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    • 专利摘要:
    METHOD OF PREPARING A CATALYST A method comprising a) drying a support material comprising silica at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with methanol to form a slurry support; c) subsequent to b) cooling the slurry support to a temperature of less than about 60°C to form a cooled slurry support; d) subsequent to c) contacting the cooled slurry support with a titanium alkoxide to form a titanized support; and e) heat treating the titanized support by heating to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to remove the methanol and yield a dry titaned support.
    公开号:BR112018005406B1
    申请号:R112018005406-2
    申请日:2016-09-15
    公开日:2022-01-25
    发明作者:Jeremy M. Praetorius；Eric D. Schwerdtfeger；Max P. Mcdaniel；Ted H. Cymbaluk；Conner D. Boxell；Kathy S. Clear；Alan L. Solenberger
    申请人:Chevron Phillips Chemical Company Lp；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present disclosure relates to catalyst compositions. More specifically, the present disclosure pertains to methods for preparing olefin polymerization catalyst compositions. FUNDAMENTALS
    [0002] Enhancements in preparation methods for olefin polymerization catalysts can reduce costs associated with catalyst production and improve process economics. Thus, there is a constant need to develop new methods of preparing olefin polymerization catalysts. SUMMARY
    [0003] Disclosed herein is a method comprising a) drying a support material comprising silica at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with methanol to form a slurry support; c) subsequent to b) cooling the slurry support to a temperature of less than about 60°C to form a cooled slurry support; d) subsequent to c) contacting the cooled slurry support with a titanium alkoxide to form a titanized support; and e) heat treating the titanized support by heating to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to remove the methanol and yield a dry titaned support.
    [0004] Also disclosed herein is a method comprising a) drying a silica support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solution comprising methanol containing less than 0.1% by weight of water and basic chromium acetate to form a chrome paste support; c) cooling the chrome slurry support to a temperature of less than about 60°C to form a cooled slurry support; d) contacting the cooled paste support with titanium n-propoxide to form a titanized paste support; e) heat treating the titanium paste support by increasing the temperature of the titanium support to 60°C to 70°C; f) prior to complete removal of methanol, contacting the slurry support by titaning with water in an amount ranging from about 0.1 mol to about 10 mol per mol of titanium to produce a mixture; g) heat treating the mixture by heating the mixture to a temperature of about 150°C to about 220°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and h) calcining the precatalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst.
    [0005] Also disclosed herein is a method comprising a) drying a silica support at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a chromium-containing compound to form a chrome support; c) contacting the chrome support with a solvent to form a paste support; d) cooling the cooled slurry support to a temperature of less than about 60°C to form a cooled support; e) contacting the cooled support with a titanium-containing compound to form a titanized support; f) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; h) heat treating the mixture by heating the mixture to a temperature of about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and i) calcining the precatalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst. BRIEF DESCRIPTION OF THE DRAWINGS
    [0006] Figure 1 represents a thermogravimetric analysis of the samples from example 2. DETAILED DESCRIPTION
    [0007] Disclosed herein are methods for preparing a polymerization catalyst. In one embodiment, the method comprises contacting a support of silica, titanium alkoxide and basic chromium acetate under conditions suitable for the formation of a polymerization catalyst. In one embodiment, a polymerization catalyst produced as disclosed herein results in lower emissions of volatile organic compounds (VOCs) during production (e.g. activation via calcination) compared to otherwise similar catalysts and is termed a higher emission catalyst. low (LEC).
    [0008] In one embodiment, an LEC comprises a silica support. A silica support suitable for use in the present disclosure may have an effective surface area and pore volume to provide for the production of an active catalyst (e.g., an LEC). In one embodiment, the silica support has a surface area in the range of from about 250 m2/gram to about 1000 m2/gram, alternatively from about 250 m2/gram to about 700 m2/gram, alternatively from about 250 m2/gram to about 600 m2/gram, or alternatively greater than 250 m2/gram. The silica support may further be characterized by a pore volume greater than about 1.0 cm 3 /gram, or alternatively greater than about 1.5 cm 3 /gram. In one embodiment, the silica support is characterized by a pore volume ranging from about 1.0 cm 3 /gram to about 2.5 cm 3 /gram. The silica support may further be characterized by an average particle size of about 10 microns to about 500 microns, alternatively about 25 microns to about 300 microns, or alternatively about 40 microns to about 150 microns. Generally, the average pore size of the silica support ranges from about 10 Angstroms to about 1000 Angstroms. In one embodiment, the average pore size of the silica support material is in the range of about 50 Angstroms to about 500 Angstroms, while in yet another embodiment the average pore size ranges from about 75 Angstroms to about 350 Angstroms. .
    [0009] The silica support may contain more than about 50 percent (%) silica, alternatively more than about 80% silica, alternatively more than about 95% silica by weight of the silica support material. The silica support can be prepared using any suitable method, for example the silica support can be prepared synthetically by hydrolyzing tetrachlorosilane (SiCl4 ) with water or by contacting sodium silicate with a mineral acid. An example of a silica support suitable for use in this disclosure includes without limitation ES70 which is a silica support material with a surface area of 300m 2 /g and a pore volume of 1.6 cm 3 /g which is commercially available from PQ Corporation . The silica support may include additional components that do not adversely affect the LEC, such as zirconia, alumina, thoria, magnesia, fluoride, sulfate, phosphate or mixtures thereof.
    [0010] The silica support may be present in the LEC in an amount from about 50 weight percent (wt%) to about 99 weight percent or, alternatively, from about 80 weight percent to about 99% in weight. Here, the silica support percentage refers to the final weight percentage of silica support associated with the catalyst per total weight of the catalyst after all processing steps (e.g. after final activation via calcination).
    [0011] In one embodiment, an LEC comprises titanium. The source of the titanium may be a titanium-containing compound, such as a titanium tetraalkoxide. In one embodiment, the titanium-containing compound is titanium n-propoxide Ti(OnPr)4.
    [0012] The amount of titanium present in the LEC can vary from about 0.1% by weight to about 10% by weight of titanium by weight of the LEC, alternatively from about 0.5% by weight to about 5% by weight of titanium, alternatively from about 1% by weight to about 4% by weight or, alternatively, from about 2% by weight to about 4% by weight. In another embodiment, the amount of titanium can range from about 1% by weight to about 5% by weight. Here, the percentage of titanium refers to the final weight percentage of titanium associated with the catalyst composition per total weight of the catalyst composition after all processing steps (e.g. after final activation via calcination).
    [0013] In one embodiment, an LEC comprises chromium. The source of the chromium can be any chromium-containing compound that is substantially soluble in methanol. Here, "substantially soluble" refers to a solubility of at least 0.1 gram/liter. Non-limiting examples of chromium-containing compounds suitable for use in the present disclosure include basic chromium acetate, chromium acetate, chromium(III) nitrate monohydrate, chromium trioxide and t-butyl chromate. In one embodiment, the LEC comprises basic chromium acetate.
    [0014] The amount of chromium present in the catalyst may vary from about 0.1% by weight to about 10% by weight of the LEC, alternatively from about 0.25% by weight to about 3% by weight, or alternatively from about 0.5% by weight to about 1.5% by weight. Here, the chromium percentage refers to the final percentage of chromium associated with the support material per total weight of the material after all processing steps (eg after final activation via calcination).
    [0015] In one embodiment, a method for preparing an LEC comprises drying the silica support. Drying of the silica support can be carried out in a temperature range of from about 150 °C to about 500 °C, alternatively from about 150 °C to about 300 °C, or alternatively from about 150 °C to at about 220°C for a period of time ranging from about 5 hours to about 24 hours, or alternatively from about 5 hours to about 12 hours. Drying of the support material can be carried out in an inert atmosphere (eg under vacuum, He, Ar, or nitrogen gas). The resulting material is called a dry support. The dryness of the silica support can be measured as weight loss upon drying at a temperature of 250°C. In one embodiment, the loss on drying of the dry support is less than about 3% by weight, alternatively less than about 2% by weight, or alternatively less than about 1% by weight.
    [0016] In one embodiment, the method for preparing an LEC further comprises slurrying the dry support with dry methanol. Here, "dry methanol" refers to methanol having a water content of less than about 0.1% by weight. The dry support can be slurried by contacting dry methanol in an amount ranging from about 1 to about 10 times the total weight of the dry support or, alternatively, from about 2 to about 3 times the total weight of the dry support. dry support. The resulting material is called a dry paste support.
    [0017] In one embodiment, the method for preparing an LEC further comprises cooling the dried support into paste. The dry paste support may be cooled to a temperature of less than about 80°C, alternatively less than about 60°C, or alternatively less than about 50°C. The resulting material is termed a cooled dry paste support.
    [0018] In one embodiment, the method for preparing an LEC further comprises adding a titanium alkoxide to the cooled paste dry support to produce a titanized dry paste cooled support. The titanium alkoxide may comprise equal to or less than twenty-four carbon atoms. Non-limiting examples of titanium alkoxides suitable for use in the present disclosure include titanium alkoxides comprising linear alkyl chains. In one embodiment, the titanium alkoxide excludes branched alkyl chains. In one embodiment, the titanium alkoxide comprises titanium n-propoxide (i.e., Ti(OnPr)4), titanium n-butoxide (i.e., Ti(OnBu)4) or combinations thereof. Titanium can be added directly to the cooled dry paste support with vigorous mixing so that the titanium is efficiently dispersed throughout the paste. Upon addition of the titanium alkoxide to the cooled slurry dry support, the resulting mixture may be stirred at room temperature for a period of time ranging from about 5 minutes to about 30 hours; alternatively from about 15 minutes to about 12 hours, or alternatively from about 30 minutes to about 5 hours.
    [0019] In one embodiment, the method for preparing an LEC further comprises adding a chromium-containing compound (e.g., basic chromium acetate) to the titanized cooled paste dry support. The resulting material is called a metallized paste support.
    [0020] In one embodiment, the method for preparing an LEC further comprises adding a chromium-containing compound (e.g., basic chromium acetate) to the cooled dry paste support. The resulting material is called a chrome-cooled dry paste support. The chrome-cooled dry paste support can then be contacted with a titanium-containing compound (e.g., Ti(OnPr) 4 ) as disclosed herein to produce a chrome-titated dry paste dry support.
    [0021] In an alternative embodiment, the method for preparing an LEC may comprise adding a chromium-containing compound (e.g., basic chromium acetate) to the dry support to result in a chrome dry support. The chrome dry support can then be slurried to produce a paste chrome dry support. The dry paste chrome support can then be cooled as described herein to produce a dry paste chrome dry support. The cooled paste chrome dry support can then be contacted with a titanium-containing compound (e.g. Ti(OnPr) 4 ) as disclosed herein to produce a titanized cooled paste chrome dry support.
    [0022] In yet another embodiment, the method for preparing an LEC further comprises adding a chromium-containing compound (eg, basic chromium acetate) to the dry paste support resulting in a dry chrome paste support. The chrome paste chrome dry support may subsequently be cooled as described herein to produce a cooled chrome paste chrome dry support. The cooled chrome slurry dry support can then be contacted with a titanium-containing compound (e.g., Ti(OnPr)4) as disclosed herein to produce a titanized cooled chrome slurry dry support.
    [0023] Here, Titanium cooled paste dry support, Titanium cooled chrome paste dry support, Titanium cooled paste chrome dry support, Titanium cooled chrome paste dry support are collectively referred to as Metallic supports.
    [0024] In each of the foregoing embodiments that result in the production of a metallated support, it will be understood that processing conditions similar to those previously disclosed herein (e.g. mixing times, stirring times, heating times, cooling times, temperatures cooling, etc.) can be applied. In one embodiment, for each of the disclosed methods of preparing a metallated support the processing conditions described herein apply.
    [0025] In various embodiments, the chromium-containing compound (e.g., basic chromium acetate) can be added at any point in the process after drying the silica and before completing the methanol removal. In some embodiments, the chromium-containing compound (e.g., basic chromium acetate) can be dissolved in the methanol solvent before slurrying the silica.
    [0026] In one embodiment, a method of preparing an LEC further comprises subjecting the metallized paste support to a heat treatment. In one embodiment, the heat treatment comprises heating the metallized slurry support to a temperature near the boiling point of methanol (i.e., from about 60°C to about 70°C). The method of the present disclosure further comprises adding water to the metallated slurry support prior to and/or during heat treatment and prior to complete removal of methanol. Here, "complete removal" of methanol removal refers to less than about 10 volume percent (10 vol. less than about 8 vol.%, alternatively less than about 7 vol. of 4% by vol., alternatively, less than about 3% by vol., alternatively, less than about 2% by vol. or, alternatively, less than about 1% by vol. Water may be added to the metallated paste support in an amount ranging from about 0.1 mol to about 10 mol per mol of titanium, alternatively from about 1 mol to about 8 mol, or alternatively from about 2 mol. moles to about 5 moles. The material resulting from the addition of water and heating to about 60°C to about 70°C is called the hydrated metallated support.
    [0027] In one embodiment, the metallized paste support may be subjected to heat treatment at a temperature of about 150°C, alternatively from about 150°C to about 300°C, or alternatively from about 150°C. °C to about 220 °C for a period of time from about 5 hours to about 30 hours or, alternatively, from about 5 hours to about 15 hours or, alternatively, from about 5 hours to about 8 hours. In one embodiment, water may be added to the metallated paste support at any point after the addition of titanium to also produce a hydrated metallated support. Water can be added in any form, i.e. solid, liquid, vapor or solution.
    [0028] The hydrated metallated support can then be subjected to further heat treatment at a temperature of about 150°C, alternatively from about 150°C to about 300°C or alternatively from about 150°C C to about 220°C for a period of time from about 5 hours to about 30 hours or, alternatively, from about 5 hours to about 15 hours, or alternatively, from about 5 hours to about 8 hours . The resulting material is called the dry pre-catalyst.
    [0029] In one embodiment, the dry pre-catalyst is heat treated (ie, calcined) to form an LEC. Heat treatment of the dry pre-catalyst can be carried out using any suitable method, for example fluidization. Without wishing to be bound by theory, heat treatment of the dry pre-catalyst can result in an increase in the amount of hexavalent chromium present in the catalyst. In one embodiment, heat treatment of the dry pre-catalyst is carried out in any suitable atmosphere, such as air, oxygen, inert gases (e.g. Ar) or carbon monoxide by treating to a temperature of about 400°C at about 400°C. 1000°C, alternatively from about 450°C to about 900°C, alternatively from about 500°C to about 800°C or alternatively from about 500°C to about 700°C. The heat treatment may be carried out for a period of time ranging from about 30 minutes to about 24 hours, alternatively from about 1 hour to about 12 hours, or alternatively from about 4 hours to about 12 hours.
    [0030] In one embodiment, one or more of the steps described earlier in this document for preparing an LEC may be performed in a reactor or reactor system. In an alternative embodiment, one or more of the steps described earlier in this document for preparing an LEC may be performed outside of a reactor or reactor system. In such embodiments, one or more preparation parameters (eg, heat treatment of the dry pre-catalyst) can be adjusted to facilitate LEC formation.
    [0031] In one embodiment, a method for preparing an LEC of the type disclosed herein comprises obtaining a prepared Cr-Si/Ti pre-catalyst. The prepared Cr-Si/Ti pre-catalyst can be slurried in methanol to produce a slurry pre-catalyst. The paste pre-catalyst can still be subjected to a heat treatment. In one embodiment, the heat treatment comprises heating the slurry precatalyst to a temperature of at least about 150°C, alternatively from about 150°C to about 300°C, or alternatively from about 150°C. C to about 220°C for a period of time from about 5 hours to about 30 hours or, alternatively, from about 5 hours to about 15 hours, or alternatively, from about 5 hours to about 8 hours . The resulting material is called the dry pre-catalyst. In one embodiment, the dry pre-catalyst is heat treated (i.e., calcined) to form an LEC.
    [0032] The method of the present disclosure further comprises adding water to the slurry pre-catalyst. Water may be added to the slurry catalyst in an amount ranging from about 0.1 mol to about 10 mol per mol of titanium, alternatively from about 1 mol to about 8 mol, or alternatively from about 2 mol. to about 5 moles. Water can be added in any form, i.e. solid, liquid, vapor or solution.
    [0033] The catalysts of the present disclosure (i.e., LECs) are suitable for use in any olefin polymerization method using various types of polymerization reactors. In one embodiment, a polymer of the present disclosure is produced by an olefin polymerization method using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. Homopolymers and/or copolymers produced in the reactor may be referred to as resin and/or polymers. The various types of reactors include, but are not limited to, those that may be referred to as batch, continuous, slurry, gas phase, solution, high pressure, tubular, autoclave or other reactor and/or reactors. Gas phase reactors may comprise fluidized bed reactors or horizontal stepped reactors. Slurry reactors may comprise vertical and/or horizontal closed loops. High pressure reactors may comprise autoclave and/or tubular reactors. Reactor types may include batch and/or continuous processes. Continuous processes may use intermittent and/or continuous product discharge or transfer. The processes may also include partial or complete direct recycling of an unreacted monomer, unreacted comonomer, catalyst and/or cocatalysts, diluents and/or other materials from the polymerization process.
    [0034] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type operated in any suitable configuration. The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer system making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, multi-reactor polymerization may include the transfer, either manually or automatically, of polymer from one reactor to reactor or subsequent reactors for further polymerization. Alternatively, multi-stage or multi-step polymerization can take place in a single reactor, where conditions are changed so that a different polymerization reaction takes place.
    [0035] The desired polymerization conditions in one of the reactors may be the same as or different from the operating conditions of any other reactors involved in the overall process of producing the polymer of the present disclosure. Multiple reactor systems may include any combination including, but not limited to, multiple closed loop reactors, multiple gas phase reactors, a combination of closed loop and gas phase reactors, multiple high pressure reactors or a combination of high pressure with closed circuit and/or gas. Multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and/or any combination of reactors may be employed to produce the polymer of the present disclosure.
    [0036] According to one embodiment, the polymerization reactor system may comprise at least one closed loop slurry reactor. These reactors are common and may comprise vertical or horizontal closed loops. Monomer, diluent, catalyst system and optionally any comonomer can be continuously fed to a closed loop slurry reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst and/or a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. Reactor effluent can be burned to remove liquids comprising the polymer diluent, monomer and/or solid comonomer. Various technologies can be used for this separation step including, but not limited to, firing which can include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; centrifugal separation; or other appropriate method of separation.
    [0037] Typical slurry polymerization processes (also known as particle shape processes) are disclosed in US Patents 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833. 415, for example, each of which is incorporated herein by reference in its entirety.
    [0038] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some closed-loop polymerization reactions can take place in bulky conditions where no diluent is used. One example is propylene monomer polymerization, as disclosed in US Patent 5,455,314, which is incorporated by reference herein in its entirety.
    [0039] According to another embodiment, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream can be taken from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas-phase reactors may comprise a process for multi-step gas-phase polymerization of olefins in which olefins are gas-phase polymerized in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in US Patents 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated by reference in its entirety herein.
    [0040] According to yet another embodiment, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have multiple zones where fresh monomer, initiators or catalysts are added. Monomer can be entrained in an inert gas stream and introduced into a reactor zone. Initiators, catalysts and/or catalyst components can be entrained in a gas stream and introduced into another zone of the reactor. The gas streams can be intermixed for polymerization. Heat and pressure can be appropriately employed to obtain optimal polymerization reaction conditions.
    [0041] In accordance with yet another embodiment, the polymerization reactor may comprise a solution polymerization reactor in which the monomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an excess of an organic diluent or monomer may be employed. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reaction product in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation can be employed to obtain better temperature control and maintain uniform polymerization mixtures throughout the polymerization zone. Suitable media are used to dissipate the exothermic heat of polymerization.
    [0042] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock system, at least one feed system for catalyst or catalyst components, and/or at least one recovery system. of polymer. Reactor systems suitable for the present disclosure may further comprise systems for feed stock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis and process control. .
    [0043] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and amount of catalyst or cocatalyst, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperatures below the depolymerization temperature according to the Gibbs Free Energy Equation. Typically this includes from about 60°C to about 280°C, for example, and/or from about 70°C to about 110°C, depending on the type of polymerization reactor and/or the polymerization process. .
    [0044] Suitable pressures will also vary depending on the reactor and the polymerization process. The pressure for liquid phase polymerization in a closed loop reactor is typically less than 1000 psig (6.9 MPa). Pressure for gas phase polymerization is generally about 200 psig (1.4 MPa) to 500 psig (3.45 MPa). High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 psig (138 MPa) to 75,000 psig (518 MPa). Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.
    [0045] The concentration of various reagents can be controlled to produce polymers with certain physical and mechanical properties. The proposed end-use product that will be formed from the polymer and the method of forming that product can be varied to determine the desired end-product properties. Mechanical properties include, but are not limited to, tests of tensile strength, flexural modulus, impact strength, creep, stress relaxation, and hardness. Physical properties include, but are not limited to, measurements of density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, melting temperature of crystallization, density, stereoregularity, crack growth, short chain branching , long-chain branching and rheological.
    [0046] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in producing specific polymer properties. The comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate poisons and/or control molecular weight. Poison concentrations can be minimized as poisons can impact reactions and/or otherwise affect polymer product properties. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
    [0047] Polymers such as homopolymers of polyethylene and copolymers of ethylene with other monoolefins can be produced in the manner described above using the LECs prepared as described herein. Polymer resins produced as disclosed herein can be formed into articles of manufacture or end-use articles using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and casting. For example, a polymer resin can be extruded into a sheet which is then thermoformed into an end-use article, such as a container, cup, tray, pallet, toy, or other product component. Examples of other end-use articles into which polymer resins can be formed include tubes, films, bottles, fibers and so on.
    [0048] In one embodiment, an LEC prepared as disclosed herein results in a reduction in the level of volatile organic compounds (VOCs) produced during catalyst preparation. For example, VOCs can comprise hydrocarbons, aromatic compounds, alcohols, ketones or combinations thereof. In one embodiment, the VOCs comprise alkenes, alternatively propylene, butene, ethylene or combinations thereof. LECs produced as disclosed herein can be characterized by VOC emissions that are reduced by about 50% to about 99% compared to emissions from an otherwise similar catalyst. Here, an "otherwise similar catalyst" refers to a chromium-silica-titania catalyst having been prepared using the same process, except without the addition of water in the amounts disclosed herein. Alternatively, VOC emissions from LECs prepared as disclosed herein are reduced by more than about 50%, alternatively more than about 75%, alternatively more than about 90%, or alternatively, more than about 99% compared to with an otherwise similar catalyst. In one embodiment, the VOC is an alcohol and the LEC has emissions from about 50% by weight to about 1% by weight based on the weight of the LEC, alternatively less than about 20% by weight, alternatively less than about 10% by weight or, alternatively, less than about 1% by weight. EXAMPLES
    [0049] The following examples are given as particular modalities of disclosure and to demonstrate the practice and advantages of the same. It is understood that the examples are given by way of illustration and are not intended to limit the specification or claims that follow in any way.
    [0050] Melt index (MI, g/10 min.) was determined according to ASTM D1238 at 190°C with a weight of 2160 grams. The high melt load index (HLMI) of a polymer resin represents the flow rate of a resin melted through a 0.0825 inch diameter orifice when subjected to a force of 21,600 grams at 190°C. HLMI values are determined in accordance with ASTM D1238 condition E.
    [0051] Polymerizations were performed in 1.2 L of isobutane at 100 °C and 550 psi of ethylene with 5 mL of 1-hexene and run to a productivity of 3,200 g PE/g catalyst. Catalyst activity was determined by dividing the mass of polymer recovered from the reaction by the amount of catalyst used and the time of active polymerization. Examples 1 and 2
    [0052] Catalysts of the type disclosed herein were prepared and their catalytic properties investigated. Specifically, a first catalyst, designated I1, was prepared using silica gel (14.74 g) that had been dried at 180°C and weighed into a flask and placed under a positive pressure of dry nitrogen. Enough dry methanol was added to the silica to make a paste. In a separate flask, basic chromium acetate (0.485 g, 0.8% by weight) was dissolved in methanol and then added to the stirred silica gel slurry. Ti(OnPr)4 (2.3 mL, 27% by weight) was added dropwise to the stirred Cr/silica slurry over 5 to 10 minutes, then the whole mixture was allowed to stir for 15 minutes. The mixture was then heated to 100°C for 16 hours to completely distill methanol and other volatiles. In the heating process, water is added to the mixture (0.74 ml, 5% by weight). After cooling, the dry pre-catalyst was loaded into a 1.88-inch diameter activator tube. The pre-catalyst was then calcined in dry air (1.2 to 1.6 scfh) at 4°C/min. at 650°C and held at that temperature for 3 hours to form the active catalyst. A second catalyst, designated I2, was prepared using the method described for preparing I1, without the addition of water.
    [0053] The catalysts were then used to prepare the polymers. The polymerization passes were carried out in a 2.65L stainless steel reactor equipped with a marine agitator rotating at 500 rpm. The reactor was surrounded by a stainless steel jacket through which a stream of hot water was circulated which allowed precise temperature control of the reactor to within half a degree centigrade, with the aid of electronic control instrumentation. A small amount of the catalyst (0.05 to 0.10 g) was first charged to the reactor in dry nitrogen. Then approximately 0.6 L of liquid isobutane was added, followed by 5 mL of 1-hexene and additional liquid isobutane to a total of 1.2 L, and the reactor heated to the set temperature of 100°C. Ethylene was then added to the reactor which was maintained at 550 psi throughout the course of the experiment. The reactor was operated to a throughput of 3200 g^polyethylene/g^catalyst, as determined by the reactor instrumentation flow controllers based on the flow of ethylene to the reactor. After the assigned throughput, the flow of ethylene to the reactor was stopped and the reactor slowly depressurized and opened to recover the granular polymer powder. Dry powder was then removed and weighed. Activity was determined from dry powder weight and time measured. The HLMI and MI of the polymers produced from these catalysts were determined and are shown in Table 1. Table 1

    [0054] These two passages show that the addition of water after the addition of Ti did not impair the activity or the potential melt index of the polymer prepared from the catalyst. However, the addition of water removed unwanted volatiles during further calcination, as shown in the following example. Example 3
    [0055] A dry Cr/silica-titania pre-catalyst (15.87 g) as prepared in example I2 was slurried in MeOH (~50 mL). To the Cr/silica-titania slurry was added water (0.8 mL) and the mixture allowed to stir for 30 min. The mixture was then heated to 100°C overnight to remove volatile components by distillation and designated I3.
    [0056] The water-treated dry pre-catalyst (I3) was compared by TGA with the same dry pre-catalyst that did not receive water treatment (C1, Figure 1) and it can be seen that water-treated I3 contains significantly less material volatile organic than C1. Both water-treated (I3) and control (C1) pre-catalysts were then activated by calcination in dry air (1.2 to 1.6 scfh) at 4°C/min. up to 650°C for 3 hours to form the active catalyst.
    [0057] The polymerization results, shown in the table below, again demonstrate no significant loss in activity or potential MI from this additional water treatment, as seen in Table 2. Table 2
    Example 4
    [0058] The solubility of alkyl titanates used in the preparation of LECs was investigated. To a flask dried under a nitrogen atmosphere were added 625 mg of basic chromium acetate and 30 ml of isopropanol. The mixture was heated to 78°C for one hour in order to dissolve the chromium which remained in solution upon cooling. After cooling the resulting green solution to room temperature, 2.8 mL of Ti(OiPr)4 was added with stirring. The solution remained homogeneous for several hours before being used in the Cr/silica-titania catalyst preparation.
    [0059] Basic chromium acetate (625 mg) and 30 mL of room temperature methanol were added to a dry flask under an atmosphere of nitrogen. The chromium readily dissolved to form a green homogeneous solution. To this solution was added 2.8 ml of Ti(OiPr)4. Precipitation of a white solid was observed to begin after three minutes demonstrating that these titanium alkoxides are not soluble in methanol. While not wishing to be bound by theory, we believe this is because of the rapid exchange of alkoxy groups to form titanium methoxide groups.
    [0060] However, methanol has had few challenges, because of the ease with which it dissolves chromium acetate and because of its low boiling point, which makes the final catalyst easier to dry. Consequently, the use of methanol greatly shortens the production process. Table 3 below shows the boiling points of other non-aqueous solvents capable of dissolving the chromium salt.Table 3
    Example 5
    [0061] An LEC of the type disclosed in this document has been prepared. Specifically, silica was dried at a temperature of about 150°C to 200°C for 5 to 24 hours. The silica was then slurried in 2 to 3 times its own weight of dry methanol containing less than 0.1% water. The slurry was then cooled to less than 40°C. Optionally, basic chromium acetate can be added to this slurry, but if the temperature is raised to dissolve the Cr, then the slurry must be subsequently cooled before adding titanium. Titanium n-propoxide was then quickly added to the cooled slurry at high stirring rate to promote rapid reaction and the mixture allowed to stir in the cooled state for 1 to 30 hours. Optionally, basic chromium acetate can be added to this slurry at this point in the process. The temperature was then raised to 65 °C. Water was then added during heating in the amount of 2 to 10 mol per mol of titanium. The mixture was allowed to stir at 65°C for 1 to 3 hours. Then, the solvent, water and n-propanol by-product were distilled off and dried at 150 °C for 5 to 30 hours to generate a pre-catalyst. The pre-catalyst was subsequently calcined between 400°C and 1000°C to generate a catalyst. ADDITIONAL DISCLOSURE
    [0062] The following enumerated embodiments are provided as non-limiting examples.
    [0063] A first embodiment which is a method comprising a) drying a support material comprising silica at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with methanol to form a slurry support; c) subsequent to b) cooling the slurry support to a temperature of less than about 60°C to form a cooled slurry support; d) subsequent to c) contacting the cooled slurry support with a titanium alkoxide to form a titanized support; and e) heat treating the titanized support by heating to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to remove the methanol and yield a dry titaned support.
    [0064] A second embodiment which is the method of the first embodiment further comprising adding a chromium-containing compound prior to the removal of methanol to form a pre-catalyst.
    [0065] A third embodiment which is the method of any of the first to second embodiments further comprising adding water in an amount ranging from about 0.1 to about 10 moles per mole of titanium after the addition of the titanium alkoxide .
    [0066] A fourth embodiment which is the method of any of the second to third embodiments further comprising calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time of about 30 minutes to about 24 hours to form a polymerization catalyst.
    [0067] A fifth embodiment which is the method of any of the first to fourth embodiments wherein the silica is dried for a period of time ranging from about 5 hours to about 24 hours and a weight loss on drying the dry support is less than about 2% by weight.
    [0068] A sixth embodiment which is the method of any of the first to fifth embodiments, wherein the methanol is present in an amount ranging from about 2 times to about 3 times the weight of the dry support.
    [0069] A seventh embodiment which is the method of any of the first through sixth embodiments wherein the methanol has a water content of less than about 0.1% by weight.
    [0070] An eighth embodiment which is the method of any of the first through seventh embodiments wherein the silica is characterized by a surface area of about 250 m2/g to about 1000 m2/g and a pore volume greater than about 1.0 cm 3 /g.
    [0071] A ninth embodiment which is the method of any of the first to eighth embodiments wherein the titanium alkoxide comprises titanium n-propoxide.
    [0072] A tenth embodiment which is the method of any of the first to ninth embodiments wherein the titanium alkoxide is present in an amount of from about 0.1% by weight to about 10% by weight by the total weight of the catalyst .
    [0073] An eleventh embodiment which is the method of any of the second to tenth embodiments, wherein the chromium-containing compound comprises basic chromium acetate.
    [0074] A twelfth embodiment which is the method of any of the second to eleventh embodiments wherein the chromium-containing compound is present in an amount of from about 0.1% by weight to about 10% by weight by total weight of the catalyst.
    [0075] A thirteenth embodiment which is the method of any of the fourth to twelfth embodiments in which an amount of volatile organic compounds (VOC) emitted during calcination at a temperature in the range of about 400°C to about 1000 °C for a period of time from about 30 minutes to about 24 hours is reduced by about 50% to about 100% compared to the amount of VOC emitted during the calcination of an otherwise similar catalyst prepared without the addition of water.
    [0076] A fourteenth embodiment which is the method of any of the fourth to thirteenth embodiments in which an amount of volatile organic compounds (VOC) emitted during calcination at a temperature in the range of about 400°C to about 1000 °C for a period of time from about 30 minutes to about 24 hours is less than about 2% by weight.
    [0077] A fifteenth embodiment which is a method comprising a) drying a silica support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solution comprising methanol containing less than 0.1% by weight of water and basic chromium acetate to form a chrome paste support; c) cooling the chrome plated slurry support to a temperature of less than about 60°C to form a cooled slurry support; d) contacting the cooled paste support with titanium n-propoxide to form a titanized paste support; e) heat treating the titanium paste support by increasing the temperature of the titanium support to 60°C to 70°C; f) prior to complete removal of methanol, contacting the slurry support by titaning with water in an amount ranging from about 0.1 mol to about 10 mol per mol of titanium to produce a mixture; g) heat treating the mixture by heating the mixture to a temperature of about 150°C to about 220°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and h) calcining the precatalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst.
    [0078] A sixteenth embodiment which is the method of the fifteenth embodiment in which the support is dried to a weight loss on drying of less than about 2% by weight, an amount of chromium is about 0.5% by weight to about 1.5% by weight based on a total weight of the polymerization catalyst, an amount of titanium is from about 1% by weight to about 5% by weight based on a total weight by weight of the polymerization catalyst and the amount of water added in step f) is from about 2 mol to about 5 mol per mol of titanium.
    [0079] A seventeenth embodiment which is the method of any of the fifteenth to sixteenth embodiments in which the pre-catalyst is calcined at a temperature in the range of about 500°C to about 700°C for a period of time from about 4 hours to about 12 hours.
    [0080] An eighteenth embodiment which is a method comprising: a) drying a silica support at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a chromium-containing compound to form a chrome support; c) contacting the chrome support with a solvent to form a paste support; d) cooling the cooled slurry support to a temperature of less than about 60°C to form a cooled support; e) contacting the cooled support with a titanium-containing compound to form a titanized support; f) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; h) heat treating the mixture by heating the mixture to a temperature of about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and i) calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst
    [0081] A nineteenth embodiment which is the method of the eighteenth embodiment wherein the solvent comprises methanol having less than about 0.1% by weight of water.
    [0082] A twentieth embodiment which is the method of any of the eighteenth to nineteenth embodiments, wherein the titanium-containing compound comprises titanium n-propoxide.
    [0083] A twenty-first embodiment which is the method of any of the eighteenth to twentieth embodiments wherein the silica support is characterized by a surface area of about 250 m2/g to about 1000 m2/g and a pore volume greater than about 1.0 cm3/g.
    [0084] A twenty-second embodiment which is a method comprising a) drying a support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solvent to form a paste support; c) subsequent to b) cooling the slurry support to a temperature less than about 50°C to form a cooled support; d) contacting the cooled support with a titanium-containing compound to form a titanized support; e) contacting the titanized support with a titanium-containing compound to form a chrome support; f) heat treating the chrome support by increasing the temperature of the chrome support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the chrome support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; and h) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst.
    [0085] A twenty-third embodiment which is the method of the twenty-second embodiment further comprising calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time of about 30 minutes to about 24 hours to form a polymerization catalyst.
    [0086] A twenty-fourth embodiment which is the method of any of the twenty-second to twenty-third embodiments wherein the silica is dried for a period of time ranging from about 5 hours to about 24 hours.
    [0087] A twenty-fifth embodiment which is the method of any of the twenty-second to twenty-fourth embodiments, wherein the solvent is present in an amount ranging from about 2 times to about 3 times the weight of the dry support.
    [0088] A twenty-sixth embodiment which is the method of any of the twenty-second to twenty-fifth embodiments wherein step (d) is performed under mixing conditions for efficient dispersion of the titanium alkoxide.
    [0089] A twenty-seventh embodiment which is the method of any of the twenty-second to twenty-sixth embodiments wherein the solvent comprises methanol having a water content of less than about 0.1% by weight.
    [0090] A twenty-eighth embodiment which is the method of any of the twenty-second to twenty-seventh embodiments wherein the support material comprises silica.
    [0091] A twenty-ninth embodiment which is the method of the twenty-eighth embodiment wherein the silica is characterized by a surface area of about 250 m2/g to about 1000 m2/g and a pore volume greater than about 1, 0 cm3/g.
    [0092] A thirtieth embodiment which is the method of any of the twenty-second to twenty-ninth embodiments, wherein the titanium-containing compound comprises titanium n-propoxide.
    [0093] A thirty-first embodiment which is the method of any of the twenty-second to thirtieth embodiments wherein the titanium-containing compound is present in an amount of from about 0.1% by weight to about 10% by weight by total weight of the catalyst.
    [0094] A thirty-second embodiment which is the method of any of the twenty-first to thirty-first embodiments, wherein the chromium-containing compound comprises basic chromium acetate.
    [0095] A thirty-third embodiment which is the method of the thirty-second embodiment wherein the chromium-containing compound is present in an amount of from about 0.1% by weight to about 10% by weight by the total weight of the catalyst.
    [0096] A thirty-fourth embodiment which is a method comprising a) drying a support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solvent to form a paste support; c) subsequent to b) cooling the dried slurry support to a temperature less than about 50°C to form a cooled support; d) contacting the cooled support with a chromium-containing compound to form a chrome support; e) contacting the chrome support with a titanium-containing compound to form a titanized support; f) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; and h) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst.
    [0097] A thirty-fifth embodiment which is the method of the thirty-fourth embodiment further comprising calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time of about 30 minutes to about 24 hours to form a polymerization catalyst.
    [0098] A thirty-sixth embodiment which is the method of any of the thirty-fourth to thirty-fifth embodiments wherein the solvent comprises methanol having less than about 0.1% by weight of water.
    [0099] A thirty-seventh embodiment which is the method of any of the thirty-fourth to thirty-sixth embodiments wherein the support material comprises silica.
    [00100] A thirty-eighth embodiment which is the method of the thirty-seventh embodiment wherein the silica is characterized by a surface area of about 250 m2/g to about 1000 m2/g and a pore volume greater than about 1, 0 cm3/g.
    [00101] A thirty-ninth embodiment which is the method of any of the thirty-fourth to thirty-eighth embodiments, wherein the titanium-containing compound comprises titanium n-propoxide.
    [00102] A fortieth embodiment which is the method of any of the thirty-fourth to thirty-fifth embodiments wherein the titanium-containing compound is present in an amount of from about 0.1% by weight to about 10% by weight by total weight of the catalyst.
    [00103] A forty-first embodiment which is the method of any of the thirty-fourth to fortieth embodiments, wherein the chromium-containing compound comprises chromium(III) acetate hydroxide.
    [00104] A forty-second embodiment which is the method of any of the thirty-fourth to forty-first embodiments wherein the chromium-containing compound is present in an amount ranging from about 0.1% by weight to about 10% by weight by total weight of catalyst.
    [00105] A forty-third embodiment which is a method comprising a) drying a silica support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a chromium-containing compound to form a chrome support; c) contacting the chrome support with a solvent to form a paste support; d) cooling the slurry support to a temperature of less than about 50°C to form a cooled support; e) contacting the cooled support with a titanium-containing compound to form a titanized support; f) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; h) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and i) calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst
    [00106] A forty-fourth embodiment which is a method comprising a) drying a silica support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solvent to form a paste support; c) contacting the dried paste support with a chromium-containing compound to form a chrome support; d) subsequent to c) cooling the chrome support to a temperature of less than about 50°C to form a cooled support; e) contacting the cooled support with a titanium-containing compound to form a titanized support; f) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; g) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; h) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and i) calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst
    [00107] A forty-fifth embodiment which is a method comprising a) obtaining a chromium-silica-titania polymerization catalyst; b) slurrying the chromium-silica-titania catalyst in methanol, wherein the methanol contains less than 0.1% by weight of water to produce a slurry catalyst; c) cooling the slurry catalyst to a temperature of less than about 50°C to produce a cooled slurry catalyst; d) heat treating the cooled slurry catalyst by increasing the temperature of the cooled support to the boiling point of the solvent; e) before reaching the boiling point of the solvent, contacting the slurry support cooled with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; f) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and g) calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst
    [00108] A forty-sixth embodiment which is the method of the forty-fifth embodiment in which an amount of volatile organic compounds (VOC) emitted during calcination is reduced by about 50% to about 100% compared to the amount of VOC emitted during the calcination of an otherwise similar catalyst.
    [00109] A forty-seventh embodiment which is a method comprising a) drying a silica support material at a temperature in the range of about 150°C to about 220°C, to form a dry support; b) contacting the dry support with a solvent comprising a chromium-containing compound to form a chrome paste support; c) cooling the chrome slurry support to a temperature of less than about 50°C to form a cooled support; d) contacting the cooled support with a titanium-containing compound to form a titanized support; e) heat treating the titanized support by increasing the temperature of the titanized support to the boiling point of the solvent; f) before reaching the boiling point of the solvent, contacting the titanized support with water in an amount ranging from about 0.1 mol to about 10 mols per mol of titanium to produce a mixture; g) heat treating the mixture by heating the mixture to a temperature equal to or greater than about 150°C for a period of time from about 5 hours to about 30 hours to form a pre-catalyst; and h) calcining the pre-catalyst at a temperature in the range of about 400°C to about 1000°C for a period of time from about 30 minutes to about 24 hours to form a polymerization catalyst
    [00110] A forty-eighth embodiment which is the method of the first embodiment further comprising, prior to the completion of step (e), wherein the completion of step (e) results in the removal of methanol from the support, adding a chromium-containing compound to the support to form a pre-catalyst.
    [00111] A forty-ninth embodiment which is the method of the forty-eighth embodiment further comprising, before, during or after any one or more of steps (a) to (e) adding a chromium-containing compound to the support to form a pre-catalyst .
    [00112] While various embodiments have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the disclosure. The embodiments described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the disclosure disclosed in this document are possible and are within the scope of the disclosure. While numerical ranges or limitations are expressly stated, these expressed ranges and limitations should be understood to include iterative ranges or limitations of similar magnitude falling within the expressly stated ranges or limitations (e.g. from about 1 to about 10 includes 2, 3 , 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.) The use of the term "optionally" with respect to any element of a claim is intended to mean that the element in question is necessary, or alternatively, not necessary. Both alternatives are intended to be within the scope of the claim. The use of broader terms such as, comprises, includes, having, etc. is to be understood as providing support for narrower terms, such as, consisting of, essentially consisting of, substantially comprised of, etc.
    [00113] Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims that follow, that scope including all equivalents of the subject matter of the claims. Any and all claims are incorporated in the specification as an embodiment of the present disclosure. Thus, the claims are a further description and are additional to the embodiments of the present disclosure. Discussion of a reference in the disclosure is not an admission that it is prior art for the present disclosure, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural, or other details supplemental to those set forth herein.
    权利要求:
    Claims (12)
    [0001]
    1. Method characterized by comprising: a) drying a support material comprising silica at a temperature in the range of 150°C to 220°C to form a dry support; b) contacting the dry support with methanol to form a slurry support; c) subsequent to b), cooling the slurry support to a temperature of less than 60°C to form a cooled slurry support; d) subsequent to c), contacting the cooled slurry support with a titanium alkoxide to form a titanized support; e) heat treating the titanized support by heating to a temperature equal to or greater than 150°C for a period of time from 5 hours to 30 hours to remove the methanol and yield a dry titanium support, further comprising adding a chromium-containing compound before the complete removal of methanol to form a pre-catalyst, and further comprising adding water in an amount ranging from 0.1 to 10 mol per mol of titanium after the addition of the titanium alkoxide.
    [0002]
    Method according to claim 1, characterized in that it further comprises calcining the pre-catalyst at a temperature in the range of 400°C to 1000°C for a period of time from 30 minutes to 24 hours to form a polymerization catalyst. .
    [0003]
    3. Method according to claim 1, characterized in that the silica is dried for a period of time ranging from 5 hours to 24 hours and a weight loss on drying the dry support is less than 2% by weight.
    [0004]
    4. Method according to claim 1, characterized in that methanol is present in an amount ranging from 2 times to 3 times the weight of the dry support.
    [0005]
    5. Method according to claim 1, characterized in that the methanol has a water content of less than 0.1% by weight.
    [0006]
    6. Method according to claim 1, characterized in that the silica has a surface area from 250 m2/g to 1000 m2/g and a pore volume greater than 1.0 cm3/g.
    [0007]
    7. Method according to claim 1, characterized in that the titanium alkoxide comprises titanium n-propoxide.
    [0008]
    8. Method according to claim 1, characterized in that the titanium alkoxide is present in an amount from 0.1% by weight to 10% by weight by the total weight of the catalyst.
    [0009]
    9. Method according to claim 1, characterized in that the chromium-containing compound comprises basic chromium acetate.
    [0010]
    10. Method according to claim 1, characterized in that the chromium-containing compound is present in an amount from 0.1% by weight to 10% by weight by the total weight of the catalyst.
    [0011]
    11. Method according to claim 1, characterized in that an amount of volatile organic compounds (VOC) emitted during calcination at a temperature in the range of 400 °C to 1000 °C for a period of time of 30 minutes at 24 hours is reduced by 50% to 100% compared to the amount of VOC emitted during the calcination of an otherwise similar catalyst prepared without the addition of water.
    [0012]
    12. Method according to claim 1, characterized in that an amount of volatile organic compounds (VOC) emitted during calcination at a temperature in the range of 400 °C to 1000 °C for a period of time of 30 minutes at 24 hours is less than 2% by weight.
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    法律状态:
    2019-08-20| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/09/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/858,512|2015-09-18|
    US14/858,512|US10213766B2|2015-09-18|2015-09-18|Methods of preparing a catalyst|
    PCT/US2016/051902|WO2017048930A1|2015-09-18|2016-09-15|Methods of preparing a catalyst|
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