a polymer product through chemical reactions.
- FIG. 1 is a schematic representation of a manufacturing process for producing polyolefins, such as polyethylene homopolymer, copolymer, and/or terpolymer, among others.
- polyolefins such as polyethylene homopolymer, copolymer, and/or terpolymer, among others.
- the catalyst preparation techniques described herein are generally described with respect to polyolefin production, the techniques can be applied to any chemical reactor system that can be modeled using a continuous ideal stirred tank reactor model. For example, the catalyst preparation techniques can be applied to other types of polymer production.
- the manufacturing system 10 includes a reactor system 12 , which receives various feedstocks, such as a catalyst complex 14 , a monomer 16 , and/or a diluent 18 .
- the catalyst complex 14 and its preparation are described in detail below.
- the monomer 16 may include one or more monomers and/or comonomers, such as, but not limited to, ethylene, propylene, butene, hexene, octene, decene, and so forth.
- the diluent 18 may include one or more diluents, such as, but not limited to, an inert hydrocarbon that is liquid at reaction conditions, such as isobutane, propane, n-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, cyclohexane, cyclopentane, methylcyclopentane, or ethylcyclohexane, among others.
- the diluent 18 may be employed to suspend catalyst particles and polymer particles within the reactor vessels of the reactor system 12 .
- the reactor system 12 may also receive other materials, such as, but not limited to, chain transfer agents (e.g. hydrogen), catalysts, co-catalysts, and other additives.
- the reactor system 12 can include one or more polymerization reactors, such as liquid-phase reactors, gas-phase reactors, or a combination thereof. Multiple reactors may be arranged in series, in parallel, or in any other suitable combination or configuration.
- the monomer 16 e.g., one or more monomers and/or comonomers
- the monomer 16 may be polymerized to form a product containing polymer particles 20 , typically called fluff or granules.
- the monomer 16 may include 1-olefins having up to 10 carbon atoms per molecule and typically no branching nearer the double bond than the 4-position.
- the monomer 16 may include monomers and comonomers such as ethylene, propylene, butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or any combination thereof.
- the polymer particles 20 may possess one or more melt, physical, rheological, and/or mechanical properties of interest, such as density, melt index (MI), melt flow rate (MFR), copolymer or comonomer content, modulus, and crystallinity.
- the reaction conditions such as temperature, pressure, flow rate, mechanical agitation, product takeoff, component concentrations, polymer production rate, and so forth, may be selected to achieve the desired properties of the polymer particles 20 .
- Product effluent which includes the formed polymer particles 20 , as well as non-polymer components, such as the diluent 18 , unreacted monomer 16 , and residual catalyst, exits the reactor system 12 and enters various systems, such as a product recovery system, an extrusion system, and/or a loadout system, to produce extruded polymer pellets.
- polymer pellets that may be produced by the manufacturing system 10 include, but are not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and enhanced polyethylene such as bimodal grades.
- the various types and grades of polyethylene pellets may be marketed, for example, under the brand names Marlex® polyethylene or MarFlex® polyethylene of Chevron-Phillips Chemical Company, LP, of The Woodlands, Tex., USA.
- the produced polymer (e.g., polyethylene) pellets can be used in the manufacture of a variety of products, components, household items and other items, including adhesives (e.g., hot-melt adhesive applications), electrical wire and cable, agricultural films, shrink film, stretch film, food packaging films, flexible food packaging, milk containers, frozen-food packaging, trash and can liners, grocery bags, heavy-duty sacks, plastic bottles, safety equipment, coatings, toys, and an array of containers and plastic products. Further, the products and components formed from the polymer pellets may be further processed and assembled prior to distribution and sale to the consumer.
- adhesives e.g., hot-melt adhesive applications
- electrical wire and cable e.g., electrical wire and cable
- agricultural films shrink film, stretch film, food packaging films, flexible food packaging, milk containers, frozen-food packaging, trash and can liners, grocery bags, heavy-duty sacks, plastic bottles, safety equipment, coatings, toys, and an array of containers and plastic products.
- the products and components formed from the polymer pellets may
- the polymer pellets are generally subjected to further processing, such as blow molding, injection molding, rotational molding, blown film, cast film, extrusion (e.g., sheet extrusion, pipe and corrugated extrusion, coating/lamination extrusion, etc.), and so on.
- further processing such as blow molding, injection molding, rotational molding, blown film, cast film, extrusion (e.g., sheet extrusion, pipe and corrugated extrusion, coating/lamination extrusion, etc.), and so on.
- the catalyst complex 14 may be prepared by combining a catalyst solution 22 , a cocatalyst 24 , and activator 26 .
- the cocatalyst 24 include, but are not limited to, organometallic compounds, such as triisobutylaluminum, triethylaluminum or tri-ethyl boron, alkyl aluminum compounds, methyl aluminoxane, and so forth.
- the activator 26 include, but are not limited to, solid super acids and chemically-treated solid oxides.
- the solid oxide can have a surface area of from about 100 to about 1000 m 2 /g.
- the solid oxide can have a surface area of from about 200 to about 800 m 2 /g.
- the solid oxide can have a surface area of from about 250 to about 600 m 2 /g.
- the activator 26 when it is a chemically-treated solid oxide, it can include a solid inorganic oxide that includes oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or that includes oxygen and one or more elements selected from the lanthanide or actinide elements (See: Hawley's Condensed Chemical Dictionary, 11 th Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6 th Ed., Wiley-Interscience, 1999).
- the inorganic oxide can include oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
- Suitable examples of solid oxide materials or compounds that can be used to form the chemically-treated solid oxide used as the activator 26 can include, but are not limited to, Al 2 O 3 , B 2 O 3 , BeO, Bi 2 O 3 , CdO, Co 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , La 2 O 3 , Mn 2 O 3 , MoO 3 , NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2 , V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , and the like, including mixed oxides thereof, coatings of one oxide with another, and combinations thereof.
- the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof.
- the catalyst solution 22 may be prepared by combining a catalyst 28 and a solvent 30 .
- the catalyst 28 may be dissolved in the solvent 30 .
- the catalyst 28 may essentially be a solid material.
- the catalyst 28 include, but are not limited to, metallocene catalysts, Ziegler-Natta catalysts, chromium-based catalysts, vanadium-based catalysts, nickel-based catalysts, or a combination thereof, among others.
- chromium-based catalysts include, but are not limited to, chrome, chromocene, chrome titanium, chrome silica, chrome with aluminum phosphate, and so forth.
- the solvent 30 examples include, but are not limited to, comonomers, such as those listed above, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or any combination thereof.
- the solvent 30 is 1-hexene and excludes toluene. Use of 1-hexene may be more desirable than toluene because 1-hexene has fewer environmental concerns than toluene.
- 1-hexene is used (i.e., chemically consumed or reacted) during polymerization and thus, would appear as a residual in the polymer particles 20 in smaller quantities than toluene, which is not used during polymerization.
- Certain catalysts 28 may be less soluble in 1-hexene than toluene.
- the heating of the catalyst solution 22 may facilitate use of 1-hexene instead of toluene and help prevent precipitation of the catalyst 28 .
- FIG. 2 depicts an embodiment of a catalyst preparation system 40 that may be used to prepare the catalyst complex 14 fed to the reactor system 12 .
- the catalyst preparation system 40 may include a catalyst tank 42 to store the catalyst 28 .
- a catalyst control valve 44 may be used as a transfer means to control the transfer of the catalyst 28 from the catalyst tank 42 to a catalyst mix/run tank 46 .
- Other catalyst transfer means can also be employed either with or without a catalyst control valve 44 .
- the catalyst 28 may be pressured (e.g., via the use of nitrogen), pumped, conveyed, or otherwise transported to the catalyst mix/run tank 46 .
- the catalyst preparation system 40 may also include a solvent tank 48 to store the solvent 30 .
- a solvent control valve 50 may be used to control the transfer of the solvent 30 to the catalyst mix/run tank 46 .
- Other solvent transfer means can also be used either with or without a solvent control valve 50 .
- the solvent 30 may be pressured from the solvent tank 48 or in certain embodiments, a pump may be used to transfer the solvent 30 from the solvent tank 48 . Indeed, in some embodiments, a pump may replace or cooperate with the solvent control valve 50 .
- the catalyst mix/run tank 46 includes an agitator 52 that is powered by a motor 54 .
- the agitator 52 may be used to dissolve and/or mix the catalyst 28 and the solvent 30 in the catalyst mix/run tank 46 .
- the agitator 52 may help speed the mixing of the catalyst 28 and the solvent 30 and/or improve the consistency of the catalyst solution 22 .
- the catalyst mix/run tank 46 may include a heating system 56 to heat the catalyst solution 22 . Examples of the heating system 56 include, but are not limited to, a heated tempered water jacket, a heated tempered water coil, an electrical clamp-on jacket, or any other suitable heating system.
- a transfer line 58 may be used to transfer the catalyst solution 22 from the catalyst mix/run tank 46 .
- the transfer line 58 may include a piping heating system 60 , such as, but not limited to, a heated tempered water jacket, electrical tracing, or any other suitable heating system, which may be used to maintain a temperature of the catalyst solution 22 above a threshold as the catalyst solution 22 travels through the transfer line 58 .
- a catalyst solution pump 62 may be coupled to the transfer line 58 and used to transfer the catalyst solution 22 from the catalyst mix/run tank 46 .
- the transfer line 58 may include a catalyst solution control valve 64 to control the transfer of the catalyst solution 22 from the catalyst mix/run tank 46 to a precontactor 66 either with or without a catalyst solution pump 62 .
- the precontactor 66 may receive the cocatalyst 24 from a cocatalyst tank 68 via a cocatalyst pump 70 .
- the cocatalyst 24 may be pressured to the precontactor 66 or otherwise transferred.
- the cocatalyst 24 may be transferred directly from the cocatalyst tank 68 to one or more reactors in the reactor system 12 , bypassing the precontactor 66 .
- An activator tank 72 may store the activator 26 before being transferred to the precontactor 66 via pressuring, a pump, or the like.
- the precontactor 66 includes a precontactor agitator 74 powered by a precontactor motor 76 .
- the precontactor agitator 74 may be used to thoroughly mix the catalyst solution 22 with the cocatalyst 24 and the activator 26 .
- the precontactor 66 may also include a precontactor heating system 78 to heat the catalyst complex 14 in the precontactor 66 .
- the precontactor heating system 78 may be similar to the heating system 56 for the catalyst mix/run tank 46 described above. In one embodiment, the precontactor heating system 78 may be used only during preparation of the catalyst complex 14 and then shut off afterwards.
- a precontactor transfer line 80 may be used to transfer the catalyst complex 14 from the precontactor 66 .
- one or more precontactor pumps 82 may be used to transfer the catalyst complex 14 from the precontactor 66 to one or more reactors in the reactor system 12 .
- operating conditions within the catalyst preparation system 40 may be controlled to produce the catalyst complex 14 with desired properties.
- a control system 90 can be employed to control operating conditions within the manufacturing system 10 , such as the catalyst preparation system 40 .
- the control system 90 may be employed to adjust the flow rates, temperatures, and/or other properties of the catalyst 28 , solvent 30 , catalyst solution 22 , cocatalyst 24 , activator 26 , and/or catalyst complex 14 .
- the control system 90 may be employed to transition from feeding one type of catalyst complex 14 to the reactor system 12 to feeding another type of catalyst complex 14 to the reactor system 12 .
- control system 90 may be employed to monitor and/or adjust operating conditions within the manufacturing system 10 , such as temperatures, pressures, the reaction rate, and the solids concentrations, among others.
- control system 90 may receive input signals 92 from sensors (such as, temperature sensors, pressure sensors, and/or flow transducers, among others) within the manufacturing system 10 that are indicative of operating conditions and may then generate control signals 102 to adjust operating conditions of the manufacturing system 10 .
- the control system 90 may receive input signals 92 from various sensors disposed within the catalyst preparation system 40 , such as, but not limited to, a catalyst mix/run tank temperature sensor 94 , a catalyst mix/run tank concentration sensor 96 , a precontactor temperature sensor 98 , a catalyst complex flow sensor 100 , and so forth. In other embodiments, the control system 90 may receive input signals 92 from other sensors disposed in the catalyst preparation system 40 and/or the manufacturing system 10 .
- the control system 90 may transmit control signals 102 to various devices and equipment disposed in the catalyst preparation system 40 , such as, but not limited to, any catalyst transfer means, the catalyst control valve 44 , any solvent transfer means, the solvent control valve 50 , the catalyst mix/run tank motor 54 , the catalyst mix/run tank heating system 56 , the transfer pipe heating system 60 , the catalyst solution transfer pump 62 , the catalyst solution control valve 64 , the cocatalyst pump 70 , the precontactor motor 76 , the precontactor pump 82 , the precontactor heating system 78 , and so forth.
- any catalyst transfer means such as, but not limited to, any catalyst transfer means, the catalyst control valve 44 , any solvent transfer means, the solvent control valve 50 , the catalyst mix/run tank motor 54 , the catalyst mix/run tank heating system 56 , the transfer pipe heating system 60 , the catalyst solution transfer pump 62 , the catalyst solution control valve 64 , the cocatalyst pump 70 , the precontactor motor 76 , the precontactor
- the input signal 92 received by the control system 90 may be indicative of a demand for the catalyst 28 in the catalyst mix/run tank 46 .
- the input signal 92 may be indicative of a concentration of the catalyst 28 in the catalyst solution 22 that is lower than a setpoint and may be transmitted by the catalyst mix/run tank concentration sensor 96 .
- the control system 90 may activate an output, such as an actuator for the catalyst control valve 44 , to supply the catalyst 28 to the catalyst mix/run tank 46 and/or other catalyst transfer means.
- the control system 90 may receive an additional input signal 92 indicative of a demand for the catalyst solution 22 in the precontactor 66 .
- the input signal 92 may be indicative of a concentration of the catalyst 28 in the catalyst complex 14 or the level of the catalyst complex 14 in the precontactor 66 that is below a setpoint.
- the control system 90 may activate an output, such as an actuator for the catalyst solution pump 62 and/or the catalyst solution control valve 64 , to supply the catalyst solution 22 to the precontactor 66 .
- the control system 90 may receive an additional input signal 92 indicative of a demand for the catalyst complex 14 in the reactor system 12 .
- the input signal 92 may be indicative of a flow rate of the catalyst complex 14 to the reactor system 12 that is below a setpoint and may be transmitted by the catalyst complex flow sensor 100 .
- control system 90 may activate an output, such as an actuator for the precontactor pump 82 , to supply more catalyst complex 14 to the reactor system 12 .
- control system 90 may receive an additional input signal 92 indicative of a temperature of the catalyst solution 22 in the catalyst mix/run tank 46 .
- the input signal 92 may be transmitted by the catalyst mix/run tank temperature sensor 94 and indicate that the temperature of the catalyst solution 22 is below a setpoint.
- the control system 90 may activate an output, such as an actuator for the heating system 56 , to supply additional heat to the catalyst mix/run tank 46 .
- the control system 90 may operate in a similar manner to supply heat to the precontactor 66 based on data acquired via an input signal 92 from the precontactor temperature sensor 98 .
- control system 90 may be a Distributed Control System (DCS).
- DCS Distributed Control System
- the control system 90 may include one or more automation controllers, microprocessors, instruction set processors, graphics processors, analog to digital converters, interface boards, and/or related chip sets.
- the control system 90 may cooperate with storage that stores executable code, data, and instructions for the control system 90 .
- the storage may store non-transitory machine-readable code for maintaining a temperature of the catalyst solution 22 above a threshold based on measured process variables.
- the storage may include volatile memory, such as random access memory, and/or non-volatile memory, such as read only memory, flash memory, a hard drive, or any other suitable optical, magnetic, or solid-state computer readable media, as well as a combination thereof.
- the control system 90 may also include a display and a user interface.
- the display and the user interface may be part of an operator workstation.
- the display may display a variety of information about the manufacturing system 10 .
- the display may display graphs, trends, mass balances, energy balances, process data, such as measured process variables, and/or predictive data, among others that facilitate user monitoring and control of the manufacturing system 10 .
- the display may display screens of the user interface that facilitate entry of user inputs. For example, a user may enter desired operating parameters (e.g., setpoints) or adjustments that should be made to the manufacturing system 10 . In certain embodiments, a user may review an essentially instantaneous reaction rate or trend shown on the display and may enter a desired catalyst feed rate value or catalyst feed rate adjustment. In another example, a user may adjust the temperature of the reactor system 12 or one or more of the feed rates through the user interface. However, in other embodiments, at least some of the operating conditions may be adjusted automatically by the control system 90 . For example, in certain embodiments, the control system 90 may automatically adjust the flow rate of catalyst 28 to the catalyst mix/run tank 46 based on a measured concentration of the catalyst 28 in the catalyst solution 22 .
- desired operating parameters e.g., setpoints
- a user may review an essentially instantaneous reaction rate or trend shown on the display and may enter a desired catalyst feed rate value or catalyst feed rate adjustment.
- a user may adjust the temperature
- the control system 90 may be used to maintain a temperature of the catalyst solution 22 and/or the catalyst complex 14 above a threshold.
- the threshold may be selected to help prevent precipitation of the catalyst 28 out of the catalyst solution 22 and/or the catalyst complex 14 .
- the threshold may be between approximately 40 degrees Celsius to approximately 50 degrees Celsius. In one embodiment, the threshold may be approximately 45 degrees Celsius.
- a not-to-exceed temperature threshold such as approximately 60 degrees Celsius or approximately 65 degrees Celsius, may be selected based on the particular catalyst 28 used to avoid degradation of the catalyst 28 . In one embodiment, the threshold may be between approximately 40 degrees Celsius and approximately 65 degrees Celsius.
- the catalyst mix/run tank temperature sensor 94 may indicate a temperature of the catalyst solution 22 and the precontactor temperature sensor 98 may indicate a temperature of the catalyst complex 14 .
- the control system 90 may send control signals 102 to the catalyst mix/run tank heating system 56 and/or the precontactor heating system 78 to maintain the temperatures of the catalyst solution 22 and/or the catalyst complex 14 , respectively, above the threshold.
- control system 90 may be used to maintain a concentration of the catalyst 28 in the catalyst solution 22 and/or the catalyst complex 14 above a threshold.
- the threshold may be selected to help provide a desired amount of the catalyst 28 to reach the reactor system 12 .
- the catalyst concentration threshold may be above approximately 0.40 weight percent in the solvent 30 . This concentration threshold may be greater than the concentration of catalyst solution 22 provided by off-site vendors because off-site vendors may be limited by transportation issues. Thus, present embodiments may enable the size of the catalyst mix/run tank 46 and associated equipment and lines to be reduced relative to traditional operations.
- the catalyst concentration threshold may be approximately 0.47 weight percent in the solvent 30 .
- the catalyst mix/run tank concentration sensor 96 may provide the input signal 92 to the control system 90 indicative of the concentration of the catalyst 28 in the catalyst solution 22 .
- the control system 90 may transmit the control signal 102 to the catalyst control valve 44 and/or the solvent control valve 50 to maintain the concentration of the catalyst 28 in the catalyst solution 22 above the threshold.
- the control signal 102 may open the catalyst control valve 44 and/or close the solvent control valve 50 if the indicated concentration of the catalyst 28 in the catalyst solution 22 is below the threshold.
- the control system 90 may close the catalyst control valve 44 and/or open the solvent control valve 50 if the concentration of the catalyst 28 in the catalyst solution 22 is above the threshold.
- control system 90 may be used to adjust one or more of the catalyst solution transfer pump 62 , catalyst solution control valve 64 , and/or cocatalyst pump 70 to adjust or maintain the concentration of the catalyst 28 in the catalyst complex 14 in the precontactor 66 .
- the precontactor 66 may include a concentration sensor similar to the catalyst mix/run tank concentration sensor 96 to provide the input signal 92 to the control system 90 .
- the control system 90 may transmit control signals 102 to the precontactor pump 82 to adjust or maintain a flow rate of the catalyst complex 14 to the reactor system 12 .
- the control system 90 may also be used to control the catalyst mix/run tank motor 54 and/or the precontactor motor 76 .
- the concentration sensor 96 shown in FIG. 2 may use various techniques, such as spectrophotometry, to determine the concentration of the catalyst 28 in the catalyst solution 22 .
- the concentration sensor 96 may be an ultraviolet-visible photometric analyzer (i.e., a UV-Vis analyzer), which may utilize the Beer-Lambert law to determine the concentration of the catalyst 28 .
- the UV-Vis analyzer may pass a wavelength of light through the catalyst solution 22 and measure the absorbance of the light at the selected wavelength. The measured absorbance may then be compared to a calibration curve to determine the concentration of the catalyst 28 .
- the specific wavelength of light may be selected to have little or no absorption by the solvent 30 , thereby reducing errors in the determined concentration.
- the absorbance of light at the selected wavelength may be essentially a function of the concentration of the catalyst 28 in the catalyst solution 22 .
- the UV-Vis analyzer may be used in various ways, such as, but not limited to, providing a continuous on-line indication of the concentration of the catalyst 28 in the catalyst solution 22 and/or the catalyst complex 14 , analyzing batches of the catalyst solution 28 and/or the catalyst complex 14 , and so forth.
- the catalyst solution 22 may include particles or other particulate matter that may affect the spectrophotometric analysis.
- the UV-Vis analyzer may include a filter or similar device to remove particles and/or other matter from the catalyst solution 22 .
- a measurement cell of the UV-Vis analyzer may be flushed on a regular basis, e.g., daily, to reduce buildup of material that may affect the accuracy of the measurement.
- other techniques may be used to determine the concentration of the catalyst 28 in the catalyst solution 22 .
- FIG. 3 depicts an embodiment of the catalyst preparation system 40 that can be employed in the manufacturing system 10 shown in FIG. 1 .
- FIG. 3 depicts a system that uses two catalysts.
- a first catalyst tank 120 may be used to store a first catalyst 122 and a first catalyst control valve 124 may be used to control the flow of the first catalyst 122 to the catalyst mix/run tank 46 .
- the catalyst preparation system 40 may also include a second catalyst tank 126 to store a second catalyst 128 and a second catalyst control valve 130 may be used to flow the second catalyst 128 to the catalyst mix/run tank 46 .
- the use of the first and second catalysts 122 and 128 may facilitate production of polymer particles 20 with certain desired characteristics compared to polymer particles 20 produced using a single catalyst.
- the catalyst preparation system 40 shown in FIG. 3 is similar to the system 40 shown in FIG. 2 .
- FIG. 4 depicts an embodiment of the catalyst preparation system 40 with two catalyst mix/run tanks Specifically, a first catalyst control valve 136 may control the flow rate of the catalyst 28 to a first catalyst mix/run tank 140 and a first solvent control valve 138 may control the flow rate of the solvent 30 to the first catalyst mix/run tank 140 .
- the first catalyst mix/run tank 140 may include a first agitator 142 driven by a first motor 144 and may be heated using a first heating system 146 .
- the first catalyst mix/run tank 140 may include a first temperature sensor 148 and a first concentration sensor 149 .
- a second catalyst control valve 145 may control the flow rate of the catalyst 28 to a second catalyst mix/run tank 150 and a second solvent control valve 147 may control the flow rate of the solvent 30 to the second catalyst mix/run tank 150 .
- the second catalyst mix/run tank 150 may include a second agitator 152 driven by a second motor 154 , a second heating system 156 , a second temperature sensor 158 , and a second concentration sensor 160 .
- the catalyst solution 122 from the first catalyst mix/run tank 140 may be transferred to the precontactor 66 through a first transfer line 162 and the catalyst solution 22 from the second catalyst mix/run tank 150 may be transferred via a second transfer line 164 .
- the first and second catalyst mix/run tanks 140 and 150 may be used as online spares for one another.
- the first catalyst mix/run tank 140 may be used to supply the catalyst solution 22 to the precontactor 66 until the first catalyst mix/run tank 140 is approximately empty, below a minimum level threshold, or otherwise out-of-service.
- the second catalyst mix/run tank 150 may be used to supply the catalyst solution 22 to the precontactor 66 while the first catalyst mix/run tank 140 is unavailable.
- the first catalyst mix/run tank 140 may be used to supply the catalyst solution 22 to the precontactor 66 .
- the catalyst preparation system 40 shown in FIG. 4 is similar to the system 40 shown in FIG. 2 .
- FIG. 5 depicts an embodiment of the catalyst preparation system 40 including separate mix and run tanks
- the catalyst preparation system 40 includes a catalyst mix tank 180 that includes a catalyst mix agitator 182 driven by catalyst mix motor 184 .
- the catalyst mix tank 180 may include a catalyst mix heating system 186 , a catalyst mix concentration sensor 187 , and a catalyst mix temperature sensor 188 .
- a catalyst mix pump 191 may be used to transfer the catalyst solution 22 from the catalyst mix tank 180 to a catalyst run tank 190 via catalyst mix transfer line 189 .
- the catalyst run tank 190 may include a catalyst run agitator 192 driven by catalyst run motor 194 , a catalyst run heating system 196 , a catalyst run concentration sensor 197 , and a catalyst run temperature sensor 198 .
- a catalyst run transfer line 200 may be used to transfer the catalyst solution 22 from the catalyst run tank 190 to the precontactor 66 .
- the catalyst mix tank 180 may be used to prepare the catalyst solution 22 and the catalyst run tank 190 may be used to supply the catalyst solution 22 to the precontactor 66 .
- the catalyst run tank 190 is approximately empty or below a minimal level threshold, the catalyst solution 22 from the catalyst mix tank 180 may be used to refill the catalyst run tank 190 . Additional catalyst solution 22 may then be prepared in the catalyst tank 180 to be transferred later to the catalyst run tank 190 .
- the catalyst preparation system 40 shown in FIG. 5 is similar to the system 40 shown in FIG. 2 .
- FIG. 6 depicts a method 210 for preparing the catalyst complex 14 .
- the method 210 may begin by mixing the catalyst 28 and the solvent 30 in the catalyst mix/run tank 46 to generate the catalyst solution 22 (block 212 ).
- the control system 90 may activate the catalyst mix/run tank agitator 52 to mix the contents of the catalyst mix/run tank 46 to generate the catalyst solution 22 .
- the catalyst solution 22 may also be prepared, for example, in the first catalyst mix/run tank 140 , the second catalyst mix/run tank 150 , or the catalyst mix tank 180 .
- the method 210 may then continue by heating the catalyst solution 22 to maintain a temperature of the catalyst solution 22 above a threshold (block 214 ).
- control system 90 may be used to control the heat provided to the catalyst solution 22 via the catalyst mix/run tank heating system 56 based on the temperature sensed by the catalyst mix/run tank temperature sensor 94 .
- control system 90 may be used to maintain the temperature of the catalyst solution 22 above the threshold in, for example, the first catalyst mix/run tank 140 , the second catalyst mix/run tank 150 , the catalyst mix tank 180 , or the catalyst run tank 190 .
- the method 210 may then continue by mixing the heated catalyst solution 22 with the cocatalyst 24 and the activator 26 in the precontactor 66 to generate the catalyst complex 14 (block 216 ).
- the control system 90 may use the precontactor agitator 74 to mix the contents of the precontactor 66 to generate the catalyst complex 14 .
- the method 210 may then continue by heating the catalyst complex 14 to maintain a temperature above a threshold (block 218 ).
- the control system 90 may use the precontactor heating system 78 to maintain the temperature of the catalyst complex 14 above the threshold as determined by the precontactor temperature sensor 98 .
- the method may then continue by transferring the heated catalyst complex 14 to the reactor system 12 (block 220 ).
- the control system 90 may be used to control the precontactor pump 82 to adjust the flow rate of the catalyst complex to the reactor system 12 as measured by the catalyst complex flow sensor 100 .
- Embodiment 1 A system, comprising: an agitator disposed inside a polymerization catalyst tank and configured to mix or dissolve at least a portion or all of a polymerization catalyst and a solvent to generate a polymerization catalyst solution; a heating system coupled to the polymerization catalyst tank and configured to maintain a temperature of the polymerization catalyst solution above a threshold; a precontactor configured to receive feed streams comprising an activator and the polymerization catalyst solution from the polymerization catalyst tank to generate a catalyst complex; and a transfer line configured to transfer the catalyst complex from an outlet of the precontactor to a reactor.
- Embodiment 2 The system of embodiment 1, wherein the precontactor comprises: a second agitator disposed inside the precontactor and configured to mix the activator and polymerization catalyst solution; and a second heating system coupled to the precontactor and configured to maintain a temperature of the catalyst complex above a second threshold.
- Embodiment 3 The system defined in any preceding embodiment, comprising the reactor configured to polymerize monomer into polymer solids in the presence of the catalyst complex.
- Embodiment 4 The system defined in any preceding embodiment, comprising a plurality of reactors configured to polymerize monomer into polymer solids in the presence of the catalyst complex.
- Embodiment 5 The system defined in any preceding embodiment, wherein the plurality of reactors are operated in a series configuration or in a parallel configuration.
- Embodiment 6 The system defined in any preceding embodiment, wherein the polymerization catalyst comprises a metallocene catalyst.
- Embodiment 7 The system defined in any preceding embodiment, wherein the solvent comprises a comonomer.
- Embodiment 8 The system defined in any preceding embodiment, wherein the comonomer comprises 1-hexene.
- Embodiment 9 The system defined in any preceding embodiment, wherein the feed streams comprise a cocatalyst.
- Embodiment 10 The system defined in any preceding embodiment, wherein the cocatalyst comprises triisobutylaluminum, triethylaluminum, or any combination thereof.
- Embodiment 11 The system defined in any preceding embodiment, wherein the activator comprises a solid super acid.
- Embodiment 12 The system defined in any preceding embodiment, wherein the heating system is configured to heat a second transfer line configured to transfer the polymerization catalyst solution from the polymerization catalyst tank to the precontactor.
- Embodiment 13 The system defined in any preceding embodiment, comprising a sensor configured to provide an indication of a concentration of the polymerization catalyst in the polymerization catalyst solution.
- Embodiment 14 A method, comprising: making a polymerization catalyst solution by dissolving a polymerization catalyst with one or more solvents in a heated polymerization catalyst tank; making a polymerization catalyst complex by combining at least a portion of the polymerization catalyst solution with an activator in a precontactor; and transferring the polymerization catalyst complex from the precontactor to a reactor.
- Embodiment 15 The method or system defined in any preceding embodiment, comprising combining a cocatalyst with the polymerization catalyst solution and the activator in the precontactor.
- Embodiment 16 The method or system defined in any preceding embodiment, comprising heating the polymerization catalyst complex in the precontactor.
- Embodiment 17 The method or system defined in any preceding embodiment, comprising maintaining the polymerization catalyst solution in the polymerization catalyst tank at a temperature between approximately 40 degrees Celsius to 50 degrees Celsius.
- Embodiment 18 The method or system defined in any preceding embodiment, comprising polymerizing a monomer in the presence of the catalyst complex to produce polymer solids in the reactor.
- Embodiment 19 The method or system defined in any preceding embodiment, comprising measuring a concentration of the polymerization catalyst in the polymerization catalyst solution using an ultraviolet-visible photometric analyzer.
- Embodiment 20 The method or system defined in any preceding embodiment, comprising maintaining the concentration of the polymerization catalyst in the polymerization catalyst solution above approximately 0.40 weight percent in the solvent.
- Embodiment 21 A system, comprising: one or more automation controllers configured to: receive a first input indicative of a demand for a metallocene catalyst in a metallocene catalyst tank; activate a first output to supply the metallocene catalyst to the metallocene catalyst tank, such that the metallocene catalyst and a solvent mix in the metallocene catalyst tank to form a metallocene catalyst solution; receive a second input indicative of a demand for the metallocene catalyst solution in a precontactor; and activate a second output to supply the metallocene catalyst solution to the precontactor; such that the metallocene catalyst solution and an activator mix in the precontactor to form a metallocene catalyst complex.
- Embodiment 22 The method or system defined in any preceding embodiment, wherein the one or more automation controllers are configured to: receive a third input indicative of a demand for the metallocene catalyst complex in a reactor; and activate a third output to supply the metallocene catalyst complex to the reactor.
- Embodiment 23 The method or system defined in any preceding embodiment, wherein the first and second outputs comprise a control valve actuator, a pump actuator, or any combination thereof.
- Embodiment 24 The method or system defined in any preceding embodiment, wherein the second input comprises a concentration of the metallocene catalyst in the metallocene catalyst tank.
- Embodiment 25 The method or system defined in any preceding embodiment, comprising a sensor configured to generate the second input, wherein the sensor comprises an ultraviolet-visible photometric analyzer.
- Embodiment 26 The method or system defined in any preceding embodiment, wherein the one or more automation controllers are configured to: receive a fourth input indicative of a temperature of the metallocene catalyst solution in the metallocene catalyst tank; and activate a fourth output to supply heat to the metallocene catalyst tank.
- Embodiment 27 A catalyst complex, comprising: a metallocene catalyst solution, comprising a mixture of a metallocene catalyst and a solvent, wherein a concentration of the metallocene catalyst in the metallocene catalyst solution is greater than approximately 0.40 weight percent in the solvent; and an activator.
- Embodiment 28 The method, system, or catalyst complex defined in any preceding embodiment, wherein the solvent comprises a comonomer, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or a combination thereof.
- the solvent comprises a comonomer, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or a combination thereof.
- Embodiment 29 The method, system, or catalyst complex defined in any preceding embodiment, comprising a cocatalyst.
- Embodiment 30 The method, system, or catalyst complex defined in any preceding embodiment, wherein the cocatalyst comprises triisobutylaluminum, triethylaluminum, or any combination thereof.
- Embodiment 31 The method, system, or catalyst complex defined in any preceding embodiment, wherein the activator comprises a solid super acid.
Abstract
Techniques are provided for catalyst preparation. A system for catalyst preparation may include an agitator disposed inside a polymerization catalyst tank and configured to mix a polymerization catalyst and a solvent to generate a polymerization catalyst solution. The system may also include a heating system coupled to the polymerization catalyst tank and configured to maintain a temperature of the polymerization catalyst solution above a threshold. The system may also include a precontactor configured to receive feed streams comprising an activator and the polymerization catalyst solution from the polymerization catalyst tank to generate a catalyst complex. The system may also include a transfer line configured to transfer the catalyst complex from an outlet of the precontactor to a reactor.
Description
- This application is a divisional of U.S. patent application Ser. No. 14/016,648, entitled “System and Method for Catalyst Preparation” filed on Oct. 18, 2012, which is incorporated by reference herein in its entirety.
- The present disclosure relates generally to catalyst preparation, and more particularly, to preparation of metallocene catalysts.
- This section is intended to introduce the reader to aspects of art that may be related to aspects of the present disclosure, which are described and/or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. Accordingly, it should be understood that these statements are to be read in this light and not as admissions of prior art.
- Catalysts can be employed to facilitate the formation of products through chemical reactions. It is often desirable to prepare the catalyst in a certain way to achieve desired properties of the catalyst and/or the products. For example, in certain polymerization manufacturing facilities, the catalyst is prepared off-site by a vendor and is then shipped to the polymerization reaction facility. At the vendor facility, the catalyst may be dissolved in a solvent to form a catalyst solution, which may be used by the polymerization manufacturing facility directly or with some additional processing or handling. However, the concentration of the catalyst in the solvent may be limited by the solubility of the catalyst in the solvent. In other words, attempting to dissolve greater amounts of the catalyst in the solution may cause precipitation of the catalyst out of solution, which may be undesirable. In addition, the solubility of the catalyst in the solvent may be affected by temperature. For example, the solubility of the catalyst may decrease at low temperatures. Thus, the concentration of the catalyst in the solvent may be less than desirable, thereby resulting in feeding the catalyst solution at high flow rates. In addition, it is now recognized that issues with catalyst concentration in the solvent may necessitate increased sizes of storage tanks, transfer lines, pumps, and other equipment associated with handling the catalyst solution to facilitate managing the high flow rates of the catalyst solution. This may add to both capital and operating expenditures of the polymerization manufacturing facility. Further, it is now recognized that the costs and other considerations associated with transporting catalyst solution may be greater than those associated with the transportation of only the catalyst.
- Advantages of the present disclosure may become apparent upon reading the following detailed description and upon reference to the drawings in which:
-
FIG. 1 is a block diagram of an embodiment of a polyolefin manufacturing system with a catalyst preparation system in accordance with present embodiments; -
FIG. 2 is a schematic flow diagram of an embodiment of a catalyst preparation system that may be employed in the polyolefin manufacturing system ofFIG. 1 , in accordance with present embodiments; -
FIG. 3 is a schematic flow diagram of an embodiment of a catalyst preparation system with more than one catalyst tank that may be employed in the polyolefin manufacturing system ofFIG. 1 , in accordance with present embodiments; -
FIG. 4 is a schematic flow diagram of an embodiment of a catalyst preparation system with more than one catalyst mix/run tank that may be employed in the polyolefin manufacturing system ofFIG. 1 , in accordance with present embodiments; -
FIG. 5 is a schematic flow diagram of an embodiment of a catalyst preparation system with separate mix and run catalyst tanks that may be employed in the polyolefin manufacturing system ofFIG. 1 , in accordance with present embodiments; and -
FIG. 6 is a flow chart depicting a method for preparing catalyst in accordance with present embodiments. - One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, not all features of an actual implementation are described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
- The present disclosure is directed to techniques for catalyst solution preparation. More specifically, the present disclosure is directed to techniques for catalyst solution preparation by an on-site catalyst preparation system. As used herein, the term “on-site” refers to being on the same location and/or integral with a polymerization manufacturing facility and any adjacent associated manufacturing facilities. The polymerization manufacturing facility may produce various polymers in a variety of different reactors, such as, but not limited to, fluidized bed reactors, gas-phase reactors, loop slurry reactors, or any combination thereof. Such reactor systems may be modeled using a continuous ideal stirred tank reactor (CISTR) model.
- Reactors of a polymerization manufacturing facility may receive a monomer, a diluent, and a catalyst complex prepared by a catalyst preparation system in accordance with present embodiments to produce polymers. In certain embodiments, a polymerization catalyst tank of the catalyst preparation system mixes a polymerization catalyst and a solvent using an agitator to generate a polymerization catalyst solution. A heating system coupled to polymerization catalyst tank may help maintain a temperature of the polymerization catalyst solution above a threshold. For example, the threshold may be determined to help prevent precipitation of the polymerization catalyst out of the polymerization catalyst solution. A precontactor of the catalyst preparation system may then receive a cocatalyst, an activator, and the polymerization catalyst solution from the polymerization catalyst tank to generate the catalyst complex. The precontactor may also include a heating system. A transfer line may be used to transfer the catalyst complex from the precontactor to the reactors of the polymerization manufacturing facility.
- By preparing the polymerization catalyst solution on-site, the polymerization catalyst may be shipped to the polymerization manufacturing facility from the vendor in solid form (e.g., a dry powder), thereby simplifying and reducing costs associated with the transportation of the polymerization catalyst. Further, the solvent used to dissolve polymerization catalyst may be selected to be particularly compatible and/or desirable for use in the reactors of the polymerization manufacturing facility. For example, in certain embodiments, the solvent may be a material already being fed to the reactor, such as a comonomer. In addition, by heating the polymerization catalyst solution in the catalyst preparation system, the concentration of the polymerization catalyst may be greater than that of catalyst solutions shipped to the polymerization manufacturing facility by vendors. Thus, the storage tanks and other equipment associated with the polymerization catalyst solution may be smaller and less expensive than equipment associated with vendor-supplied catalyst solutions. In addition, the frequency of preparing batches of catalyst solution may be reduced. Further, use of high-concentration catalyst solution may improve the control of the polymerization reaction. For example, the ratio of high-molecular weight polymer to low-molecular weight polymer may be facilitated by using high-concentration catalyst solution.
-
FIG. 1 depicts an embodiment of amanufacturing system 10 that employs catalysts to produce a polymer product through chemical reactions. In particular,FIG. 1 is a schematic representation of a manufacturing process for producing polyolefins, such as polyethylene homopolymer, copolymer, and/or terpolymer, among others. Although the catalyst preparation techniques described herein are generally described with respect to polyolefin production, the techniques can be applied to any chemical reactor system that can be modeled using a continuous ideal stirred tank reactor model. For example, the catalyst preparation techniques can be applied to other types of polymer production. - As shown in
FIG. 1 , themanufacturing system 10 includes areactor system 12, which receives various feedstocks, such as acatalyst complex 14, amonomer 16, and/or a diluent 18. Thecatalyst complex 14 and its preparation are described in detail below. Themonomer 16 may include one or more monomers and/or comonomers, such as, but not limited to, ethylene, propylene, butene, hexene, octene, decene, and so forth. The diluent 18 may include one or more diluents, such as, but not limited to, an inert hydrocarbon that is liquid at reaction conditions, such as isobutane, propane, n-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, cyclohexane, cyclopentane, methylcyclopentane, or ethylcyclohexane, among others. In certain embodiments, the diluent 18 may be employed to suspend catalyst particles and polymer particles within the reactor vessels of thereactor system 12. In further embodiments, thereactor system 12 may also receive other materials, such as, but not limited to, chain transfer agents (e.g. hydrogen), catalysts, co-catalysts, and other additives. - The
reactor system 12 can include one or more polymerization reactors, such as liquid-phase reactors, gas-phase reactors, or a combination thereof. Multiple reactors may be arranged in series, in parallel, or in any other suitable combination or configuration. Within the polymerization reactors, the monomer 16 (e.g., one or more monomers and/or comonomers) may be polymerized to form a product containingpolymer particles 20, typically called fluff or granules. According to certain embodiments, themonomer 16 may include 1-olefins having up to 10 carbon atoms per molecule and typically no branching nearer the double bond than the 4-position. For example, themonomer 16 may include monomers and comonomers such as ethylene, propylene, butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or any combination thereof. Thepolymer particles 20 may possess one or more melt, physical, rheological, and/or mechanical properties of interest, such as density, melt index (MI), melt flow rate (MFR), copolymer or comonomer content, modulus, and crystallinity. The reaction conditions, such as temperature, pressure, flow rate, mechanical agitation, product takeoff, component concentrations, polymer production rate, and so forth, may be selected to achieve the desired properties of thepolymer particles 20. - Product effluent, which includes the formed
polymer particles 20, as well as non-polymer components, such as the diluent 18,unreacted monomer 16, and residual catalyst, exits thereactor system 12 and enters various systems, such as a product recovery system, an extrusion system, and/or a loadout system, to produce extruded polymer pellets. Examples of polymer pellets that may be produced by themanufacturing system 10 include, but are not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and enhanced polyethylene such as bimodal grades. The various types and grades of polyethylene pellets may be marketed, for example, under the brand names Marlex® polyethylene or MarFlex® polyethylene of Chevron-Phillips Chemical Company, LP, of The Woodlands, Tex., USA. - The produced polymer (e.g., polyethylene) pellets can be used in the manufacture of a variety of products, components, household items and other items, including adhesives (e.g., hot-melt adhesive applications), electrical wire and cable, agricultural films, shrink film, stretch film, food packaging films, flexible food packaging, milk containers, frozen-food packaging, trash and can liners, grocery bags, heavy-duty sacks, plastic bottles, safety equipment, coatings, toys, and an array of containers and plastic products. Further, the products and components formed from the polymer pellets may be further processed and assembled prior to distribution and sale to the consumer. For example, the polymer pellets are generally subjected to further processing, such as blow molding, injection molding, rotational molding, blown film, cast film, extrusion (e.g., sheet extrusion, pipe and corrugated extrusion, coating/lamination extrusion, etc.), and so on.
- Returning to
FIG. 1 , thecatalyst complex 14 may be prepared by combining acatalyst solution 22, acocatalyst 24, andactivator 26. Examples of thecocatalyst 24 include, but are not limited to, organometallic compounds, such as triisobutylaluminum, triethylaluminum or tri-ethyl boron, alkyl aluminum compounds, methyl aluminoxane, and so forth. Examples of theactivator 26 include, but are not limited to, solid super acids and chemically-treated solid oxides. In one embodiment, the solid oxide can have a surface area of from about 100 to about 1000 m2/g. In yet another embodiment, the solid oxide can have a surface area of from about 200 to about 800 m2/g. In still another embodiment, the solid oxide can have a surface area of from about 250 to about 600 m2/g. - When the
activator 26 is a chemically-treated solid oxide, it can include a solid inorganic oxide that includes oxygen and one or more elements selected fromGroup - Suitable examples of solid oxide materials or compounds that can be used to form the chemically-treated solid oxide used as the
activator 26 can include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, coatings of one oxide with another, and combinations thereof. For example, the solid oxide can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof. - Returning to
FIG. 1 , thecatalyst solution 22 may be prepared by combining acatalyst 28 and a solvent 30. Specifically, thecatalyst 28 may be dissolved in the solvent 30. In one embodiment, thecatalyst 28 may essentially be a solid material. Examples of thecatalyst 28 include, but are not limited to, metallocene catalysts, Ziegler-Natta catalysts, chromium-based catalysts, vanadium-based catalysts, nickel-based catalysts, or a combination thereof, among others. Examples of chromium-based catalysts include, but are not limited to, chrome, chromocene, chrome titanium, chrome silica, chrome with aluminum phosphate, and so forth. Examples of the solvent 30 include, but are not limited to, comonomers, such as those listed above, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or any combination thereof. In a certain embodiment, the solvent 30 is 1-hexene and excludes toluene. Use of 1-hexene may be more desirable than toluene because 1-hexene has fewer environmental concerns than toluene. In addition, 1-hexene is used (i.e., chemically consumed or reacted) during polymerization and thus, would appear as a residual in thepolymer particles 20 in smaller quantities than toluene, which is not used during polymerization.Certain catalysts 28 may be less soluble in 1-hexene than toluene. Thus, the heating of thecatalyst solution 22, as described in detail below, may facilitate use of 1-hexene instead of toluene and help prevent precipitation of thecatalyst 28. -
FIG. 2 depicts an embodiment of acatalyst preparation system 40 that may be used to prepare thecatalyst complex 14 fed to thereactor system 12. Specifically, thecatalyst preparation system 40 may include acatalyst tank 42 to store thecatalyst 28. In one embodiment, acatalyst control valve 44 may be used as a transfer means to control the transfer of thecatalyst 28 from thecatalyst tank 42 to a catalyst mix/run tank 46. Other catalyst transfer means can also be employed either with or without acatalyst control valve 44. For example, thecatalyst 28 may be pressured (e.g., via the use of nitrogen), pumped, conveyed, or otherwise transported to the catalyst mix/run tank 46. Thecatalyst preparation system 40 may also include asolvent tank 48 to store the solvent 30. In one embodiment, asolvent control valve 50 may be used to control the transfer of the solvent 30 to the catalyst mix/run tank 46. Other solvent transfer means can also be used either with or without asolvent control valve 50. For example, the solvent 30 may be pressured from thesolvent tank 48 or in certain embodiments, a pump may be used to transfer the solvent 30 from thesolvent tank 48. Indeed, in some embodiments, a pump may replace or cooperate with thesolvent control valve 50. - As shown in
FIG. 2 , the catalyst mix/run tank 46 includes anagitator 52 that is powered by amotor 54. Theagitator 52 may be used to dissolve and/or mix thecatalyst 28 and the solvent 30 in the catalyst mix/run tank 46. Thus, theagitator 52 may help speed the mixing of thecatalyst 28 and the solvent 30 and/or improve the consistency of thecatalyst solution 22. In certain embodiments, the catalyst mix/run tank 46 may include aheating system 56 to heat thecatalyst solution 22. Examples of theheating system 56 include, but are not limited to, a heated tempered water jacket, a heated tempered water coil, an electrical clamp-on jacket, or any other suitable heating system. By heating thecatalyst solution 22 with theheating system 56, greater concentrations ofcatalyst 28 may be achieved without resulting in precipitation of thecatalyst 28. In addition, theheating system 56 may be used whenever both thecatalyst 28 and the solvent 30 are present at the same time to help prevent precipitation of thecatalyst 28 at low temperatures. Atransfer line 58 may be used to transfer thecatalyst solution 22 from the catalyst mix/run tank 46. Thetransfer line 58 may include apiping heating system 60, such as, but not limited to, a heated tempered water jacket, electrical tracing, or any other suitable heating system, which may be used to maintain a temperature of thecatalyst solution 22 above a threshold as thecatalyst solution 22 travels through thetransfer line 58. Acatalyst solution pump 62 may be coupled to thetransfer line 58 and used to transfer thecatalyst solution 22 from the catalyst mix/run tank 46. In addition, thetransfer line 58 may include a catalystsolution control valve 64 to control the transfer of thecatalyst solution 22 from the catalyst mix/run tank 46 to aprecontactor 66 either with or without acatalyst solution pump 62. - In addition to the
catalyst solution 22 from the catalyst mix/run tank 46, theprecontactor 66 may receive thecocatalyst 24 from acocatalyst tank 68 via acocatalyst pump 70. In other embodiments, thecocatalyst 24 may be pressured to theprecontactor 66 or otherwise transferred. In further embodiments, thecocatalyst 24 may be transferred directly from thecocatalyst tank 68 to one or more reactors in thereactor system 12, bypassing theprecontactor 66. Anactivator tank 72 may store theactivator 26 before being transferred to theprecontactor 66 via pressuring, a pump, or the like. Theprecontactor 66 includes aprecontactor agitator 74 powered by aprecontactor motor 76. Theprecontactor agitator 74 may be used to thoroughly mix thecatalyst solution 22 with thecocatalyst 24 and theactivator 26. Theprecontactor 66 may also include aprecontactor heating system 78 to heat the catalyst complex 14 in theprecontactor 66. Theprecontactor heating system 78 may be similar to theheating system 56 for the catalyst mix/run tank 46 described above. In one embodiment, theprecontactor heating system 78 may be used only during preparation of thecatalyst complex 14 and then shut off afterwards. Aprecontactor transfer line 80 may be used to transfer the catalyst complex 14 from theprecontactor 66. In certain embodiments, one or more precontactor pumps 82 may be used to transfer the catalyst complex 14 from theprecontactor 66 to one or more reactors in thereactor system 12. - Regardless of the
specific catalyst 28 used, operating conditions within thecatalyst preparation system 40 may be controlled to produce the catalyst complex 14 with desired properties. For example, acontrol system 90 can be employed to control operating conditions within themanufacturing system 10, such as thecatalyst preparation system 40. For example, thecontrol system 90 may be employed to adjust the flow rates, temperatures, and/or other properties of thecatalyst 28, solvent 30,catalyst solution 22,cocatalyst 24,activator 26, and/orcatalyst complex 14. Further, thecontrol system 90 may be employed to transition from feeding one type of catalyst complex 14 to thereactor system 12 to feeding another type of catalyst complex 14 to thereactor system 12. Moreover, thecontrol system 90 may be employed to monitor and/or adjust operating conditions within themanufacturing system 10, such as temperatures, pressures, the reaction rate, and the solids concentrations, among others. According to certain embodiments, thecontrol system 90 may receive input signals 92 from sensors (such as, temperature sensors, pressure sensors, and/or flow transducers, among others) within themanufacturing system 10 that are indicative of operating conditions and may then generatecontrol signals 102 to adjust operating conditions of themanufacturing system 10. - Specifically, as shown in
FIG. 2 , thecontrol system 90 may receive input signals 92 from various sensors disposed within thecatalyst preparation system 40, such as, but not limited to, a catalyst mix/runtank temperature sensor 94, a catalyst mix/runtank concentration sensor 96, aprecontactor temperature sensor 98, a catalystcomplex flow sensor 100, and so forth. In other embodiments, thecontrol system 90 may receive input signals 92 from other sensors disposed in thecatalyst preparation system 40 and/or themanufacturing system 10. Based on the input signals 92, thecontrol system 90 may transmitcontrol signals 102 to various devices and equipment disposed in thecatalyst preparation system 40, such as, but not limited to, any catalyst transfer means, thecatalyst control valve 44, any solvent transfer means, thesolvent control valve 50, the catalyst mix/run tank motor 54, the catalyst mix/runtank heating system 56, the transferpipe heating system 60, the catalystsolution transfer pump 62, the catalystsolution control valve 64, thecocatalyst pump 70, theprecontactor motor 76, theprecontactor pump 82, theprecontactor heating system 78, and so forth. - In certain embodiments, the
input signal 92 received by thecontrol system 90 may be indicative of a demand for thecatalyst 28 in the catalyst mix/run tank 46. For example, theinput signal 92 may be indicative of a concentration of thecatalyst 28 in thecatalyst solution 22 that is lower than a setpoint and may be transmitted by the catalyst mix/runtank concentration sensor 96. In response, thecontrol system 90 may activate an output, such as an actuator for thecatalyst control valve 44, to supply thecatalyst 28 to the catalyst mix/run tank 46 and/or other catalyst transfer means. Thecontrol system 90 may receive anadditional input signal 92 indicative of a demand for thecatalyst solution 22 in theprecontactor 66. For example, theinput signal 92 may be indicative of a concentration of thecatalyst 28 in the catalyst complex 14 or the level of the catalyst complex 14 in theprecontactor 66 that is below a setpoint. In response, thecontrol system 90 may activate an output, such as an actuator for thecatalyst solution pump 62 and/or the catalystsolution control valve 64, to supply thecatalyst solution 22 to theprecontactor 66. In other embodiments, thecontrol system 90 may receive anadditional input signal 92 indicative of a demand for the catalyst complex 14 in thereactor system 12. For example, theinput signal 92 may be indicative of a flow rate of the catalyst complex 14 to thereactor system 12 that is below a setpoint and may be transmitted by the catalystcomplex flow sensor 100. In response, thecontrol system 90 may activate an output, such as an actuator for theprecontactor pump 82, to supply more catalyst complex 14 to thereactor system 12. In further embodiments, thecontrol system 90 may receive anadditional input signal 92 indicative of a temperature of thecatalyst solution 22 in the catalyst mix/run tank 46. For example, theinput signal 92 may be transmitted by the catalyst mix/runtank temperature sensor 94 and indicate that the temperature of thecatalyst solution 22 is below a setpoint. In response, thecontrol system 90 may activate an output, such as an actuator for theheating system 56, to supply additional heat to the catalyst mix/run tank 46. Thecontrol system 90 may operate in a similar manner to supply heat to theprecontactor 66 based on data acquired via aninput signal 92 from theprecontactor temperature sensor 98. - According to certain embodiments, the
control system 90 may be a Distributed Control System (DCS). Thecontrol system 90 may include one or more automation controllers, microprocessors, instruction set processors, graphics processors, analog to digital converters, interface boards, and/or related chip sets. Further, thecontrol system 90 may cooperate with storage that stores executable code, data, and instructions for thecontrol system 90. For example, the storage may store non-transitory machine-readable code for maintaining a temperature of thecatalyst solution 22 above a threshold based on measured process variables. The storage may include volatile memory, such as random access memory, and/or non-volatile memory, such as read only memory, flash memory, a hard drive, or any other suitable optical, magnetic, or solid-state computer readable media, as well as a combination thereof. Thecontrol system 90 may also include a display and a user interface. According to certain embodiments, the display and the user interface may be part of an operator workstation. The display may display a variety of information about themanufacturing system 10. For example, the display may display graphs, trends, mass balances, energy balances, process data, such as measured process variables, and/or predictive data, among others that facilitate user monitoring and control of themanufacturing system 10. - According to certain embodiments, the display may display screens of the user interface that facilitate entry of user inputs. For example, a user may enter desired operating parameters (e.g., setpoints) or adjustments that should be made to the
manufacturing system 10. In certain embodiments, a user may review an essentially instantaneous reaction rate or trend shown on the display and may enter a desired catalyst feed rate value or catalyst feed rate adjustment. In another example, a user may adjust the temperature of thereactor system 12 or one or more of the feed rates through the user interface. However, in other embodiments, at least some of the operating conditions may be adjusted automatically by thecontrol system 90. For example, in certain embodiments, thecontrol system 90 may automatically adjust the flow rate ofcatalyst 28 to the catalyst mix/run tank 46 based on a measured concentration of thecatalyst 28 in thecatalyst solution 22. - In certain embodiments, the
control system 90 may be used to maintain a temperature of thecatalyst solution 22 and/or thecatalyst complex 14 above a threshold. The threshold may be selected to help prevent precipitation of thecatalyst 28 out of thecatalyst solution 22 and/or thecatalyst complex 14. In certain embodiments, the threshold may be between approximately 40 degrees Celsius to approximately 50 degrees Celsius. In one embodiment, the threshold may be approximately 45 degrees Celsius. A not-to-exceed temperature threshold, such as approximately 60 degrees Celsius or approximately 65 degrees Celsius, may be selected based on theparticular catalyst 28 used to avoid degradation of thecatalyst 28. In one embodiment, the threshold may be between approximately 40 degrees Celsius and approximately 65 degrees Celsius. The catalyst mix/runtank temperature sensor 94 may indicate a temperature of thecatalyst solution 22 and theprecontactor temperature sensor 98 may indicate a temperature of thecatalyst complex 14. Based on the input signals 92 received from thetemperature sensors 96 and/or 98, thecontrol system 90 may sendcontrol signals 102 to the catalyst mix/runtank heating system 56 and/or theprecontactor heating system 78 to maintain the temperatures of thecatalyst solution 22 and/or thecatalyst complex 14, respectively, above the threshold. - In other embodiments, the
control system 90 may be used to maintain a concentration of thecatalyst 28 in thecatalyst solution 22 and/or thecatalyst complex 14 above a threshold. The threshold may be selected to help provide a desired amount of thecatalyst 28 to reach thereactor system 12. In certain embodiments, the catalyst concentration threshold may be above approximately 0.40 weight percent in the solvent 30. This concentration threshold may be greater than the concentration ofcatalyst solution 22 provided by off-site vendors because off-site vendors may be limited by transportation issues. Thus, present embodiments may enable the size of the catalyst mix/run tank 46 and associated equipment and lines to be reduced relative to traditional operations. In a certain embodiment, the catalyst concentration threshold may be approximately 0.47 weight percent in the solvent 30. The catalyst mix/runtank concentration sensor 96 may provide theinput signal 92 to thecontrol system 90 indicative of the concentration of thecatalyst 28 in thecatalyst solution 22. In response to theinput signal 92 from the catalyst mix/runtank concentration sensor 96, thecontrol system 90 may transmit thecontrol signal 102 to thecatalyst control valve 44 and/or thesolvent control valve 50 to maintain the concentration of thecatalyst 28 in thecatalyst solution 22 above the threshold. For example, thecontrol signal 102 may open thecatalyst control valve 44 and/or close thesolvent control valve 50 if the indicated concentration of thecatalyst 28 in thecatalyst solution 22 is below the threshold. Similarly, thecontrol system 90 may close thecatalyst control valve 44 and/or open thesolvent control valve 50 if the concentration of thecatalyst 28 in thecatalyst solution 22 is above the threshold. In a similar manner, thecontrol system 90 may be used to adjust one or more of the catalystsolution transfer pump 62, catalystsolution control valve 64, and/orcocatalyst pump 70 to adjust or maintain the concentration of thecatalyst 28 in the catalyst complex 14 in theprecontactor 66. In such embodiments, theprecontactor 66 may include a concentration sensor similar to the catalyst mix/runtank concentration sensor 96 to provide theinput signal 92 to thecontrol system 90. Further, thecontrol system 90 may transmitcontrol signals 102 to theprecontactor pump 82 to adjust or maintain a flow rate of the catalyst complex 14 to thereactor system 12. In other embodiments, thecontrol system 90 may also be used to control the catalyst mix/run tank motor 54 and/or theprecontactor motor 76. - The
concentration sensor 96 shown inFIG. 2 may use various techniques, such as spectrophotometry, to determine the concentration of thecatalyst 28 in thecatalyst solution 22. In one embodiment, theconcentration sensor 96 may be an ultraviolet-visible photometric analyzer (i.e., a UV-Vis analyzer), which may utilize the Beer-Lambert law to determine the concentration of thecatalyst 28. Specifically, the UV-Vis analyzer may pass a wavelength of light through thecatalyst solution 22 and measure the absorbance of the light at the selected wavelength. The measured absorbance may then be compared to a calibration curve to determine the concentration of thecatalyst 28. The specific wavelength of light may be selected to have little or no absorption by the solvent 30, thereby reducing errors in the determined concentration. Thus, the absorbance of light at the selected wavelength may be essentially a function of the concentration of thecatalyst 28 in thecatalyst solution 22. The UV-Vis analyzer may used in various ways, such as, but not limited to, providing a continuous on-line indication of the concentration of thecatalyst 28 in thecatalyst solution 22 and/or thecatalyst complex 14, analyzing batches of thecatalyst solution 28 and/or thecatalyst complex 14, and so forth. In certain embodiments, thecatalyst solution 22 may include particles or other particulate matter that may affect the spectrophotometric analysis. Thus, in certain embodiments, the UV-Vis analyzer may include a filter or similar device to remove particles and/or other matter from thecatalyst solution 22. In addition, in other embodiments, a measurement cell of the UV-Vis analyzer may be flushed on a regular basis, e.g., daily, to reduce buildup of material that may affect the accuracy of the measurement. In further embodiments, other techniques may be used to determine the concentration of thecatalyst 28 in thecatalyst solution 22. -
FIG. 3 depicts an embodiment of thecatalyst preparation system 40 that can be employed in themanufacturing system 10 shown inFIG. 1 . In particular,FIG. 3 depicts a system that uses two catalysts. For example, afirst catalyst tank 120 may be used to store afirst catalyst 122 and a firstcatalyst control valve 124 may be used to control the flow of thefirst catalyst 122 to the catalyst mix/run tank 46. Thecatalyst preparation system 40 may also include asecond catalyst tank 126 to store asecond catalyst 128 and a secondcatalyst control valve 130 may be used to flow thesecond catalyst 128 to the catalyst mix/run tank 46. The use of the first andsecond catalysts polymer particles 20 with certain desired characteristics compared topolymer particles 20 produced using a single catalyst. In other respects, thecatalyst preparation system 40 shown inFIG. 3 is similar to thesystem 40 shown inFIG. 2 . -
FIG. 4 depicts an embodiment of thecatalyst preparation system 40 with two catalyst mix/run tanks Specifically, a firstcatalyst control valve 136 may control the flow rate of thecatalyst 28 to a first catalyst mix/run tank 140 and a firstsolvent control valve 138 may control the flow rate of the solvent 30 to the first catalyst mix/run tank 140. The first catalyst mix/run tank 140 may include afirst agitator 142 driven by afirst motor 144 and may be heated using afirst heating system 146. In addition, the first catalyst mix/run tank 140 may include afirst temperature sensor 148 and afirst concentration sensor 149. Similarly, a secondcatalyst control valve 145 may control the flow rate of thecatalyst 28 to a second catalyst mix/run tank 150 and a secondsolvent control valve 147 may control the flow rate of the solvent 30 to the second catalyst mix/run tank 150. The second catalyst mix/run tank 150 may include asecond agitator 152 driven by asecond motor 154, asecond heating system 156, asecond temperature sensor 158, and asecond concentration sensor 160. Thecatalyst solution 122 from the first catalyst mix/run tank 140 may be transferred to theprecontactor 66 through a first transfer line 162 and thecatalyst solution 22 from the second catalyst mix/run tank 150 may be transferred via asecond transfer line 164. The first and second catalyst mix/run tanks run tank 140 may be used to supply thecatalyst solution 22 to theprecontactor 66 until the first catalyst mix/run tank 140 is approximately empty, below a minimum level threshold, or otherwise out-of-service. At that point, the second catalyst mix/run tank 150 may be used to supply thecatalyst solution 22 to theprecontactor 66 while the first catalyst mix/run tank 140 is unavailable. Similarly, when the second catalyst mix/run tank 150 is approximately empty, below a minimum level threshold, or otherwise out-of-service, the first catalyst mix/run tank 140 may be used to supply thecatalyst solution 22 to theprecontactor 66. In other respects, thecatalyst preparation system 40 shown inFIG. 4 is similar to thesystem 40 shown inFIG. 2 . -
FIG. 5 depicts an embodiment of thecatalyst preparation system 40 including separate mix and run tanks Specifically, thecatalyst preparation system 40 includes acatalyst mix tank 180 that includes acatalyst mix agitator 182 driven bycatalyst mix motor 184. Thecatalyst mix tank 180 may include a catalystmix heating system 186, a catalystmix concentration sensor 187, and a catalystmix temperature sensor 188. Acatalyst mix pump 191 may be used to transfer thecatalyst solution 22 from thecatalyst mix tank 180 to acatalyst run tank 190 via catalystmix transfer line 189. Thecatalyst run tank 190 may include acatalyst run agitator 192 driven by catalyst runmotor 194, a catalyst runheating system 196, a catalystrun concentration sensor 197, and a catalystrun temperature sensor 198. A catalyst runtransfer line 200 may be used to transfer thecatalyst solution 22 from thecatalyst run tank 190 to theprecontactor 66. As shown inFIG. 5 , thecatalyst mix tank 180 may be used to prepare thecatalyst solution 22 and thecatalyst run tank 190 may be used to supply thecatalyst solution 22 to theprecontactor 66. When thecatalyst run tank 190 is approximately empty or below a minimal level threshold, thecatalyst solution 22 from thecatalyst mix tank 180 may be used to refill thecatalyst run tank 190.Additional catalyst solution 22 may then be prepared in thecatalyst tank 180 to be transferred later to thecatalyst run tank 190. In other respects, thecatalyst preparation system 40 shown inFIG. 5 is similar to thesystem 40 shown inFIG. 2 . -
FIG. 6 depicts amethod 210 for preparing thecatalyst complex 14. Themethod 210 may begin by mixing thecatalyst 28 and the solvent 30 in the catalyst mix/run tank 46 to generate the catalyst solution 22 (block 212). For example, thecontrol system 90 may activate the catalyst mix/run tank agitator 52 to mix the contents of the catalyst mix/run tank 46 to generate thecatalyst solution 22. Thecatalyst solution 22 may also be prepared, for example, in the first catalyst mix/run tank 140, the second catalyst mix/run tank 150, or thecatalyst mix tank 180. Themethod 210 may then continue by heating thecatalyst solution 22 to maintain a temperature of thecatalyst solution 22 above a threshold (block 214). For example, thecontrol system 90 may be used to control the heat provided to thecatalyst solution 22 via the catalyst mix/runtank heating system 56 based on the temperature sensed by the catalyst mix/runtank temperature sensor 94. In other embodiments, thecontrol system 90 may be used to maintain the temperature of thecatalyst solution 22 above the threshold in, for example, the first catalyst mix/run tank 140, the second catalyst mix/run tank 150, thecatalyst mix tank 180, or thecatalyst run tank 190. Themethod 210 may then continue by mixing theheated catalyst solution 22 with thecocatalyst 24 and theactivator 26 in theprecontactor 66 to generate the catalyst complex 14 (block 216). For example, thecontrol system 90 may use theprecontactor agitator 74 to mix the contents of theprecontactor 66 to generate thecatalyst complex 14. - The
method 210 may then continue by heating the catalyst complex 14 to maintain a temperature above a threshold (block 218). For example, thecontrol system 90 may use theprecontactor heating system 78 to maintain the temperature of thecatalyst complex 14 above the threshold as determined by theprecontactor temperature sensor 98. The method may then continue by transferring the heated catalyst complex 14 to the reactor system 12 (block 220). In certain embodiments, thecontrol system 90 may be used to control theprecontactor pump 82 to adjust the flow rate of the catalyst complex to thereactor system 12 as measured by the catalystcomplex flow sensor 100. - Systems and methods for catalyst preparation have been described. The following clauses are offered as further description of the disclosure.
-
Embodiment 1. A system, comprising: an agitator disposed inside a polymerization catalyst tank and configured to mix or dissolve at least a portion or all of a polymerization catalyst and a solvent to generate a polymerization catalyst solution; a heating system coupled to the polymerization catalyst tank and configured to maintain a temperature of the polymerization catalyst solution above a threshold; a precontactor configured to receive feed streams comprising an activator and the polymerization catalyst solution from the polymerization catalyst tank to generate a catalyst complex; and a transfer line configured to transfer the catalyst complex from an outlet of the precontactor to a reactor. - Embodiment 2. The system of
embodiment 1, wherein the precontactor comprises: a second agitator disposed inside the precontactor and configured to mix the activator and polymerization catalyst solution; and a second heating system coupled to the precontactor and configured to maintain a temperature of the catalyst complex above a second threshold. -
Embodiment 3. The system defined in any preceding embodiment, comprising the reactor configured to polymerize monomer into polymer solids in the presence of the catalyst complex. - Embodiment 4. The system defined in any preceding embodiment, comprising a plurality of reactors configured to polymerize monomer into polymer solids in the presence of the catalyst complex.
- Embodiment 5. The system defined in any preceding embodiment, wherein the plurality of reactors are operated in a series configuration or in a parallel configuration.
-
Embodiment 6. The system defined in any preceding embodiment, wherein the polymerization catalyst comprises a metallocene catalyst. - Embodiment 7. The system defined in any preceding embodiment, wherein the solvent comprises a comonomer.
- Embodiment 8. The system defined in any preceding embodiment, wherein the comonomer comprises 1-hexene.
- Embodiment 9. The system defined in any preceding embodiment, wherein the feed streams comprise a cocatalyst.
-
Embodiment 10. The system defined in any preceding embodiment, wherein the cocatalyst comprises triisobutylaluminum, triethylaluminum, or any combination thereof. - Embodiment 11. The system defined in any preceding embodiment, wherein the activator comprises a solid super acid.
-
Embodiment 12. The system defined in any preceding embodiment, wherein the heating system is configured to heat a second transfer line configured to transfer the polymerization catalyst solution from the polymerization catalyst tank to the precontactor. - Embodiment 13. The system defined in any preceding embodiment, comprising a sensor configured to provide an indication of a concentration of the polymerization catalyst in the polymerization catalyst solution.
-
Embodiment 14. A method, comprising: making a polymerization catalyst solution by dissolving a polymerization catalyst with one or more solvents in a heated polymerization catalyst tank; making a polymerization catalyst complex by combining at least a portion of the polymerization catalyst solution with an activator in a precontactor; and transferring the polymerization catalyst complex from the precontactor to a reactor. - Embodiment 15. The method or system defined in any preceding embodiment, comprising combining a cocatalyst with the polymerization catalyst solution and the activator in the precontactor.
-
Embodiment 16. The method or system defined in any preceding embodiment, comprising heating the polymerization catalyst complex in the precontactor. - Embodiment 17. The method or system defined in any preceding embodiment, comprising maintaining the polymerization catalyst solution in the polymerization catalyst tank at a temperature between approximately 40 degrees Celsius to 50 degrees Celsius.
-
Embodiment 18. The method or system defined in any preceding embodiment, comprising polymerizing a monomer in the presence of the catalyst complex to produce polymer solids in the reactor. - Embodiment 19. The method or system defined in any preceding embodiment, comprising measuring a concentration of the polymerization catalyst in the polymerization catalyst solution using an ultraviolet-visible photometric analyzer.
-
Embodiment 20. The method or system defined in any preceding embodiment, comprising maintaining the concentration of the polymerization catalyst in the polymerization catalyst solution above approximately 0.40 weight percent in the solvent. - Embodiment 21. A system, comprising: one or more automation controllers configured to: receive a first input indicative of a demand for a metallocene catalyst in a metallocene catalyst tank; activate a first output to supply the metallocene catalyst to the metallocene catalyst tank, such that the metallocene catalyst and a solvent mix in the metallocene catalyst tank to form a metallocene catalyst solution; receive a second input indicative of a demand for the metallocene catalyst solution in a precontactor; and activate a second output to supply the metallocene catalyst solution to the precontactor; such that the metallocene catalyst solution and an activator mix in the precontactor to form a metallocene catalyst complex.
-
Embodiment 22. The method or system defined in any preceding embodiment, wherein the one or more automation controllers are configured to: receive a third input indicative of a demand for the metallocene catalyst complex in a reactor; and activate a third output to supply the metallocene catalyst complex to the reactor. - Embodiment 23. The method or system defined in any preceding embodiment, wherein the first and second outputs comprise a control valve actuator, a pump actuator, or any combination thereof.
-
Embodiment 24. The method or system defined in any preceding embodiment, wherein the second input comprises a concentration of the metallocene catalyst in the metallocene catalyst tank. - Embodiment 25. The method or system defined in any preceding embodiment, comprising a sensor configured to generate the second input, wherein the sensor comprises an ultraviolet-visible photometric analyzer.
-
Embodiment 26. The method or system defined in any preceding embodiment, wherein the one or more automation controllers are configured to: receive a fourth input indicative of a temperature of the metallocene catalyst solution in the metallocene catalyst tank; and activate a fourth output to supply heat to the metallocene catalyst tank. - Embodiment 27. A catalyst complex, comprising: a metallocene catalyst solution, comprising a mixture of a metallocene catalyst and a solvent, wherein a concentration of the metallocene catalyst in the metallocene catalyst solution is greater than approximately 0.40 weight percent in the solvent; and an activator.
-
Embodiment 28. The method, system, or catalyst complex defined in any preceding embodiment, wherein the solvent comprises a comonomer, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or a combination thereof. - Embodiment 29. The method, system, or catalyst complex defined in any preceding embodiment, comprising a cocatalyst.
-
Embodiment 30. The method, system, or catalyst complex defined in any preceding embodiment, wherein the cocatalyst comprises triisobutylaluminum, triethylaluminum, or any combination thereof. - Embodiment 31. The method, system, or catalyst complex defined in any preceding embodiment, wherein the activator comprises a solid super acid.
- While the present disclosure may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and tables and have been described in detail herein. However, it should be understood that the embodiments are not intended to be limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the following appended claims. Further, although individual embodiments are discussed herein, the disclosure is intended to cover all combinations of these embodiments.
Claims (20)
1. A method, comprising:
making a polymerization catalyst solution by heating a mixture of a solvent and a polymerization catalyst in a polymerization catalyst tank;
making a polymerization catalyst complex by combining at least a portion of the polymerization catalyst solution with an activator in a precontactor; and
transferring the polymerization catalyst complex from the precontactor to a reactor using a reactor transfer line.
2. The method of claim 1 , comprising combining a cocatalyst with the polymerization catalyst solution and the activator in the precontactor.
3. The method of claim 1 , comprising maintaining a temperature of the polymerization catalyst solution within the polymerization catalyst tank above a catalyst threshold using a catalyst heating system coupled to the polymerization catalyst tank.
4. The method of claim 3 , comprising maintaining the polymerization catalyst solution in the polymerization catalyst tank at a temperature between approximately 40 degrees Celsius to 50 degrees Celsius using the catalyst heating system.
5. The method of claim 1 , comprising heating the polymerization catalyst complex in the precontactor using a precontactor heating system coupled to the precontactor.
6. The method of claim 5 , comprising maintaining a temperature of the polymerization catalyst complex within the precontactor above a precontactor threshold using the precontactor heating system.
7. The method of claim 1 , comprising polymerizing a monomer into polymer solids in the reactor in the presence of the catalyst complex and existing polymer solids therein.
8. The method of claim 1 , comprising polymerizing monomer into polymer solids in a plurality of reactors in the presence of the catalyst complex and existing polymer solids therein.
9. The method of claim 1 , comprising measuring a concentration of the polymerization catalyst in the polymerization catalyst solution using an ultraviolet-visible photometric analyzer.
10. The method of claim 9 , comprising maintaining the concentration of the polymerization catalyst in the polymerization catalyst solution above approximately 0.40 weight percent in the solvent.
11. The method of claim 1 , comprising actively mixing the polymerization catalyst and the solvent using a catalyst agitator disposed inside the polymerization catalyst tank.
12. The method of claim 1 , comprising actively mixing the activator and polymerization catalyst solution using a precontactor agitator disposed inside the precontactor.
13. The method of claim 1 , comprising:
transferring the polymerization catalyst solution from the polymerization catalyst tank to the precontactor using a precontactor transfer line; and
heating the precontactor transfer line using a transfer line heating system.
14. A catalyst complex, comprising:
a metallocene catalyst solution, comprising a mixture of a metallocene catalyst and a solvent, wherein a concentration of the metallocene catalyst in the metallocene catalyst solution is greater than approximately 0.40 weight percent in the solvent; and
an activator.
15. The catalyst complex of claim 14 , wherein the solvent comprises a comonomer, 1-hexene, cyclohexane, heptane, an alkene, an alkane, a cycloalkene, a cycloalkane, or a combination thereof.
16. The catalyst complex of claim 14 , comprising a cocatalyst.
17. The catalyst complex of claim 16 , wherein the cocatalyst comprises triisobutylaluminum, triethylaluminum, or any combination thereof.
18. The catalyst complex of claim 14 , wherein the activator comprises a solid super acid.
19. A method for making the catalyst complex of claim 14 , comprising:
making the metallocene catalyst solution by heating the mixture of the solvent and the metallocene catalyst in a polymerization catalyst tank;
making the catalyst complex by combining at least a portion of the metallocene catalyst solution with the activator in a precontactor; and
transferring the catalyst complex from the precontactor to a reactor using a reactor transfer line.
20. A catalyst complex, comprising:
a metallocene catalyst solution, comprising a mixture of a metallocene catalyst and a solvent, wherein a concentration of the metallocene catalyst in the metallocene catalyst solution is greater than approximately 0.40 weight percent in the solvent; and
an activator, wherein the catalyst complex is made by a method comprising the steps of:
making the metallocene catalyst solution by heating the mixture of the solvent and the metallocene catalyst in a polymerization catalyst tank; and
making the catalyst complex by combining at least a portion of the metallocene catalyst solution with the activator in a precontactor.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/340,205 US20140336345A1 (en) | 2012-10-18 | 2014-07-24 | System and method for catalyst preparation |
US15/216,742 US20160325252A1 (en) | 2012-10-18 | 2016-07-22 | System and Method for Catalyst Preparation |
US16/248,960 US10828613B2 (en) | 2012-10-18 | 2019-01-16 | System and method for catalyst preparation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/655,024 US8821800B2 (en) | 2012-10-18 | 2012-10-18 | System and method for catalyst preparation |
US14/340,205 US20140336345A1 (en) | 2012-10-18 | 2014-07-24 | System and method for catalyst preparation |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/655,024 Division US8821800B2 (en) | 2012-10-18 | 2012-10-18 | System and method for catalyst preparation |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/216,742 Continuation US20160325252A1 (en) | 2012-10-18 | 2016-07-22 | System and Method for Catalyst Preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
US20140336345A1 true US20140336345A1 (en) | 2014-11-13 |
Family
ID=49485833
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/655,024 Active US8821800B2 (en) | 2012-10-18 | 2012-10-18 | System and method for catalyst preparation |
US14/340,205 Abandoned US20140336345A1 (en) | 2012-10-18 | 2014-07-24 | System and method for catalyst preparation |
US15/216,742 Abandoned US20160325252A1 (en) | 2012-10-18 | 2016-07-22 | System and Method for Catalyst Preparation |
US16/248,960 Active 2033-01-11 US10828613B2 (en) | 2012-10-18 | 2019-01-16 | System and method for catalyst preparation |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/655,024 Active US8821800B2 (en) | 2012-10-18 | 2012-10-18 | System and method for catalyst preparation |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/216,742 Abandoned US20160325252A1 (en) | 2012-10-18 | 2016-07-22 | System and Method for Catalyst Preparation |
US16/248,960 Active 2033-01-11 US10828613B2 (en) | 2012-10-18 | 2019-01-16 | System and method for catalyst preparation |
Country Status (9)
Country | Link |
---|---|
US (4) | US8821800B2 (en) |
EP (1) | EP2908941B1 (en) |
CN (1) | CN105102115B (en) |
CA (1) | CA2888781C (en) |
MX (1) | MX351101B (en) |
RU (1) | RU2644173C2 (en) |
SA (1) | SA515360295B1 (en) |
SG (1) | SG11201503062WA (en) |
WO (1) | WO2014062643A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10030086B1 (en) | 2017-07-21 | 2018-07-24 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10507445B2 (en) | 2018-03-29 | 2019-12-17 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10679734B2 (en) | 2018-03-29 | 2020-06-09 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10697889B2 (en) | 2017-07-21 | 2020-06-30 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8821800B2 (en) * | 2012-10-18 | 2014-09-02 | Chevron Phillips Chemical Company Lp | System and method for catalyst preparation |
US9303106B1 (en) | 2014-10-17 | 2016-04-05 | Chevron Phillips Chemical Company Lp | Processes for preparing solid metallocene-based catalyst systems |
US9864823B2 (en) | 2015-03-30 | 2018-01-09 | Uop Llc | Cleansing system for a feed composition based on environmental factors |
US9970869B2 (en) * | 2015-07-24 | 2018-05-15 | Chevron Phillips Chemical Company Lp | Use of turbidimeter for measurement of solid catalyst system component in a reactor feed |
RU2738204C2 (en) * | 2016-06-23 | 2020-12-09 | Чайна Петролеум Энд Кемикал Корпорейшн | Device for preliminary contact of catalyst for continuous polymerisation of olefins and method of preliminary contact of catalyst |
US10222787B2 (en) | 2016-09-16 | 2019-03-05 | Uop Llc | Interactive petrochemical plant diagnostic system and method for chemical process model analysis |
US10684631B2 (en) | 2017-03-27 | 2020-06-16 | Uop Llc | Measuring and determining hot spots in slide valves for petrochemical plants or refineries |
US10678272B2 (en) | 2017-03-27 | 2020-06-09 | Uop Llc | Early prediction and detection of slide valve sticking in petrochemical plants or refineries |
US10754359B2 (en) | 2017-03-27 | 2020-08-25 | Uop Llc | Operating slide valves in petrochemical plants or refineries |
US11130111B2 (en) | 2017-03-28 | 2021-09-28 | Uop Llc | Air-cooled heat exchangers |
US10844290B2 (en) | 2017-03-28 | 2020-11-24 | Uop Llc | Rotating equipment in a petrochemical plant or refinery |
US10663238B2 (en) | 2017-03-28 | 2020-05-26 | Uop Llc | Detecting and correcting maldistribution in heat exchangers in a petrochemical plant or refinery |
US11037376B2 (en) | 2017-03-28 | 2021-06-15 | Uop Llc | Sensor location for rotating equipment in a petrochemical plant or refinery |
US10962302B2 (en) | 2017-03-28 | 2021-03-30 | Uop Llc | Heat exchangers in a petrochemical plant or refinery |
US10670353B2 (en) | 2017-03-28 | 2020-06-02 | Uop Llc | Detecting and correcting cross-leakage in heat exchangers in a petrochemical plant or refinery |
US10794401B2 (en) | 2017-03-28 | 2020-10-06 | Uop Llc | Reactor loop fouling monitor for rotating equipment in a petrochemical plant or refinery |
US10752845B2 (en) | 2017-03-28 | 2020-08-25 | Uop Llc | Using molecular weight and invariant mapping to determine performance of rotating equipment in a petrochemical plant or refinery |
US10670027B2 (en) | 2017-03-28 | 2020-06-02 | Uop Llc | Determining quality of gas for rotating equipment in a petrochemical plant or refinery |
US11396002B2 (en) | 2017-03-28 | 2022-07-26 | Uop Llc | Detecting and correcting problems in liquid lifting in heat exchangers |
US10752844B2 (en) | 2017-03-28 | 2020-08-25 | Uop Llc | Rotating equipment in a petrochemical plant or refinery |
US10794644B2 (en) | 2017-03-28 | 2020-10-06 | Uop Llc | Detecting and correcting thermal stresses in heat exchangers in a petrochemical plant or refinery |
US10816947B2 (en) | 2017-03-28 | 2020-10-27 | Uop Llc | Early surge detection of rotating equipment in a petrochemical plant or refinery |
US9968899B1 (en) * | 2017-04-28 | 2018-05-15 | Uop Llc | Catalyst transfer pipe plug detection |
US10695711B2 (en) | 2017-04-28 | 2020-06-30 | Uop Llc | Remote monitoring of adsorber process units |
US10913905B2 (en) | 2017-06-19 | 2021-02-09 | Uop Llc | Catalyst cycle length prediction using eigen analysis |
US11365886B2 (en) | 2017-06-19 | 2022-06-21 | Uop Llc | Remote monitoring of fired heaters |
US10739798B2 (en) | 2017-06-20 | 2020-08-11 | Uop Llc | Incipient temperature excursion mitigation and control |
US11130692B2 (en) | 2017-06-28 | 2021-09-28 | Uop Llc | Process and apparatus for dosing nutrients to a bioreactor |
US10994240B2 (en) | 2017-09-18 | 2021-05-04 | Uop Llc | Remote monitoring of pressure swing adsorption units |
US11194317B2 (en) | 2017-10-02 | 2021-12-07 | Uop Llc | Remote monitoring of chloride treaters using a process simulator based chloride distribution estimate |
US11676061B2 (en) | 2017-10-05 | 2023-06-13 | Honeywell International Inc. | Harnessing machine learning and data analytics for a real time predictive model for a FCC pre-treatment unit |
US11105787B2 (en) | 2017-10-20 | 2021-08-31 | Honeywell International Inc. | System and method to optimize crude oil distillation or other processing by inline analysis of crude oil properties |
WO2019104655A1 (en) | 2017-11-30 | 2019-06-06 | 中国科学院大连化学物理研究所 | Molecular sieve-based catalyst modification apparatus, and method |
US10901403B2 (en) | 2018-02-20 | 2021-01-26 | Uop Llc | Developing linear process models using reactor kinetic equations |
US10734098B2 (en) | 2018-03-30 | 2020-08-04 | Uop Llc | Catalytic dehydrogenation catalyst health index |
KR20210057723A (en) * | 2018-09-17 | 2021-05-21 | 셰브론 필립스 케미컬 컴퍼니 엘피 | Modified supported chromium catalyst and ethylene polymer prepared therefrom |
US10953377B2 (en) | 2018-12-10 | 2021-03-23 | Uop Llc | Delta temperature control of catalytic dehydrogenation process reactors |
US11098140B2 (en) * | 2020-01-03 | 2021-08-24 | Saudi Arabian Oil Company | Production of 1-butene and ultra-high-molecular-weight polyethylene |
CN112582627B (en) * | 2020-12-30 | 2024-02-23 | 江苏氢导智能装备有限公司 | Catalyst preparation system and control method thereof |
CN114534632A (en) * | 2022-02-10 | 2022-05-27 | 迈瑞尔实验设备(上海)有限公司 | Slurry catalyst feed system |
WO2024039463A1 (en) | 2022-08-15 | 2024-02-22 | Exxonmobil Chemical Patents Inc. | Spectroscopic characterization methods for supported multi-component catalyst |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6300271B1 (en) * | 1998-05-18 | 2001-10-09 | Phillips Petroleum Company | Compositions that can produce polymers |
US20100029877A1 (en) * | 2006-12-19 | 2010-02-04 | Mitsui Chemicals, Inc. | Solid catalyst for olefin polymerization, olefin polymerization method, and olefin polymer particle produced by the method |
US20100317904A1 (en) * | 2009-06-16 | 2010-12-16 | Chevron Phillips Chemical Company Lp | Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends |
US8821800B2 (en) * | 2012-10-18 | 2014-09-02 | Chevron Phillips Chemical Company Lp | System and method for catalyst preparation |
Family Cites Families (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE560662A (en) | 1956-09-10 | |||
US3248179A (en) | 1962-02-26 | 1966-04-26 | Phillips Petroleum Co | Method and apparatus for the production of solid polymers of olefins |
US3242099A (en) | 1964-03-27 | 1966-03-22 | Union Carbide Corp | Olefin polymerization catalysts |
US4501885A (en) | 1981-10-14 | 1985-02-26 | Phillips Petroleum Company | Diluent and inert gas recovery from a polymerization process |
US4588790A (en) | 1982-03-24 | 1986-05-13 | Union Carbide Corporation | Method for fluidized bed polymerization |
US4808561A (en) | 1985-06-21 | 1989-02-28 | Exxon Chemical Patents Inc. | Supported polymerization catalyst |
US4794096A (en) | 1987-04-03 | 1988-12-27 | Fina Technology, Inc. | Hafnium metallocene catalyst for the polymerization of olefins |
US5565175A (en) | 1990-10-01 | 1996-10-15 | Phillips Petroleum Company | Apparatus and method for producing ethylene polymer |
US5575979A (en) | 1991-03-04 | 1996-11-19 | Phillips Petroleum Company | Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator |
US5436304A (en) | 1992-03-19 | 1995-07-25 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5272346A (en) | 1992-04-09 | 1993-12-21 | Nalco Chemical Company | Ultraviolet spectrographic monitoring of water soluble corrosion inhibitors |
KR0126658B1 (en) | 1993-10-05 | 1997-12-29 | 구자홍 | The sample rate conversion device for signal processing of non-standard tv. |
US5576259A (en) | 1993-10-14 | 1996-11-19 | Tosoh Corporation | Process for producing α-olefin polymer |
EP0727443B1 (en) | 1995-02-20 | 2001-01-17 | Tosoh Corporation | Catalyst for olefin polymerization and process for producing olefin polymers |
US5856567A (en) | 1995-06-07 | 1999-01-05 | Novus International, Inc. | Continuous hydrolysis process for preparing 2-hydroxy-4-methylthiobutanioc acid or salts thereof |
KR100437238B1 (en) | 1996-03-27 | 2004-08-16 | 다우 글로벌 테크놀로지스 인크. | Highly soluble olefin polymerization catalyst activator |
US5723804A (en) | 1996-07-10 | 1998-03-03 | Gibson Guitar Corp. | Electric monophonic/stereophonic stringed resonator instrument |
US6239235B1 (en) | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
KR100531628B1 (en) | 1998-03-20 | 2005-11-29 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Continuous slurry polymerization volatile removal |
US6165929A (en) | 1998-05-18 | 2000-12-26 | Phillips Petroleum Company | Compositions that can produce polymers |
US6107230A (en) | 1998-05-18 | 2000-08-22 | Phillips Petroleum Company | Compositions that can produce polymers |
US20040002420A1 (en) | 1998-10-23 | 2004-01-01 | Feng-Jung Wu | Stable catalysts and co-catalyst compositions formed from hydroxyaluminoxane and their use |
US6294494B1 (en) | 1998-12-18 | 2001-09-25 | Phillips Petroleum Company | Olefin polymerization processes and products thereof |
US6262191B1 (en) | 1999-03-09 | 2001-07-17 | Phillips Petroleum Company | Diluent slip stream to give catalyst wetting agent |
US6479597B1 (en) | 1999-07-30 | 2002-11-12 | Exxonmobil Chemical Patents Inc. | Raman analysis system for olefin polymerization control |
US6355594B1 (en) | 1999-09-27 | 2002-03-12 | Phillips Petroleum Company | Organometal catalyst compositions |
US6376415B1 (en) | 1999-09-28 | 2002-04-23 | Phillips Petroleum Company | Organometal catalyst compositions |
US6395666B1 (en) | 1999-09-29 | 2002-05-28 | Phillips Petroleum Company | Organometal catalyst compositions |
US6548441B1 (en) | 1999-10-27 | 2003-04-15 | Phillips Petroleum Company | Organometal catalyst compositions |
US6391816B1 (en) | 1999-10-27 | 2002-05-21 | Phillips Petroleum | Organometal compound catalyst |
US6613712B1 (en) | 1999-11-24 | 2003-09-02 | Phillips Petroleum Company | Organometal catalyst compositions with solid oxide supports treated with fluorine and boron |
US6548442B1 (en) | 1999-12-03 | 2003-04-15 | Phillips Petroleum Company | Organometal compound catalyst |
US6750302B1 (en) | 1999-12-16 | 2004-06-15 | Phillips Petroleum Company | Organometal catalyst compositions |
US6524987B1 (en) | 1999-12-22 | 2003-02-25 | Phillips Petroleum Company | Organometal catalyst compositions |
US6632894B1 (en) | 1999-12-30 | 2003-10-14 | Phillips Petroleum Company | Organometal catalyst compositions |
US7041617B2 (en) | 2004-01-09 | 2006-05-09 | Chevron Phillips Chemical Company, L.P. | Catalyst compositions and polyolefins for extrusion coating applications |
US6667274B1 (en) | 1999-12-30 | 2003-12-23 | Phillips Petroleum Company | Polymerization catalysts |
US6576583B1 (en) | 2000-02-11 | 2003-06-10 | Phillips Petroleum Company | Organometal catalyst composition |
US6388017B1 (en) | 2000-05-24 | 2002-05-14 | Phillips Petroleum Company | Process for producing a polymer composition |
US6916892B2 (en) * | 2001-12-03 | 2005-07-12 | Fina Technology, Inc. | Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropylene |
US6908971B2 (en) | 2002-09-16 | 2005-06-21 | Chevron Phillips Chemical Company, Lp | Catalyst slurry feeding assembly for a polymerization reactor |
US7400941B2 (en) | 2004-01-14 | 2008-07-15 | Chrevron Phillips Chemical Company Lp | Method and apparatus for monitoring polyolefin production |
WO2005068516A2 (en) | 2004-01-14 | 2005-07-28 | Chevron Phillips Chemical Company Lp | Method and apparatus for monitoring polyolefin production |
EA010549B1 (en) * | 2004-02-13 | 2008-10-30 | Тотал Петрокемикалс Рисерч Фелюй | Method and apparatus for preparing and supplying catalyst slurry to a polymerisation reactor |
US20050272891A1 (en) | 2004-02-13 | 2005-12-08 | Atofina Research S.A. | Double loop technology |
US7531606B2 (en) | 2004-05-26 | 2009-05-12 | Chevron Phillips Chemical Company Lp | Method for operating a gas phase polymerization reactor |
US7294599B2 (en) | 2004-06-25 | 2007-11-13 | Chevron Phillips Chemical Co. | Acidic activator-supports and catalysts for olefin polymerization |
PL1791875T3 (en) | 2004-08-27 | 2013-11-29 | Chevron Phillips Chemical Co Lp | Energy efficient polyolefin producction process |
US7598327B2 (en) | 2004-11-10 | 2009-10-06 | Chevron Phillips Chemical Company Lp | Method for polymerizing olefins in a gas phase reactor using a seedbed during start-up |
US7199073B2 (en) | 2004-11-10 | 2007-04-03 | Chevron Phillips Chemical Company, Lp | Resins that yield low haze films and the process for their production |
US7026494B1 (en) | 2005-01-10 | 2006-04-11 | Chevron Phillips Chemical Company, Lp | Polymerization catalysts for producing high melt index polymers without the use of hydrogen |
US7312283B2 (en) | 2005-08-22 | 2007-12-25 | Chevron Phillips Chemical Company Lp | Polymerization catalysts and process for producing bimodal polymers in a single reactor |
US7226886B2 (en) | 2005-09-15 | 2007-06-05 | Chevron Phillips Chemical Company, L.P. | Polymerization catalysts and process for producing bimodal polymers in a single reactor |
US7615596B2 (en) | 2005-09-30 | 2009-11-10 | Chevron Phillips Chemical Company Lp | Multiple component feed methods and systems |
US7517939B2 (en) | 2006-02-02 | 2009-04-14 | Chevron Phillips Chemical Company, Lp | Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching |
MY157264A (en) | 2006-11-14 | 2016-05-31 | Univation Tech Llc | Catalyst systems and polymerization processes |
US8077309B2 (en) * | 2007-01-29 | 2011-12-13 | Applied Instrument Technologies, Inc. | Chemical analyzer for industrial process control |
US8119553B2 (en) | 2007-09-28 | 2012-02-21 | Chevron Phillips Chemical Company Lp | Polymerization catalysts for producing polymers with low melt elasticity |
US8080681B2 (en) | 2007-12-28 | 2011-12-20 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
US7884163B2 (en) | 2008-03-20 | 2011-02-08 | Chevron Phillips Chemical Company Lp | Silica-coated alumina activator-supports for metallocene catalyst compositions |
US7884165B2 (en) | 2008-07-14 | 2011-02-08 | Chevron Phillips Chemical Company Lp | Half-metallocene catalyst compositions and their polymer products |
US8114946B2 (en) | 2008-12-18 | 2012-02-14 | Chevron Phillips Chemical Company Lp | Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches |
US8309485B2 (en) | 2009-03-09 | 2012-11-13 | Chevron Phillips Chemical Company Lp | Methods for producing metal-containing sulfated activator-supports |
US7919639B2 (en) | 2009-06-23 | 2011-04-05 | Chevron Phillips Chemical Company Lp | Nano-linked heteronuclear metallocene catalyst compositions and their polymer products |
US8329834B2 (en) | 2009-06-29 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates |
CN101805445B (en) * | 2010-01-29 | 2012-01-25 | 成强 | Chemical treating method for melt polycondensation high polymer old material regeneration |
US8288487B2 (en) | 2010-07-06 | 2012-10-16 | Chevron Phillips Chemical Company Lp | Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen |
US8629292B2 (en) | 2010-10-07 | 2014-01-14 | Chevron Phillips Chemical Company Lp | Stereoselective synthesis of bridged metallocene complexes |
US8609793B2 (en) | 2010-10-07 | 2013-12-17 | Chevron Phillips Chemical Company Lp | Catalyst systems containing a bridged metallocene |
US8843324B2 (en) | 2011-02-03 | 2014-09-23 | Nova Chemicals (International) S.A. | Double derivative NIR process control |
US8680218B1 (en) | 2013-01-30 | 2014-03-25 | Chevron Phillips Chemical Company Lp | Methods for controlling dual catalyst olefin polymerizations with an organozinc compound |
US8703886B1 (en) | 2013-02-27 | 2014-04-22 | Chevron Phillips Chemical Company Lp | Dual activator-support catalyst systems |
US8623973B1 (en) | 2013-03-08 | 2014-01-07 | Chevron Phillips Chemical Company Lp | Activator supports impregnated with group VIII transition metals for polymer property control |
US8822608B1 (en) | 2013-03-12 | 2014-09-02 | Chevron Phillips Chemical Co. LP. | Polyolefin production with different diluents in multiple polymerization reactors |
US9163098B2 (en) | 2014-01-10 | 2015-10-20 | Chevron Phillips Chemical Company Lp | Processes for preparing metallocene-based catalyst systems |
US9708426B2 (en) | 2015-06-01 | 2017-07-18 | Chevron Phillips Chemical Company Lp | Liquid-solid sampling system for a loop slurry reactor |
US9540457B1 (en) | 2015-09-24 | 2017-01-10 | Chevron Phillips Chemical Company Lp | Ziegler-natta—metallocene dual catalyst systems with activator-supports |
-
2012
- 2012-10-18 US US13/655,024 patent/US8821800B2/en active Active
-
2013
- 2013-10-15 MX MX2015004909A patent/MX351101B/en active IP Right Grant
- 2013-10-15 CN CN201380054175.4A patent/CN105102115B/en active Active
- 2013-10-15 RU RU2015113933A patent/RU2644173C2/en active
- 2013-10-15 EP EP13782924.8A patent/EP2908941B1/en active Active
- 2013-10-15 WO PCT/US2013/064984 patent/WO2014062643A1/en active Application Filing
- 2013-10-15 CA CA2888781A patent/CA2888781C/en active Active
- 2013-10-15 SG SG11201503062WA patent/SG11201503062WA/en unknown
-
2014
- 2014-07-24 US US14/340,205 patent/US20140336345A1/en not_active Abandoned
-
2015
- 2015-04-16 SA SA515360295A patent/SA515360295B1/en unknown
-
2016
- 2016-07-22 US US15/216,742 patent/US20160325252A1/en not_active Abandoned
-
2019
- 2019-01-16 US US16/248,960 patent/US10828613B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6300271B1 (en) * | 1998-05-18 | 2001-10-09 | Phillips Petroleum Company | Compositions that can produce polymers |
US20100029877A1 (en) * | 2006-12-19 | 2010-02-04 | Mitsui Chemicals, Inc. | Solid catalyst for olefin polymerization, olefin polymerization method, and olefin polymer particle produced by the method |
US20100317904A1 (en) * | 2009-06-16 | 2010-12-16 | Chevron Phillips Chemical Company Lp | Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends |
US8821800B2 (en) * | 2012-10-18 | 2014-09-02 | Chevron Phillips Chemical Company Lp | System and method for catalyst preparation |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10030086B1 (en) | 2017-07-21 | 2018-07-24 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10501567B2 (en) | 2017-07-21 | 2019-12-10 | Chevron Philips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10697889B2 (en) | 2017-07-21 | 2020-06-30 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10507445B2 (en) | 2018-03-29 | 2019-12-17 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10679734B2 (en) | 2018-03-29 | 2020-06-09 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US10870094B2 (en) | 2018-03-29 | 2020-12-22 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US11170874B2 (en) | 2018-03-29 | 2021-11-09 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
US11735293B2 (en) | 2018-03-29 | 2023-08-22 | Chevron Phillips Chemical Company Lp | Methods for determining transition metal compound concentrations in multicomponent liquid systems |
Also Published As
Publication number | Publication date |
---|---|
MX351101B (en) | 2017-10-02 |
MX2015004909A (en) | 2015-07-21 |
US20190143287A1 (en) | 2019-05-16 |
WO2014062643A1 (en) | 2014-04-24 |
CN105102115A (en) | 2015-11-25 |
CA2888781C (en) | 2019-12-31 |
US20160325252A1 (en) | 2016-11-10 |
CN105102115B (en) | 2020-02-07 |
US10828613B2 (en) | 2020-11-10 |
SA515360295B1 (en) | 2016-04-03 |
RU2015113933A (en) | 2016-12-10 |
US20140114039A1 (en) | 2014-04-24 |
SG11201503062WA (en) | 2015-05-28 |
EP2908941B1 (en) | 2024-04-24 |
US8821800B2 (en) | 2014-09-02 |
RU2644173C2 (en) | 2018-02-08 |
CA2888781A1 (en) | 2014-04-24 |
EP2908941A1 (en) | 2015-08-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10828613B2 (en) | System and method for catalyst preparation | |
US9079986B2 (en) | Polyolefin production with different diluents in multiple polymerization reactors | |
US9403921B2 (en) | Chain transfer agent removal between polyolefin polymerization reactors | |
US10894840B2 (en) | Unified cooling for multiple polyolefin polymerization reactors | |
US9963523B2 (en) | Polyethylene production with multiple polymerization reactors | |
CA2894862C (en) | Polyethylene production with multiple polymerization reactors | |
US10913046B2 (en) | Cooling between multiple polyolefin polymerization reactors | |
US10072103B2 (en) | Unified cooling for multiple polyolefin polymerization reactors |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |