Catalysts and methods for dimerizing propylene

Abstract

A catalyst for producing branched aliphatic alkenes is described. The catalyst may comprise a catalytic alkali metal or alkali metal complex on a mixed metal oxide support comprising a first row metal and at least one of a third row metal, a fourth row metal, or a lanthanide. The catalyst may have less than 50 wt. % metal carbonate. A method for producing branched aliphatic alkenes by contacting the catalyst of the present invention with an aliphatic alpha-olefin is also described.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority under U.S. Provisional Application No. 62 / 696,504, filed on 11 July 2018, which is incorporated herein by reference in its entirety.

[0002] A. Field of Invention The present invention relates to a method for producing branched aliphatic alkenes via a dimerization reaction. In particular, the present invention relates to producing branched aliphatic alkenes by reacting a feed stream containing an aliphatic alphaolefin with a supported alkali metal or alkali metal composite catalyst. The catalyst support may include a mixed metal oxide comprising a first-row metal and at least one third-row metal, fourth-row metal, lanthanide metal, or any combination thereof. [Background technology]

[0003] B. Description of related technologies Catalysts for the dimerization of α-olefins are known. For example, industrially viable routes to products produced from the dimerization of propylene (e.g., 4-methyl-1-pentene) with high selectivity include the use of potassium metal and potassium carbonate, or specially designed metallocene catalysts. One such example is U.S. Patent No. 4,774,215 by Drake et al. (Patent Document 1). This patent describes a catalyst comprising an alkali metal and a segmented glass on an alkali metal carbonate support with any metal oxide in which the metal oxide to alkali metal carbonate ratio is 1:1 to 1:10. Another example is U.S. Patent No. 6,262,325 by Narbeshuber et al. (Patent Document 2), which describes a catalyst for the side-chain alkylation or alkenylation of alkyl aromatic or alkyl alicyclic compounds by olefins or diolefins. In particular, this patent uses a catalyst having an alkali metal on a support containing a divalent metal disposed on a Ti, Zr, Hf, or TiZr oxide material. The selectivity of the catalyst for methylpentene was less than 40%. In yet another example, Hasselbring's U.S. Patent No. 5,105,049 (Patent Document 3) describes a dimerization catalyst containing an alkali metal on an alkali metal carbonate support.

[0004] Alkali metals on carbonate catalysts exhibit high selectivity for side-chain reactions of methylpropene or aromatic compounds, but they have the disadvantages of relatively long induction times (e.g., 10 hours or more) and the potential for structural degradation during use. Furthermore, the use of metallic potassium can severely limit the properties of the support material. Potassium metal exhibits strong reducing and reactivity with many typical support materials (e.g., converting alumina to potassium aluminate and silica to potassium silicate). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 4,774,215 [Patent Document 2] U.S. Patent No. 6,262,325 [Patent Document 3] U.S. Patent No. 5,105,049 [Overview of the project]

[0006] Discoveries have been made to address at least some of the problems associated with catalysts used in the dimerization of olefins to produce hydrocarbons with a higher number of carbon atoms (e.g., the production of branched aliphatic alkenes by dimerization of aliphatic alpha-olefins). This solution presupposes the use of alkali metals supported on a mixed metal oxide support to convert aliphatic alpha-olefins to branched aliphatic alkenes. The mixed metal oxide comprises a first-row metal and at least one of a third-row metal, a fourth-row metal, or a lanthanide metal. The support contains less than 50 wt% of metal carbonate (e.g., 0 to less than 49 wt% of K2CO3).

[0007] One aspect of the present invention describes a method for producing a branched aliphatic alkene. The method may include reacting a feed stream containing an aliphatic alpha-olefin (e.g., an olefin having 1 to 5, 2 to 4, or about 3 carbon atoms) with a supported alkali metal or alkali metal composite catalyst to produce a branched aliphatic alkene (e.g., a branched aliphatic alkene having 4 to 10, preferably 4 to 8, more preferably 6 carbon atoms, more preferably 4-methyl-1-propene). The feed stream may contain propylene, optionally ethylene, saturated hydrocarbons, or mixtures thereof. The support material may include a mixed metal oxide comprising a first-row metal (e.g., sodium (Na), potassium (K), and cesium (Cs), preferably K), at least one third-row metal (e.g., scandium (Sc) or yttrium (Y), preferably Y), a fourth-row metal (e.g., titanium (Ti), zirconium (Zr), hafnium (Hf), preferably Zr), or a lanthanide oxide (e.g., lanthanum (La), cerium (Ce), promethium (Pm), or praseodymium (Pr), preferably La) or a composite thereof. The support may contain less than 50% by weight of metal carbonates. The alkali metal may be Na, K, Cs, or a composite or mixture thereof. In one example, the alkali metal is K. In another example, the alkali metal is a NaK composite or amalgam. The catalyst may contain alkali metals in an amount of 0.1–10% by weight, preferably 1–9% by weight, more preferably 3–8% by weight, and all ranges and values ​​in between. In some cases, the catalyst may be a K metal supported on sodium yttriate, potassium zirconate, or a mixture thereof. In another example, the catalyst may be a NaK metal composite supported on sodium yttriate, potassium zirconate, or a mixture thereof. The support material may be macroporous (pores with a diameter greater than 50 nanometers (nm)), mesoporous (pores with a diameter of 2 nm to 50 nm), or microporous (pores with a diameter of less than 2 nm), or a combination thereof. In some cases, the catalyst may have an average particle diameter of 100–600 microns, an average pore volume of 0.03–0.30 mL / g, or both.Reaction conditions may include temperature, pressure, liquid-space velocity (LHSV), or a combination thereof. The reaction temperature may be in the range of 120°C to 200°C, more preferably 140°C to 170°C. The reaction pressure may be in the range of 5 MPa to 10 MPa. The LHSV range is 0.1 h. -1 ~2h -1 The range may be as follows. In some embodiments, the dimerization reaction is carried out in a reaction system including a pressurized reactor. Preferably, the pressurized reactor is a fixed-bed reactor with a cooling jacket. In some aspects, the reaction system may include two or more reactors, preferably two to five, operating in parallel. Catalysts in two or more reactors may have different activity levels. In some cases, at least one of the two or more reactors may be in regeneration mode, in which the reactor is not operating to produce branched aliphatic alkenes while the catalyst is being regenerated. In some embodiments, the reaction system may include a first and second reactor operating in series and may include a separation column located downstream of the first reactor and upstream of the second reactor. The separation column may be configured to separate branched aliphatic alkenes and their isomers from the effluent of the first reactor to produce an inlet flow for the second reactor. In certain examples, the catalyst is a potassium metal or NaK complex on sodium zirconate, and the selectivity for branched aliphatic alkenes may be at least 92% after 6 hours. In some embodiments, the catalyst may be a NaK complex on potassium zirconate, and the selectivity for branched aliphatic alkenes can be at least 97%.

[0008] In yet another example, a catalyst for generating branched aliphatic alkenes is described. The catalyst may include a potassium (K) metal or NaK metal complex on a metal oxide support containing a mixed metal oxide of a first-row metal and at least a third-row metal, a fourth-row metal, a lanthanide metal, or a composite thereof, and the catalyst has less than 50% by weight of carbonate.

[0009] Other aspects of the present invention are discussed throughout this application. Any aspect discussed in relation to one aspect of the present invention is applicable to other aspects of the present invention, and vice versa. Each aspect described herein is understood to be an aspect of the present invention applicable to other aspects of the present invention. Any aspect discussed herein can be implemented in relation to any method or composition of the present invention, and vice versa. Furthermore, the methods of the present invention can be achieved using the compositions and kits of the present invention.

[0010] The following are definitions of various terms and phrases used throughout this specification.

[0011] Aliphatic compounds are acyclic or cyclic, saturated or unsaturated carbon groups, excluding aromatic compounds. Linear aliphatic groups do not contain tertiary or quaternary carbons. Branched aliphatic groups contain at least one tertiary and / or quaternary carbon. Cyclic aliphatic groups contain at least one ring in their structure. Polycyclic aliphatic groups may include condensed groups, e.g., decalin, and / or spiro groups, e.g., spiro[5.5]undecane, and polycyclic groups.

[0012] The terms “about” or “approximately” are defined as being close to what is understood by those skilled in the art. In one non-limiting embodiment, the terms are defined as being within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0013] The terms "weight %", "volume %", and "mol %" refer to the weight percentage, volume percentage, or mole percentage of an ingredient, respectively, based on the total weight, volume, or total number of moles of the ingredient. In a non-restrictive example, 10 grams of an ingredient in 100 grams of material constitutes 10 weight percent of the ingredient.

[0014] The term "substantially" and its variations are defined to include ranges of 10%, 5%, 1%, or 0.5%.

[0015] When used in the claims and / or the specification, the terms "inhibit" or "reduce" or "prevent" or "avoid", or any variation of these terms, include a measurable decrease or complete inhibition to achieve the desired result.

[0016] The term "effective", when used in the specification and / or the claims, means appropriate to achieve the desired, expected, or intended result.

[0017] When used in combination with any of the terms "comprising", "including", "containing", or "having" in the claims or the specification, the use of the term "a" or "an" may mean "one", but is also consistent with the meaning of "one or more", "at least one", "one or more than one".

[0018] "Comprising" (and any form of "comprising" such as "comprise", "comprises", etc.), "having" (and any form of "having" such as "have", "has", etc.), "including" (and any form of "including" such as "includes", "include", etc.) or "containing" (and any form of "containing" such as "contains", "contain", etc.) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0019] The methods and catalysts of the present invention may “contain,” “essentially consist of,” or “consist of” certain components, elements, compositions, etc., disclosed throughout this specification. In one non-limiting context, with respect to the transitional phrase “essentially consist of,” a fundamental and novel feature of the catalysts and methods of the present invention is their ability to catalyze the dimerization of olefins (e.g., from propylene to 4-methylpentene (4M1P)).

[0020] Other objects, features, and advantages of the present invention will become apparent from the following figures, detailed description, and examples. However, it should be understood that the figures, detailed description, and examples illustrate certain aspects of the present invention, but are given only as examples and are not intended to limit it. Furthermore, changes and modifications within the spirit and scope of the present invention are intended to become apparent to those skilled in the art from this detailed description. In further embodiments, features from a particular embodiment can be combined with features from other embodiments. For example, features from one embodiment can be combined with features from any of the other embodiments. In further embodiments, additional features can be added to the particular embodiments described herein. [Brief explanation of the drawing]

[0021] The advantages of the present invention may become apparent to those skilled in the art from the advantages described in the following detailed description and from reference to the accompanying drawings.

[0022] [Figure 1A] Figures 1A to 1C show schematic diagrams of a system for carrying out the method of the present invention. Figure 1A shows a schematic diagram of a system including a single reactor containing a catalyst for catalyzing the dimerization of olefins. [Figure 1B] Figures 1A to 1C show schematic diagrams of a system for carrying out the method of the present invention. Figure 1B shows a schematic diagram of a system including two parallel reactors containing catalysts for catalyzing the dimerization of olefins. [Figure 1C]Figures 1A to 1C show schematic diagrams of a system for carrying out the method of the present invention. Figure 1C shows a schematic diagram of a system including two reactors, each containing a catalyst for catalyzing the dimerization of an olefin, wherein unreacted olefins in the effluent from the first reactor are supplied to the second reactor. [Figure 2] This is an X-ray diffraction (XRD) image of the potassium zirconate support material of the present invention. [Figure 3] This is the XRD of the sodium yttriumate support material of the present invention.

[0023] While various modifications and alternative forms are possible for this invention, specific embodiments are shown in the drawings as examples. The drawings may not be to a constant scale. [Modes for carrying out the invention]

[0024] Detailed description of the invention A discovery has been made that provides solutions to at least some of the problems associated with using carbonates as support materials for dimerization reactions. This discovery is based on the idea of ​​reacting a feed stream containing a reactive olefin with a catalyst alkali metal on a mixed metal oxide support containing less than 50 wt% carbonate material. The use of such a catalyst provides a more efficient catalyst generation method, improved induction time (e.g., minutes instead of hours), and improved structural properties (e.g., the catalyst does not disintegrate or degrade over time). The support may comprise a first-row metal oxide and at least one of a third-row metal oxide, a fourth-row metal oxide, a lanthanide oxide, or a composite thereof. When used to dimerize propylene, the catalyst may have at least 95% selectivity for 4-methyl-1-pentene. The catalyst may be macroporous, mesoporous, or microporous, or a combination thereof. In some embodiments, the catalyst may be 100-600 microns, or At least 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, 550 microns, and 600 microns, Equivalent to 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, 550 microns, and 600 microns, or Between any two of the following: 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, 550 microns, and 600 microns The average particle diameter may be 0.03~0.30 mL / g, or At least 0.3 mL / g, 0.5 mL / g, 1 mL / g, 1.5 mL / g, 2 mL / g, 2.5 mL / g, and 3 mL / g, Equivalent to 0.3 mL / g, 0.5 mL / g, 1 mL / g, 1.5 mL / g, 2 mL / g, 2.5 mL / g, and 3 mL / g, or Any two of the following: 0.3 mL / g, 0.5 mL / g, 1 mL / g, 1.5 mL / g, 2 mL / g, 2.5 mL / g, and 3 mL / g It may have an average pore volume of [value missing].

[0025] These and other non-limiting aspects of the present invention will be discussed in further detail in the following paragraphs.

[0026] C. Catalyst 1. Support material The support material may be a mixed metal oxide containing first-row metal oxides and / or third-row, fourth-row metal oxides, and lanthanide oxides, or mixtures or composites thereof. Non-limiting examples of first-row metals include Na, K, and Cs. Non-limiting examples of third-row, fourth-row, and lanthanides include scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), lanthanum (La), cerium (Ce), promethium (Pm), or praseodymium (Pr). The support may also contain bicarbonates (HCO3) and metallic carbonates. The amount of carbonate may range from 0.0% by weight to a maximum of 49% by weight, or 49% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, 5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, and less than 0.0% by weight, Equivalent to 49% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, 5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, and 0.0% by weight, or Between 49% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, 5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, and 0.0% by weight. The remainder is an oxide material (e.g., first row, third row, fourth row, or lanthanide oxide). In some cases, the prepared support may contain 0.0 to 35% by weight of a metal precursor (e.g., nitrate, carbonate, etc.) used to make the support. Non-limiting examples of support materials include potassium zirconate, potassium yttriate, etc. Potassium zirconate may contain one or more active phases. Non-limiting examples of active phases include K2Zr8O 17 (Powder Diffraction File (PDF) 00-014-0021), Orthogonal K2ZrO3 (PDF 00-018-1046), Hexagonal or Orthogonal K2Zr2O5 (PDF 00-020-0960), Tetragonal K2Zr3O7 (PDF 00-020-0960), Hexagonal K4Zr 11 O 24 (PDF 00-030-1021), triclinic K4ZrO4 (PDF 00-031-1142), and hexagonal K4Zr5O 12(PDF 00-052-0353, PDF 01-071-1857, etc. are included.) Although I do not wish to be bound by theory, the main crystal structure is K4Zr5O 12 It is thought to be similar to K4Zr5O 12 It has a perovskite-like crystalline structure of potassium ions coordinated as cuboctahedrons, with zirconium ions inserted between the third and fourth layers as hexagonal rings. Other crystalline structures of potassium zirconate may also exist (see, for example, the characterization of supports in the paragraph of non-limiting examples).

[0027] Sodium yttriate may contain one or more phases. Non-limiting examples of sodium yttriate phases include cubic NaYO2 (PDF 00-032-1203), monoclinic NaYO2 (PDF 01-070-1422), or mixtures of these two. In the case of non-stoichiometric sodium yttriate, the entire solid is a complex made up of sodium yttriate phases, and excess elements can take the form of sodium oxide or yttrium oxide.

[0028] Support materials can be prepared using known metal oxide support synthesis methodologies or as shown in a non-limiting manner in the examples. Non-limiting examples of preparation methods include coprecipitation, solid-state chemistry, sol-gel chemistry, molten salt chemistry, flame spray pyrolysis, hot water spray and freeze-drying, precursor impregnation, or combinations thereof. In some embodiments, a method for preparing a support may involve coprecipitation of a metal precursor (e.g., nitrates, chlorides, acetates, carbonates, sulfates) in a protic solvent using a precipitating agent such as sodium hydroxide, lithium hydroxide, ammonium hydroxide, or carbonates or bicarbonates. The resulting solid can then be filtered, dried, and calcined at a predetermined temperature. In another embodiment, support materials can be prepared using solid-state chemistry methodologies. These methodologies may involve grinding or pulverizing solid powders of metal oxides, metal carbonates, and / or metal bicarbonates at high energy for a predetermined time. The resulting solid can then be calcined at a predetermined temperature. Another preparation method may involve sol-gel chemistry. Sol-gel chemistry may involve dissolving a metal precursor (e.g., nitrates, chlorides, acetates, carbonates, sulfates) in a protic solvent and reacting the salt with an organic compound (e.g., a carboxylic acid or amine) in the first step to form an organometallic complex. The organometallic complex can be heated to promote polymerization and evaporate the solvent. The resulting gel can then be dried and calcined to a predetermined temperature. Support materials can also be prepared using the molten salt method. In this method, third- and / or fourth-column metal nitrates and / or lanthanides can be mixed with first-column metal nitrites of the periodic table. The reaction between the two solids can produce a highly exothermic reaction, which results in a molten state from which the desired mixed metal oxide can be produced. In some embodiments, the support material may contain up to 60% by weight of precursors used to prepare the support material.

[0029] In the above methodology, the baking temperature is in the range of 600°C to 1200°C, 800°C to 1100°C, or At least 600 °C, 650 °C, 700 °C, 750 °C, 800 °C, 850 °C, 900 °C, 950 °C, 1000 °C, 1050 °C, 1100 °C, 1150 °C, and 1200 °C, equal to 600 °C, 650 °C, 700 °C, 750 °C, 800 °C, 850 °C, 900 °C, 950 °C, 1000 °C, 1050 °C, 1100 °C, 1150 °C, and 1200 °C, or between any two of 600 °C, 650 °C, 700 °C, 750 °C, 800 °C, 850 °C, 900 °C, 950 °C, 1000 °C, 1050 °C, 1100 °C, 1150 °C, and 1200 °C it can be.

[0030] The support material can be formed into various forms (e.g., tablets, leaves, spheres, etc.). As an example, the support can be formed into a cylindrical tablet (open or closed) by direct compression using known tableting methods. The support material can be mixed with a binder (e.g., stearic acid) and / or a lubricant (e.g., graphite). In other embodiments, the support material can be formed into a three - or four - leaf form using extrusion techniques. As an example, the carrier can be mixed with a solvent (e.g., water or alcohol), a binder (e.g., starch, cellulose, etc.), and a surfactant to form a paste that can flow freely through the die of an extruder.

[0031] 2. Catalytic Metal The catalyst can include a catalytic alkali metal or a complex thereof. Non - limiting examples of alkali metals include sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Non - limiting examples of alkali metal complexes include NaK, NaCs, NaRb, KRb, KCs, and RbCs. In some embodiments, the catalytic alkali metal is K or a NaK complex. Na 23 K 77 - eutectics are available from commercial sources.

[0032] The catalyst of the present invention may contain up to 10% by weight of the metal, which may range from 0.01% to 10% by weight, or 0.3% to 3% by weight, and all of the weight, or At least 0.01% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, and 10% by weight, Equivalent to 0.01% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, and 10% by weight, or Any two of the following: 0.01% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, and 10% by weight. That is the case.

[0033] Catalyst metals can be combined with support materials using solution impregnation or molten state impregnation methodologies, or as shown in a manner not limited to the examples. In solution impregnation, alkali metal precursors (e.g., nitrates, carbonates, sulfates, chlorides) can be impregnated into the support material using dry (solvent-free) or wet (solvent-inclusive) techniques. The resulting solid can be dried and calcined to a predetermined temperature. In aspects of the present invention, catalyst metals can be coated onto the support material via chemical vapor deposition (MOCVD). Prior to the reaction, the catalyst can be exposed to hydrogen to ensure that the catalyst metal remains in a metallic state, as some oxidation occurs during calcination. In molten state impregnation, alkali metals or mixtures thereof can be impregnated at 25°C to 125°C, or 50°C to 100°C, or At least 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, and 125°C, Equivalent to 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, and 125°C, or Between any two of the following temperatures: 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, and 125℃ The molten metal can be heated to a molten state at a certain temperature. Next, the molten metal can be added to a molded support in transit to provide a uniform dispersion of the molten metal on the support.

[0034] D. Method for generating branched aliphatic alkenes Sufficient conditions for the formation of branched aliphatic alkenes (e.g., 4-methyl-1-pentene) include temperature, time, aliphatic alpha-olefin concentration, space velocity, and pressure. The temperature range for the formation of branched aliphatic alkenes is approximately 120°C to 200°C, or 140°C to 170°C, or At least 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and 200°C, Equivalent to 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and 200°C, or Between 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and 200°C This is possible. The liquid space velocity (LHSV) of the reactant feed is 0.1h -1 Faster, or 0.1-2 hours -1 It is possible. The conversion of aliphatic alphaolefins can be performed at 5 MPa to 10 MPa, or At least 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, and 10 MPa, Equivalent to 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, and 10 MPa, or Between any two of the following: 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, and 10 MPa This can be carried out at a pressure of [specify pressure]. The conditions for branched aliphatic alkene formation may be varied depending on the type of reactor.

[0035] The reactions of the methods and systems disclosed herein may occur in fixed-bed processes or reactors, plug-flow reactors, circulating catalytic-bed processes or reactors, or batch reactors. The methods and systems may further include producing petrochemicals or polymers using the resulting branched aliphatic alkenes, and collecting or storing the resulting branched aliphatic alkene products.

[0036] Referring to Figure 1A, a system 100 is shown that can be used to convert aliphatic alphaolefins to branched aliphatic alkenes using the mixed metal oxide-supported alkali metal catalyst of the present invention. System 100 may include a feed source 12 containing aliphatic alphaolefins and optional ethylene, a first reactor 13, an effluent separation column 14, and a product purification fractionation column 15. System 100 may further include one or more standby reactors 19 in a regeneration mode or standby mode, in which the catalyst of the standby reactor 19 is regenerated, while the first reactor 13 is operating to convert aliphatic alphaolefins to branched aliphatic alkenes. The feed source 12 may be in fluid communication with the first reactor 13 via a reactor inlet (not shown). The aliphatic alphaolefin source may be configured to regulate the amount of aliphatic alphaolefin feed entering the first reactor 13.

[0037] The aliphatic alpha-olefin feed stream (e.g., olefins with 1-5, 2-4, or approximately 3 carbon atoms) can be obtained from other process units and / or commercial sources. The aliphatic alpha-olefin feed stream should be at least 50 vol% or 82-95 vol% or 88-92 vol% or 50 vol%, 51 vol%, 52 vol%, 53 vol%, 54 vol%, 55 vol%, 56 vol%, 57 vol%, 58 vol%, 59 vol%, 60 vol%, 61 vol%, 62 vol%, 63 vol%, 64 vol%, 65 vol%, 66 vol%, 67 vol%, 68 vol%, 69 vol%, 70 vol%, 71 vol%, 72 vol%, 73 vol%, 74 vol%) The feed stream may contain aliphatic alpha-olefins in product %, 75 vol%, 76 vol%, 77 vol%, 78 vol%, 79 vol%, 80 vol%, 81 vol%, 82 vol%, 83 vol%, 84 vol%, 85 vol%, 86 vol%, 87 vol%, 88 vol%, 89 vol%, 90 vol%, 91 vol%, 92 vol%, 93 vol%, 94 vol%, 95 vol%, or any value or range in between, with the remainder being ethylene, saturated hydrocarbons, an inert gas, or a combination thereof. Inert gases include nitrogen, helium, argon, or a combination thereof. In some embodiments, the feed stream is a mixture of propylene and ethylene and / or saturated hydrocarbons, with the remainder being an inert gas.

[0038] The first reactor 13 and / or standby reactor 19 may include a reaction zone 16 having an alkali metal catalyst 18 supported by the mixed metal oxide of the present invention. The amount of aliphatic alphaolefin in the feed source 12 and catalyst 18 used can be changed as necessary to achieve a given amount of product produced by the system 100. Non-limiting examples of reactors that can be used include fixed-bed reactors, fluidized-bed reactors, bubbling-bed reactors, slurry reactors, rotary kiln reactors, plug-flow reactors, or any combination thereof when two or more reactors are used. A circulating catalyst-bed reactor can allow for the regeneration of spent / inactivated catalysts in a continuous process. The first reactor 13 can be flushed with an inert gas to remove trace amounts of water and air. The catalyst 18 can be activated by flowing a hydrogen source (e.g., a gas stream of hydrogen and argon) over the catalyst at a desired temperature (e.g., 150-350°C). Contact between aliphatic alpha-olefins and a catalyst can accelerate the dimerization of olefins, generating effluent 20. Effluent 20 may contain dimerized products such as branched aliphatic alkene products generated in reaction zone 16. Other products include hexane, branched C6 hydrocarbons, branched or linear C9 hydrocarbons, and branched or linear C9 hydrocarbons. 12Hydrocarbons may be present. The by-products of the reaction may vary depending on the composition of the feed stream. The effluent 20 may further contain unreacted aliphatic alphaolefins. The effluent 20 can exit the reactor 13 and enter the effluent separation column 14. The effluent separation column 14 may be configured to separate the effluent 20 to form an upper stream 21 containing unreacted aliphatic alphaolefins and a lower stream 22 containing dimerization products (e.g., branched aliphatic alkenes) and their isomers. The upper stream 21 may be divided into a recirculation stream 23 mainly containing unreacted aliphatic alphaolefins and a purge stream 24. The recirculation stream 23 may be further combined with the feed source 12 to form a combined feed stream 27, which then flows into the first reactor 13. The bottom stream 22 can be further fractionated in the purification column 15 to form a product stream 25 containing a dimerization product mainly consisting of a branched aliphatic alkene (e.g., 4M1P) and an isomer stream 26 mainly consisting of one or more isomers of the dimerization product.

[0039] The first reactor 13 and the standby reactor 19 may be pressurized reactors. The first reactor 13 and the standby reactor may include one or more heating and / or cooling devices (e.g., insulation, electric heaters, wall-jacketed heat exchangers) or controllers (e.g., computers, flow valves, auto-values, etc.) which are necessary to control the flow of reactants, the reaction temperature, and / or the pressure of the reaction mixture. The heating and / or cooling devices may use pressurized water and / or organic compounds as the cooling medium. Although only one reactor is shown, it should be understood that multiple reactors can be housed in one unit, or multiple reactors can be housed in one heat transfer unit.

[0040] Referring to Figure 1B, a system 200 is shown that can be used to convert aliphatic alphaolefins to branched aliphatic alkenes using the mixed metal oxide-supported catalyst alkali metal catalyst of the present invention. In aspects of the present invention, system 200 includes all the units and flows of system 100 and further includes a second reactor 28 operating in parallel with a first reactor 13. In system 200, the combined feed stream 27 may be divided into a first feed stream 29 supplied to the inlet of the first reactor 13 and a second feed stream 30 supplied to the inlet of the second reactor 28. The second reactor 28 may contain the same or substantially the same catalyst as the first reactor 13. In some aspects, the catalyst of the first reactor 13 and the catalyst of the second reactor 28 may have different levels of catalytic activity. For example, the first reactor 13 may contain a new catalyst and the second reactor 28 may contain a partially deactivated catalyst. The first effluent flow 31 from the first reactor 13 and the second effluent flow 32 from the second reactor 28 can be combined to form an effluent flow 20, which flows into the effluent separation tower 14, as shown in Figure 1B. In aspects of the present invention, the system 200 may include more than two reactors (not shown), preferably two to five reactors, in a parallel configuration. The catalytic activity levels of the more than two reactors may differ. The catalytic activity level of each reactor may be in the range of 30 to 100% of the new catalyst, as well as all ranges and values ​​in between, including the ranges of 30 to 40%, 40 to 50%, 50 to 60%, 60 to 70%, 70 to 80%, 80 to 90%, and 90 to 100%. In aspects of the present invention, the two or more reactors may contain equal or different amounts of catalyst. The catalyst ratio between two or more reactors can be in the range of 10–100%, as well as all ranges and values ​​in between, including the ranges of 10–20%, 20–30%, 30–40%, 40–50%, 50–60%, 60–70%, 70–80%, 80–90%, and 90–100%. Compared to system 100 as shown in Figure 1A, system 200 has the advantage of less variability in productivity and therefore less variability in tower operation.

[0041] Referring to Figure 1C, a system 300 is shown that can be used to convert aliphatic alphaolefins to branched aliphatic alkenes using the mixed metal oxide-supported alkali metal catalyst of the present invention. System 300 may include all the units and flows of system 100 and may further include (i) a third reactor 33 located downstream of the first reactor 13, and (ii) an intermediate separation column 34 located downstream of the first reactor 13 and upstream of the third reactor 33. According to an embodiment of the present invention, the feed flow 27 may be divided into a first reactor feed flow 44 and an F splitting flow 35 that flow into the first reactor 13. In an embodiment of the present invention, the first reactor outflow flow 36 of the first reactor 13 may flow into the intermediate separation column 34, which is configured to separate the first reactor outflow flow 36 into (a) a first upper flow 37 containing unreacted aliphatic alphaolefins and (b) a first bottom flow 38 containing dimerization products and their isomers. The first upper flow 37 can be combined with the F splitting flow 35 to form a third reactor feed flow 39, which flows into the third reactor 33. In embodiments of the present invention, the first reactor 13 and the third reactor 33 contain the same catalyst of alkali metal supported by the mixed metal oxide of the present invention. The first reactor 13 and the third reactor 33 may be the same or substantially the same. The third reactor 33 may be configured to convert the aliphatic alphaolefins of the third reactor feed flow 39 into branched aliphatic alkenes. In embodiments of the present invention, the third reactor effluent flow 40 from the third reactor 33 is separated in the effluent separation column 14 to form an upper flow 21 containing unreacted aliphatic alphaolefins and a bottom flow 22 containing dimerization products (e.g., branched aliphatic alkenes) and their isomers. Similar to system 100, in system 300, the upper flow 21 can be divided into a recirculating flow 23 mainly containing unreacted aliphatic alphaolefins and a purge flow 24. The recirculating flow 23 can be further combined with the feed source 12 to form a combined feed flow 27. The bottom flow 22 can be combined with the first bottom flow 38 to form a fractionation column feed flow 41.The fractionation column feed stream 41 can be separated in the purification fractionation column 15 to form a product stream 25 containing a dimerization product mainly consisting of a branched aliphatic alkene (e.g., 4M1P) and an isomer stream 26 mainly consisting of one or more isomers of the dimerization product. According to an aspect of the present invention, the system 300 does not have to include the F splitting stream 35, such that the feed stream 27 flows directly into the first reactor 13 and the first reactor 13 and the third reactor 33 are in series. In an aspect of the present invention, the system 300 may include two or more reactors in series with a separation column located between two adjacent reactors. Each separation column between two nearest reactors may be configured to remove the dimerization product and its isomers from the effluent flow of the reactor located upstream of the separation column so that the unreacted aliphatic alphaolefin supplied to the next reactor is not diluted. A separation column positioned between the two nearest reactors can prevent further isomerization of the target dimerization product, including branched aliphatic alkenes (e.g., 4M1P), by separating the dimerization product and its isomers from the feed stream of the reactor downstream of the separation column. A system 300, including two or more reactors in series, may have the ability to increase the overall productivity of the target dimerization product, including branched aliphatic alkenes (e.g., 4M1P), compared to system 100 shown in Figure 1A. [Examples]

[0042] The present invention will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize various non-essential parameters that can be changed or modified to produce essentially the same results.

[0043] Example 1 (Synthesis of potassium zirconate support) Potassium zirconate material was synthesized using the solid-state method. Samples were prepared by using appropriate stoichiometric ratios to produce the desired composition. 20 g of K5ZrO 4.5A representative procedure for preparing the following was provided. K2CO3 (19.45 g) and ZrO2 (6.87 g), precursors of K and Zr, were mixed and ground in a mortar and pestle. The mixed material was placed in a muffle furnace and heated to 1050°C for 12 hours at a rising rate of 5°C / min. The resulting material was then cooled using the same rate of increase. The cooled material was ground and heated again, and this process was repeated three times. Other compositions were prepared in the same manner by varying the heating temperature and immersion time. The resulting powder mixtures were characterized as having a polyphase system consisting of pure potassium zirconate or one or more potassium zirconate phases with traces of other phases from the precursors.

[0044] The starting precursor of zirconium oxide (ZrO2) used in this process had a monoclinic crystal structure. The potassium carbonate (K4C2O6) phase precursor could be used in either a hexagonal or monoclinic structure. A hexagonal structure was used, each having a corresponding space group. After calcination, approximately 5% by weight of the precursor remained.

[0045] The potassium zirconate phase was characterized by X-ray diffraction (XRD) using a PANalytical Empyrean diffractometer (Malvern Panalytical, UK). Samples were scanned at room temperature (25°C) on a standard sample holder used in the range of °5 < °2θ < °100. The step size was °0.0130, and the fixed divergent slit had a slit size of °0.2177. The anode material used was copper, and the typical generator settings were 40 mA, 45 kV. Figure 2 shows the XRD patterns of the potassium zirconate support prepared using the procedure of Example 1. The following phases were observed: triclinic K4ZrO4 (PDF 00-031-1142), and KZrO and K5ZrO x Then, a hexagonal crystal system was detected.

[0046] The main predicted potassium zirconate phase is K4Zr5O 12 It is thought to have a similar crystal structure to K4Zr5O 12According to the literature, it has a perovskite-like crystal structure of potassium ions coordinated as a cuboctahedron, with zirconium ions inserted between the third and fourth layers as a hexagonal ring.

[0047] Example 2 (Synthesis of sodium yttriumate support material) Sodium yttriate material was synthesized using the coprecipitation method. The starting precursor, yttrium nitrate (Y(NO3)3.6H2O, 13.31 g), was dissolved in a minimum amount of water (20 mL). A corresponding amount of sodium carbonate (Na2CO3, 3.72 g) was added to the solution. The solution was heated to 70°C. Coprecipitation occurred as the water evaporated. The solid was collected, dried, and then calcined at 1050°C until the crystalline structure of sodium yttriate was formed. The powder was sieved to obtain a powder with a particle size of 100-300 microns.

[0048] The resulting powder mixture was characterized by XRD as having a multiphase system consisting of pure sodium yttriate or a single sodium yttriate phase with other phases from the precursor present. The generated sodium yttriate contained a cubic NaYO2 (PDF 00-032-1203) phase. In the case of non-stoichiometric sodium yttriate, the entire solid is a composite of the sodium yttriate phase and an excess element considered to be sodium oxide or yttrium oxide. Figure 3 shows NaYO x and Na3YO x The XRD pattern is shown.

[0049] Example 3 (Synthesis of metallic sodium on a sodium yttriate support material) A sodium yttriumate support material (10 g) from Example 2, with a particle size of 100-300 microns, was placed in a container. The container was flushed with an inert gas to remove trace amounts of water and air. The sealed container was heated to 300°C while stirring for 2 hours. Next, the temperature was set to 200°C, and potassium metal (5% by weight of the total catalyst weight) was introduced into the container. The resulting mixture was stirred for 1 hour to uniformly distribute the molten metal onto the support material.

[0050] Example 4 (Synthesis of metallic sodium or NaK on potassium zirconate support material) Potassium zirconate (49 g, Example 1) was mixed with graphite (2 wt%) based on the total weight of the catalyst) in a blender to ensure uniform distribution of the additive before tableting into 3x3 mm tablets. The resulting tablets exhibited radial and axial mechanical strengths of 200–400 daN and densities of 1 g–4 g per cubic centimeter as a function of the particle size used. The as-prepared tablets (approximately 10 g by weight) were placed in a container and flushed with an inert gas to remove water and oxygen. The container was stirred and heated at 300°C for 2 hours. The fine particles generated in the first stage of the process were removed from the container. The container was stirred again at 200°C and potassium metal or potassium and sodium metal (5 wt%) based on the total weight of the catalyst was introduced. The resulting mixture was kept under stirring for 1 hour to ensure uniform distribution of the molten metal on the potassium zirconate tablets.

[0051] Example 5 (Synthesis of branched aliphatic alkenes from propylene - batch reactor) The catalyst from Example 3 (2 g) or the K2CO3 and stirring rod of the comparative example sample were placed in an autoclave. The reactor was closed and the weight was recorded. The reactor was cooled to 0°C and placed on a balance, and propylene was allowed to condense in the reactor until a weight increase of 8.5 times the original weight (17 g) was achieved. Subsequently, the reactor was carefully evacuated until the weight increase was exactly 8.5 times the original weight (17 g). Next, the reactor was placed in an oil bath and maintained at 150°C with stirring. A gas manifold was connected to the head valve of the autoclave to allow sampling in two consecutive vacuum stages. Samples (0.2 mL of product) were taken at regular time intervals and analyzed by GC. After 24 hours, the final weight of the reactor was recorded, the reactor was cooled to 0°C, and the pressure was carefully reduced. The final weight was recorded to determine the yield. The liquid product and spent catalyst were separated by filtration (diluted with heptane if necessary). Liquids were analyzed by GC-MS (equipped with Agilent 5977A-MSD / DB1 column and FID detector (Agilent Technologies, USA)), and solids were analyzed by XRD. The results are shown in Table 1. The selectivity of 4-methyl-1-pentene (4M1P) is given by the following formula: The calculation was performed using TIFF0007859825000001.tif11128.

[0052] [Table 1]

[0053] Example 6 (Synthesis of branched aliphatic alkenes from propylene - plug flow reactor) Approximately 4 g of the K2CO3 molding catalyst from Example 4 or the comparative example catalyst was placed in a reactor under an inert atmosphere. The reactor was then connected to the gas supply section and placed inside the furnace to ensure temperature control. The entire system was flushed with inert gas to ensure the removal of trace amounts of water and air. Next, propylene was used at 75 bar (7.5 MPa) at a temperature of 145-165°C and for 0.2-1 hour. -1The reaction was carried out using LHSV. Pressure was controlled by a back pressure adjustment system, and the outlet gas composition was continuously analyzed by gas chromatography. The results are shown in Table 2. C6 refers to the total amount of linear and branched C6 hydrocarbons. The conversion is given by the following equation: The determination was made using TIFF0007859825000003.tif10128.

[0054] [Table 2]

[0055] The data revealed that catalytically active alkali metals on a mixed oxide support containing an alkali metal and at least one of the third, fourth, or lanthanide metals can effectively catalyze the conversion of aliphatic alpha-olefins (e.g., propylene) to branched aliphatic alkenes (e.g., 4-methyl-1-pentene). Specifically, when x balances with the valence of the mixed metal oxide, K5ZrO x The above K or NaK complex of 7 wt% produces 4-methyl-1-pentene with a conversion rate similar to that of potassium carbonate, and with a selectivity similar to or even higher than that of potassium carbonate, thus providing a technical solution to the problems associated with carbonate catalysts (e.g., structural breakdown of the catalyst).

[0056] Example 7 (Synthesis of branched aliphatic alkenes in a single reactor system) The simulation was performed using ASPEN® Plus (version 10) for the reaction system shown in Figure 1A. The reaction kinetics within the reactor were obtained from experiments performed on a laboratory-scale single-reactor 4M1P production system. The simulation was set to produce 99.0 mol% 4M1P in the product stream (labeled product stream 25 in Figure 1A), achieved by adjusting the parameters of the separation apparatus (e.g., effluent separation column 14 and product purification fractionation column 15 in Figure 1A). Table 3 shows the composition, flow rate, and conditions (temperature and pressure) for each stream in the reaction system as shown in Figure 1A. The overall conversion rate of C3H6 was 50.8%. The selectivity of 4M1P was 89.9%. The product flow rate of the system was 6.42 tons / hour.

[0057] [Table 3]

[0058] Example 8 (Synthesis of branched aliphatic alkenes in a system including two parallel reactors) The simulation was performed using ASPEN® Plus (version 10) for the reaction system shown in Figure 1B. The reaction kinetics within the reactor of the reaction system were obtained from experiments performed on a laboratory-scale single-reactor 4M1P production system. The simulation was set to produce 99.0 mol% 4M1P in the product stream (labeled product stream 25 in Figure 1B), achieved by adjusting the parameters of the separation apparatus (e.g., effluent separation column 14 and product purification fractionation column 15 in Figure 1B). The composition, flow rate, and conditions (temperature and pressure) of each stream in the reaction system as shown in Figure 1B are shown in Table 4. The conversion rates in the first reactor (labeled first reactor 13 in Figure 1B) and the second reactor (labeled second reactor 28 in Figure 1B) were 46.6% and 40.3%, respectively. The overall conversion rate for C3H6 was 43.4%. The selectivity of 4M1P in the first and second reactors was 90.1% and 90.5%, respectively. The overall selectivity of 4M1P was 90.3%. The system's product flow rate was 6.38 tons / hour.

[0059] [Table 4]

[0060] Example 9 (Synthesis of branched aliphatic alkenes in a system including two series reactors) The simulation was performed using ASPEN® Plus (version 10) for the reaction system shown in Figure 1C. The reaction kinetics within the reactor of the reaction system were obtained from experiments performed on a laboratory-scale single-reactor 4M1P production system. The simulation was set to produce 99.0 mol% 4M1P in the product stream (labeled product stream 25 in Figure 1C), achieved by adjusting the parameters of the separation apparatus (e.g., effluent separation column 14 and product purification fractionation column 15 in Figure 1C). The composition, flow rate, and conditions (temperature and pressure) of each stream in the reaction system as shown in Figure 1C are shown in Table 5. The conversion rates in the first reactor (labeled first reactor 13 in Figure 1C) and the third reactor (labeled third reactor 33 in Figure 1C) were 48.9% and 47.3%, respectively. The overall conversion rate for C3H6 was 64.3%. The selectivity of 4M1P in the first and third reactors was 90.1% and 90.4%, respectively. The overall selectivity of 4M1P was 90.2%. The system's product flow rate was 6.38 tons / hour.

[0061] The systems and processes described herein may also include various devices known to those skilled in the art of chemical processing, which are not illustrated. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, etc., may not be shown.

[0062] In the context of the present invention, at least the following 23 embodiments are shown. Embodiment 1 is a method for producing a branched aliphatic alkene. This method comprises the step of reacting a feed stream containing an aliphatic alphaolefin with a supported alkali metal or alkali metal composite catalyst to produce a branched aliphatic alkene, wherein the support comprises a mixed metal oxide containing a first-row metal and at least one of a third-row metal, a fourth-row metal, or a lanthanide, and the catalyst has less than 50% by weight of metal carbonate. Embodiment 2 is the method according to Embodiment 1, wherein the alkali metal is sodium (Na), potassium (K), cesium (Cs), or a composite or mixture thereof. Embodiment 3 is the method according to Embodiment 2, wherein the alkali metal is K, or the alkali metal composite is NaK. Embodiment 4 is the method according to any one of Embodiments 1 to 3, wherein the third row metal oxide comprises scandium (Sc) or yttrium (Y), preferably Y. Embodiment 5 is the method according to any one of Embodiments 1 to 4, wherein the fourth-row metal oxide is titanium (Ti), zirconium (Zr), hafnium (Hf), or a combination thereof, preferably containing Zr. Embodiment 6 is the method according to any one of Embodiments 1 to 5, wherein the lanthanide oxide comprises lanthanum (La), cerium (Ce), promethium (Pm), or praseodymium (Pr), preferably La. Embodiment 7 is the method according to any one of Embodiments 1 to 6, wherein the first row metal oxide comprises Na, K, or Cs, more preferably K. Embodiment 8 is the method according to any one of Embodiments 1 to 7, wherein the catalyst contains 0.1 to 10% by weight, preferably 1 to 9% by weight, and more preferably 3 to 8% by weight of an alkali metal. Embodiment 9 is the method according to any one of Embodiments 2 to 8, wherein the catalyst is a K metal supported on sodium yttriate, potassium zirconate, or a mixture thereof. Embodiment 10 is the method according to any one of Embodiments 2 to 8, wherein the catalyst is a NaK metal composite supported on sodium yttriate, potassium zirconate, or a mixture thereof. Embodiment 11 is the method according to any one of Embodiments 1 to 10, wherein the support is macroporous, mesoporous, or microporous, or a combination thereof. Embodiment 12 is the method according to any one of Embodiments 1 to 11, wherein the catalyst has an average particle diameter of 100 to 600 microns, an average pore volume of 0.03 to 0.30 mL / g, or both. Embodiment 13 is the method according to any one of Embodiments 1 to 12, wherein the aliphatic alphaolefin has 1 to 5 carbon atoms, preferably 2 to 4, and more preferably 3 carbon atoms. Embodiment 14 is the method according to any one of Embodiments 1 to 13, wherein the supply flow contains propylene. Embodiment 15 is the method according to Embodiment 14, wherein the feed stream further comprises ethylene, saturated hydrocarbons, or both. Embodiment 16 is the method according to any one of Embodiments 1 to 15, wherein the branched aliphatic alkene has 4 to 10 carbon atoms, preferably 4 to 8, more preferably 6, and more preferably 4-methyl-1-propene. Embodiment 17 is characterized by a reaction pressure of 5 MPa to 10 MPa, a reaction temperature of 120 to 200°C, more preferably 140 to 170°C, or both, or a liquid space velocity of 0.1 to 2 h -1 The method is as described in any one of embodiments 1 to 16. Embodiment 18 is the method according to Embodiment 17, wherein the reaction is carried out in a reaction system including a pressurized reactor. Embodiment 19 is the method according to Embodiment 18, wherein the reaction system comprises 2 to 5 reactors in parallel, at least 2 of the 2 to 5 reactors have catalysts having different catalytic activity levels, and at least 1 of the 2 to 5 reactors is in regenerative mode. Embodiment 20 is the method according to Embodiment 18, wherein the reaction system comprises a first reactor and a second reactor in series, and a separation column downstream of the first reactor and upstream of the second reactor, the separation column being configured to remove branched aliphatic alkenes and their isomers from the effluent of the first reactor in order to generate an inlet flow for the second reactor. Embodiment 21 is the method according to any one of Embodiments 17 to 20, wherein the catalyst is a potassium metal or NaK complex on sodium zirconate, and the selectivity for branched aliphatic alkenes is at least 60% after 6 hours. Embodiment 22 is the method according to Embodiment 21, wherein the catalyst is a NaK complex on potassium zirconate, and the ratio of 4-methyl-1-pentene to methylpentene is at least 93%. Embodiment 23 is a catalyst for producing branched aliphatic alkenes. This catalyst comprises a potassium (K) metal or NaK metal composite on a metal oxide support containing a mixed metal oxide of a first-row metal and at least one of a third-row metal, a fourth-row metal, or a lanthanide, and this catalyst has less than 50% by weight of metal carbonate.

[0063] While the aspects of this application and their advantages have been described in detail, it should be understood that various modifications, substitutions, and alternatives can be made herein without departing from the spirit and scope of the aspects defined by the appended claims. Furthermore, the scope of this application is not intended to be limited to any particular aspects of the processes, machines, manufactures, compositions of materials, means, methods, and stages described in the specification. Those skilled in the art will readily understand from the above disclosure that existing or subsequently developed processes, machines, manufactures, compositions of materials, means, methods, or stages may be available that perform substantially the same function or achieve substantially the same results as the corresponding aspects described herein. Accordingly, the appended claims are intended to include such processes, machines, manufactures, compositions of materials, means, methods, or stages within their scope.

[0064] [Table 5]

Claims

1. A method for producing a branched aliphatic alkene by dimerization of an aliphatic alphaolefin, comprising the step of reacting a feed stream containing an aliphatic alphaolefin with a supported alkali metal or alkali metal composite catalyst in order to produce a branched aliphatic alkene, The support comprises a mixed metal oxide containing a first-row metal and at least one of a third-row metal, a fourth-row metal, or a lanthanide, and the catalyst has less than 50% by weight of metal carbonate; The catalyst has an average particle diameter of 100 to 600 microns and an average pore volume of 0.03 to 0.30 mL / g. The reaction pressure is 5 MPa to 10 MPa, the reaction temperature is 120 to 200°C, and the liquid space velocity is 0.1 to 2 h. -1 And; The reaction is carried out in a reaction system including a pressurized reactor; The reaction system comprises a first reactor and a second reactor in series, and a separation column downstream of the first reactor and upstream of the second reactor, wherein the separation column is configured to remove the branched aliphatic alkenes and their isomers from the effluent of the first reactor in order to generate an inlet flow for the second reactor. The aforementioned method.

2. The method according to claim 1, wherein the alkali metal is sodium (Na), potassium (K), cesium (Cs), or a composite or mixture thereof.

3. The method according to claim 2, wherein the alkali metal is K, or the alkali metal composite is NaK.

4. The method according to claim 1, wherein the catalyst comprises the third-row metal oxide, and the third-row metal oxide comprises scandium (Sc) or yttrium (Y).

5. The method according to claim 1, wherein the fourth row of metal oxides includes titanium (Ti), zirconium (Zr), hafnium (Hf), or a combination thereof.

6. The method according to claim 1, wherein the lanthanide oxide comprises lanthanum (La), cerium (Ce), promethium (Pm), or praseodymium (Pr).

7. The method according to claim 1, wherein the first row of metal oxides comprises Na, K, or Cs.

8. The method according to claim 1, wherein the catalyst contains 0.1 to 10% by weight of an alkali metal.

9. The method according to claim 2, wherein the catalyst is a K metal supported on sodium yttriate, potassium zirconate, or a mixture thereof.

10. The method according to claim 2, wherein the catalyst is a NaK metal composite supported on sodium yttriate, potassium zirconate, or a mixture thereof.

11. The method according to claim 1, wherein the support is macroporous, mesoporous, or microporous, or a combination thereof.

12. The method according to claim 1, wherein the aliphatic alphaolefin has 3 to 5 carbon atoms.

13. The method according to claim 1, wherein the supply flow contains propylene.

14. The method according to claim 13, wherein the supply flow further comprises ethylene, saturated hydrocarbons, or both.

15. The method according to claim 1, wherein the branched aliphatic alkene has 6 to 10 carbon atoms.

16. The method according to claim 1, wherein the reaction temperature is 140 to 170°C.

17. The method according to claim 16, wherein the catalyst is a potassium metal or NaK complex on sodium zirconate, and the selectivity of the branched aliphatic alkene is at least 60% after 6 hours.

18. The catalyst is a NaK complex on potassium zirconate. The method according to claim 10, wherein the aliphatic alphaolefin is propylene, and methylpentene containing 4-methyl-1-pentene is produced by dimerization of the propylene, the ratio of 4-methyl-1-pentene to the methylpentene is at least 93%.

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