HUACUJA RAFAEL (US)
NETT ALEX J (US)
ROSEN MARI S (US)
EWART SEAN W (US)
STRONG GARRET (US)
GAO LIJUN (US)
WANG NICHOLAS (US)
DASILVA VANESSA (US)
GUIRONNET DAMIEN S (US)
SCOTT SUSANNA (US)
UNIV CALIFORNIA (US)
UNIV ILLINOIS (US)
CN105348557B | 2018-11-27 | |||
US20110021858A1 | 2011-01-27 |
CLAIMS 1. A process for converting saturated polyethylene to at least an alkene product of chemical formula CmH2m, the process comprising contacting the saturated polyethylene with three or more catalyst components in a reactor, the reactor comprising an alkene reactant of chemical formula CnH2n; where: m is an integer from 3 to 20 n is an integer from 2 to 20; the three or more catalyst components comprise a metathesis catalyst component, an isomerization catalyst component, and a dehydrogenation catalyst component; and contacting causes at least a portion of the saturated polyethylene to undergo dehydrogenation reactions to form unsaturated polyethylene and at least a portion of the unsaturated polyethylene, or products derived therefrom, to undergo metathesis reactions and isomerization reactions to produce an effluent comprising at least the alkene product of chemical formula CmH2m. 2. The process of any of the previous claims, wherein a pressure of the alkene reactant in the reactor during the contacting is from 0 pounds per square inch gauge (psig) to 3000 psig. 3. The process of any of the previous claims, wherein a temperature of the reactor during the contacting is less than or equal to 400 °C. 4. The process of any of the previous claims, wherein the alkene reactant comprises ethylene, propylene, butenes, pentenes, or combinations thereof. 5. The process of any of the previous claims, wherein the alkene product comprises propylene, butenes, pentenes, or combinations thereof. 6. The process of any of the previous claims, wherein the metathesis catalyst component comprises an element selected from International Union of Pure and Applied Chemistry (IUPAC) groups 5-10. 7. The process of any of the previous claims, wherein the metathesis catalyst component comprises rhenium, ruthenium, tungsten, molybdenum, vanadium, or combinations thereof. 8. The process of any of the previous claims, wherein the metathesis catalyst component comprises methyltrioxorhenium (MTO). 9. The process of any of the previous claims, wherein the isomerization catalyst component comprises an element selected from IUPAC groups 5-10. 10. The process of any of the previous claims, wherein the isomerization catalyst component comprises alumina, silica, iridium, palladium, ruthenium or combinations thereof. 11. The process of any of the previous claims, wherein the dehydrogenation catalyst component comprises an element selected from IUPAC groups 5-10. 12. The process of any of the previous claims, wherein the dehydrogenation catalyst component comprises platinum, iridium, ruthenium, rhenium, or combinations thereof. 13. The process of any of the previous claims, wherein a first catalyst composition comprises the metathesis catalyst component and the isomerization catalyst component, and wherein the first catalyst composition comprises MTO on alumina. 14. The process of any of the previous claims, wherein a second catalyst composition comprises the isomerization catalyst component and the dehydrogenation catalyst component, and wherein the second catalyst composition comprises platinum on alumina, platinum on silica, [tert- butyl-POCOP]Ir[C2H4] or combinations thereof. 15. The process of any of the previous claims, wherein a first catalyst composition comprising MTO on alumina and a second catalyst composition comprising platinum on alumina contact the saturated polyethylene in the reactor. |
[0029] In examples 8-10, catalytic processes according to the present disclosure were carried out in a batch reactor. Hydrocarbons in the gas fraction product (C1-C6) were analyzed quantitatively on a Shimadzu GC-2010 gas chromatograph equipped with a capillary column (Supelco Alumina Sulfate plot, 30 m x 0.32 mm) and a flame ionization detector (FID). The signal coefficient is dependent on the carbon number for each hydrocarbon species. The injector and detector temperatures were 200 °C. The temperature ramp program was as follows: 90 °C (hold 3 min), ramp 10 °C /min to 150 °C (hold 20 min). Helium was used as carrier gas. H 2 , C 2 H 4 , and C 2 H 6 were quantified on a Shimadzu GC-8AIT gas chromatograph equipped with a packed column (ShinCarbon ST 80/100, 2 m x 2 mm) and a thermal conductivity detector (TCD). The linear response of the TCD signal to the injected volumes of H2, C2H4, and C2H6 was confirmed using standard gas mixtures. The response factors were obtained as the slopes of fitted lines. The column, injector and detector temperatures were 130 °C. The TCD current was 70 mA and the carrier gas pressure was 300 kPa (N2). Liquid phase products (>C5) were analyzed on an Agilent 6890N Network Gas Chromatograph equipped with a DB-5 column and an FID detector. [0030] Example 1. Preparation of CH3ReO3/Cl-Al2O3 catalyst composition [0031] The catalyst composition of Example 1, 4 wt.% CH3ReO3/Cl-Al2O3, was synthesized using the following procedure: γ-Al 2 O 3 (Strem Chemicals, Inc.) was calcined at 550 °C in air for 4 hours (h), followed by evacuation at 450 °C under dynamic vacuum (10 -4 Torr) overnight. This partially dehydrated and dehydroxylated alumina was chlorinated in a stream of CCl4-saturated Ar (Airgas, UHP, 10 mL/min) in a fixed bed reactor at 300 °C for 1 h. CCl4 was distilled prior to use. The resulting Cl-Al 2 O 3 was evacuated at 450 °C overnight and modified with CH 3 ReO 3 (MTO, Sigma-Aldrich) by vacuum sublimation (ca. 10 −4 Torr) at room temperature to obtain a material containing 4 wt.% MTO and 4 wt.% Cl based on the total weight of the material. Periodically, the solid was shaken vigorously to promote uniform deposition of MTO. After grafting the MTO on the Cl-Al2O3, the catalyst was evacuated 30 min at room temperature to remove physisorbed material and the catalyst was stored in a N2-filled glovebox to prevent deactivation in air. [0032] Example 2. Preparation of 1.5% Pt/γ-Al 2 O 3 catalyst composition [0033] The catalyst composition of Example 2, 1.5% Pt/γ-Al2O3, was synthesized using the following procedure: γ-Al2O3 (Strem Chemicals, Inc., 186 m 2 g -1 , pore volume 0.50 cm 3 g -1 ) was calcined in air at 500 °C for 4 h, followed by evacuation (10 −4 Torr) at 450 °C for 12 h. Volatile trimethyl(cyclopentadienyl)platinum (32 ± 1 mg) was deposited onto dry alumina (1.300 ± 0.020 g) by vacuum sublimation (ca. 10 −4 Torr) at room temperature to obtain materials with 1.5 wt% Pt. The reactor was shaken vigorously during the procedure to promote uniform deposition followed by evacuation at room temperature for 1 h to remove physisorbed PtCp(CH3)3. The resulting solid was reduced in flowing H2 (4.0% in Ar, 30 mL/min) as the temperature was ramped to 250 °C at a rate of 2 °C/min. The material was held at this temperature for 2 h, then cooled to room temperature and evacuated for 15 min. The reduced catalyst was stored in a N 2 -filled glovebox until use to avoid re-oxidation in air. [0034] Example 3. Preparation of 1.5% Pt/Cl-Al2O3 catalyst composition [0035] The catalyst composition of Example 3, 1.5% Pt/Cl-Al 2 O 3 , was synthesized using the following procedure: γ-Al2O3 (Strem Chemicals, Inc., 186 m 2 g -1 , pore volume 0.50 cm 3 g -1 ) was calcined in air at 500 °C for 4 h. 1.5 g of calcined alumina was impregnated with 0.6 ml aqueous solution containing 45.0 mg of Pt(NH 3 ) 4 (NO 3 ) 2 and 46 mg HCl (from concentrated HCl), followed by drying in the oven at 80 °C for 2 h and calcination at 500 °C for 3 hours under static air, with a ramp rate of 2 °C/min. The resulting material was then reduced under H2 (5.0% in Ar, 30 mL/min) 280 °C for 2 hours, with a ramp rate of 2 °C/min, which was followed by evacuation under ca. 10 -4 Torr at room temperature for 30 minutes. The reduced catalyst was stored in a N 2 - filled glovebox until use to avoid re-oxidation in air. [0036] Example 4. Preparation of 1.5% Pt/SiO2 catalyst composition [0037] The catalyst composition of Example 4, 1.5% Pt/SiO 2 , was synthesized using the following procedure: 1.5 g of calcined SiO2 (Sylopol 952) was impregnated with 1.5 mL of an aqueous solution containing 45.0 mg of Pt(NH3)4(NO3)2, followed by drying in the oven at 80 °C overnight and calcination at 350 °C for 3 hours under static air, with a ramp rate of 2 °C/min. The resulting material was then reduced under 5.0% H2/Ar at 280 °C for 2 hours, with a ramp rate of 2 °C/min, which was followed by evacuation under ca. 10 -4 Torr at room temperature for 30 minutes. The catalyst comprising 1.5 wt.% Pt was stored in a N 2 -filled glovebox until use to avoid re-oxidation in air. [0038] Example 5. Preparation of Re2O7/γ-Al2O3 catalyst composition [0039] The catalyst composition of Example 5, Re2O7/γ-Al2O3, was synthesized using the following procedure: Re 2 O 7 /γ-Al 2 O 3 was prepared by incipient wetness impregnation of γ-Al 2 O 3 (Strem Chemicals, Inc.) with ammonium perrhenate to obtain a material containing 10 wt.% Re. Prior to impregnation, γ-Al2O3 was calcined at 550 °C for 4 h within 2 h. After impregnation, the dried material was activated by calcination in oxygen at 650 °C at 5 °C/min for 8 h. The calcined catalyst was stored in a N 2 -filled glovebox until use to avoid deactivation in air. [0040] Example 6. Preparation of PtRe/SiO 2 catalyst composition [0041] The catalyst composition of Example 6, PtRe/SiO2, was prepared using the following procedure: PtRe/SiO2 was prepared by incipient wetness impregnation of silica powder with ammonium perrhenate to obtain a material containing 1-5 wt% Re. After impregnation, the material was calcined at 500 °C. Pt was deposited on the material by incipient wetness impregnation in toluene with platinum acetylacetonate to obtain a material containing 1-5 wt% Pt. The resulting solid was dried in air at 120 °C for 4 h after which the temperature was increased to 210 °C for 4 h. The material was reduced in H2 at 150 °C for 1 h. The reduced catalyst was stored in a N2 atmosphere until use to avoid re-oxidation in air. The PtRe/SiO2 catalyst was calcined at 500 o C for 4 h followed by reduction with H 2 at 280 o C for 2 h. The heating rate is 2 o C/min. After reduction, the catalyst was evacuated 30 min at room temperature to remove physisorbed H 2 and stored in N2-filled glovebox to prevent deactivation in air. [0042] Example 7. Preparation of [ tBu POCOP]Ir[C2H4] catalyst composition [0043] The catalyst composition of Example 7, [ tBu POCOP]Ir[C 2 H 4 ], was prepared according to “Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis” Science 2006, 312, 257-261. [C6H3-2,6-[OP(t-Bu)2]2]Ir[H][Cl] and NaO-t-Bu were weighed into an oven- dried Schlenk flask in a molar ratio of 1 to 1.2, respectively. The solids were then put under a flow of argon. 40 mL of toluene was added to the flask via syringe, and the resulting suspension was stirred for 10 min at room temperature. Ethylene was bubbled through the solution for 1-2 hours. The solution was cannula-filtered through a pad of Celite, volatiles were evaporated under vacuum, and the resulting red solid was dried under vacuum overnight to afford the product in 60% yield. [0044] Example 8. Catalytic conversion of saturated polyethylene in a batch reactor to form alkenes [0045] In Example 8, saturated polyethylene was reacted with ethylene over the catalysts of Example 2 and Example 5 in a 25 mL batch reactor (Parr reactor, Series 4590). In an N2-filled glovebox, 199 mg of Example 5, 199 mg of Example 2, and 120 mg of saturated polyethylene were loaded into a 25 mL reactor equipped with a pressure gauge and type K thermocouple. Ethylene (99.999 %, Airgas) was passed through a moisture/oxygen trap (Supelco) before use. Gas lines were purged of residual air for three 5-min cycles before ethylene was introduced into the reactor. After pressurization, the total pressure was 40 bar. Reactor heating was initiated, and reaction time was tracked after reaching a desired temperature of 200 °C. After a reaction time of 24 hours, the reactor was cooled in flowing air. Aliquots of gas from the reactor headspace were taken for GC analysis before venting the rest of the headspace in a fume hood. The remaining solid and liquid was transferred onto a fine glass filter (4.0-5.5 µm) and filtered to remove insoluble material by washing with hot (50 °C) CHCl3. Soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 Torr). The insoluble material, including the catalyst and hydrocarbons insoluble in hot CHCl 3 , was recovered from the filter. The results of the products formed in Example 8 are shown in Table 2. Table 2 [0046] Example 9. Catalytic conversion of saturated polyethylene in a batch reactor at varied reaction times to form alkenes [0047] In example 9, saturated polyethylene was reacted with ethylene over a first catalyst composition (CC 1) and a second catalyst composition (CC 2) in a 10 mL batch reactor (Parr reactor, Series 2500) according to Table 3. The reaction time was varied. In an N2-filled glovebox, the first catalyst composition, the second catalyst composition, and the saturated polyethylene were loaded into a Parr 2500 reactor equipped with a pressure gauge and type J thermocouple. 28 psi of argon was added as an internal standard. Ethylene (99.999 %, Airgas) was passed through a moisture/oxygen trap (Supelco) before use. Gas lines were purged of residual air for three 5-min cycles before ethylene was introduced into the reactor. Reactor heating was initiated, and reaction time was tracked after the desired temperature setpoint of 200 °C was reached. After the designated reaction time, the reactor was cooled in flowing air. Aliquots of gas from the reactor headspace were taken for GC analysis before venting the rest of the headspace in a fume hood. The remaining solid and liquid was transferred onto a fine glass filter (4.0-5.5 µm) and filtered to remove insoluble material by washing with hot (50 °C) CHCl 3 . Soluble hydrocarbons were recovered by evaporating the solvent under reduced pressure (0.1 Torr). The insoluble material, including the catalyst and hydrocarbons insoluble in hot CHCl3, was recovered from the filter. The results of the products formed in Examples 9A, 9B, and 9C are shown in Table 4. Table 3 Table 4 [0048] Example 10. Catalytic conversion of n-octadecane over various catalyst compositions in a batch reactor at varied reaction times and reaction temperatures to form alkenes [0049] In example 10, n-octadecane was reacted with ethylene over two catalyst compositions in a batch reactor (Parr reactor, Series 2500) according to Table 5. In an N2-filled glovebox, a first catalyst composition (CC 1), a second catalyst composition (CC 2), and n-octadecane were loaded into a 10 mL reactor (Parr 2500) equipped with a pressure gauge and type J thermocouple. Ethylene (99.999 %, Airgas) was passed through a moisture/oxygen trap (Supelco) before use. Gas lines were purged of residual air for three 5-min cycles before ethylene was introduced into the reactor. Reactor heating was initiated, and reaction time was tracked after the desired temperature setpoint was reached. After the designated reaction time, the reactor was cooled in flowing air. Aliquots of gas and liquids from the reactor headspace were taken for gas chromatography analysis with a flame ionization detector (GC-FID). The results of the products formed in Examples 10A-D and 10E-H are shown in Table 6 and Table 7, respectively. Table 5 *Ethylene was added in Example 10H at a measured mass. Table 6 Table 7 [0050] Example 11. Catalytic conversion of saturated polyethylene in a flow reactor to form alkenes [0051] In Example 11, a flow reactor was used, as shown in FIG 1. A 20 mL glass reaction sleeve (ID=19.56 mm, OD=22.15 mm) was placed into a 40 mL stainless-steel stirred-tank reactor (ID=22.16 mm, OD=40 mm), and the reactor was housed within an aluminum heating jacket. The temperature of the heating jacket was controlled by a hotplate and thermocouple (IKA C-MAG HS7 digital). The reactor has two inlet ports, one for liquid substrates and a second for gaseous substrates. Liquid substrates were delivered into the setup using a Hamilton gas-tight syringe (5 mL) and a Kd Scientific Legato 100 Syringe Pump. Gaseous substrates were supplied from a pressurized tank whose flow was set by an Alicat mass flow controller (MCS series). The outlet stream led to an Equilibar backpressure regulator which was used to control the reaction pressure. Attached downstream from the regulator was an Agilent 6850 gas chromatograph (GC). The GC was equipped with a 6-port VICI-Valco gas-sampling valve. A continuous flow of ethylene was used as an internal standard to quantify olefin formation rates. Stainless-steel tubing and fittings were purchased from McMaster-Carr and Swagelok. The GC was equipped with an FID and a Petrocol DH Capillary GC Column (100mm x 0.25mm x 0.5 μm film thickness). The column was held at 45 PSI and the gaseous sample was split 50:1. The column conditions and product elution times are shown in Table 8 and Table 9, respectively. Table 8 Table 9 [0052] Within an Ar-filled glovebox, 249 mg of saturated polyethylene, 146 mg of Example 1, and 36.6 mg of Example 7 were loaded into a stirred-tank reactor. After loading, the reactor was removed from the glovebox, placed within an aluminum heating jacket, and connected to an ethylene delivery source. The Ar-atmosphere within the reactor was evacuated using a continuous flow of ethylene fed at 5 mL/min for at least 15 minutes. For 19.5 hours, ethylene gas (10.1 mL/min) was continuously flown into the reactor which was heated to and held at 130 °C and 1 atm. To monitor reaction progression, a sample of the gaseous effluent (0.25 mL) was analyzed via GC every 34.2 minutes for the 19.5-hour duration of the reaction. The results of Example 11 are shown in Table 10. The maximum propylene formation rate detected while catalyst is on- stream (RC3, max), in millimoles per hour (mmol h -1 ), was measured. The maximum propylene selectivity (SC3, max) while the catalyst was on-stream was measured. The formation rate of propylene is normalized by the cumulative olefin formation rate for a given reaction time. The average of the selectivity of propylene (S C3 , avg ) and butylene (S C4,avg ) were evaluated at each sampling point during the course of the continuous reaction for each species. The polyethylene conversion, in weight percent, was also estimated by calculating the mass of polyethylene consumed per olefin produced, according to equation 1: where i represents the number of carbon units within the olefin, MW i represents the molecular weight of species “i”, nci is the moles of species “i” formed during the experiment, and mPE,o is the initial loading of polyethylene, assuming each molecule of olefin formed contains two carbons from ethylene. Table 10 [0053] It is noted that one or more of the following claims utilize the term “where” or “in which” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” For the purposes of defining the present technology, the transitional phrase “consisting of” may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of” may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non- recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of” and “consisting essentially of” may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of” and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of” components A, B, and C as well as a composition “consisting essentially of” components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of” and “consisting essentially of.” [0054] As used in the Specification and appended Claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced. [0055] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of one or more embodiments does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.
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