Process for the preparation of mixed alcohols from a purge stream containing octenes

Abstract

The present disclosure provides a method. In one embodiment, the method includes providing a purge stream comprising octene isomers. The method includes subjecting the purge stream to hydroformylation conditions and forming a reaction product comprising nonanal.

Description

Background Art

[0001] In the production of ethylene / octene copolymer, under suitable reaction conditions (in the presence of solvent and chain-transfer agent), ethylene, octene comonomer and polymerization catalyst are introduced into polymerization reactor to produce ethylene / octene copolymer polymer product stream. From reactor, take out product stream and this product stream contains ethylene / octene copolymer, and the hydrocarbon material of unreacted monomer (ethylene), unreacted comonomer (octene) and other relevant hydrocarbons (hydrogen, ethane, methane, propane, pentane, hexane, butane). Through devolatilization, ethylene / octene copolymer is separated from solvent and unreacted monomer and unreacted comonomer. Subsequently, granular ethylene / octene copolymer is collected after granulation and cooling. After ethylene / octene copolymer separates from product stream, hydrocarbon material is recycled back in polymerization reactor or purged from system.

[0002] Reusing purged hydrocarbons is one of the biggest challenges facing large-scale polyolefin production. For example, octene comonomer conversion in ethylene / octene copolymer production is typically very low, ranging from 10% to 20%. This means that 80% to 90% of the octene can pass through the reactor without being converted into polymer.

[0003] Ideally, the octene comonomer is recycled back to the polymerization reactor. Although recycling of volatile monomers such as ethylene is very effective, recycling of octene is difficult, especially when other saturated hydrocarbons are present in the product stream. The boiling point of octene is very close to the boiling points of other saturated and unsaturated substances present in the product stream, making octene separation difficult. The fresh octene stream also contains other isomers of octene (1 wt % to 5 wt % octene isomers based on the total weight of octene). Octene isomers generally do not react with ethylene during the polymerization process. Therefore, octene isomers aggregate or otherwise "accumulate" in the continuous recycle of the recycle stream, thereby reducing the recycling efficiency as a feed stream. In this way, octene isomers can accumulate to as much as 70% of the total recycle stream.

[0004] Thus, the art recognizes a continuing need for a way to utilize the purge stream hydrocarbon material that avoids simply discarding the purge stream hydrocarbon material.There is also a need to utilize the octene monomer present in the purge stream. Summary of the Invention

[0005] The present disclosure provides a method. In one embodiment, the method includes providing a purge stream comprising octene isomers. The method includes subjecting the purge stream to hydroformylation conditions and forming a reaction product comprising nonanal. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 is a schematic diagram of a hydroformylation reactor system for providing hydroformylation conditions according to an embodiment of the present disclosure.

[0007] Figure 2 is a temperature-time graph for overhead separation according to an embodiment of the present disclosure.

[0008] definition

[0009] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. Groups of elements in this table are referred to by a new notation for numbering the groups.

[0010] For purposes of U.S. patent practice, the contents of any cited patent, patent application, or publication are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference), particularly with respect to definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and common general knowledge in the art.

[0011] The numerical ranges disclosed herein include all values from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing clear values (e.g., 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two clear values is included (e.g., the above range 1-7 includes subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0012] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0013] An "alcohol" is a compound having a hydroxyl group (-OH) attached to a hydrocarbon group.

[0014] "Aldehyde" is a compound having a carbonyl functional group (C=O) attached to a hydrocarbon group and a hydrogen atom.

[0015] "Olefins" are hydrocarbons containing a carbon-carbon double bond.

[0016] As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. The blend may or may not be miscible (not phase separated at the molecular level). The blend may or may not be phase separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.

[0017] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0018] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. Conversely, the term "consisting essentially of excludes from the scope of any subsequently recited content any other components, steps, or procedures (except those that are not essential to operability). The term "consisting of excludes any component, step, or procedure not specifically recited or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0019] "Alkenals" are aldehyde compounds containing a carbon-carbon double bond. Alkenals can be formed by the aldol (or crossed aldol) condensation of aldehydes, followed by dehydration of the resulting intermediate compound. A non-limiting example of an aldol is 2-ethylhexenal, which is produced by the self-condensation of a C4 aldehyde as shown below:

[0020]

[0021] An "enol" is an alcohol containing a carbon-carbon double bond. Enols can be formed by partial hydrogenation of enals.

[0022] An "ethylene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and, optionally, may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" are used interchangeably.

[0023] A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. A "hydrocarbyl" (or "hydrocarbyl group") is a hydrocarbon having a valence (usually monovalent).

[0024] As used herein, the term "1-octene" is a 1-octene having the molecular formula C8H 16 An unsaturated hydrocarbon with unsaturation at the α position is an α-olefin. 1-Octene has the molecular structure (A) shown below.

[0025] Structure (A)

[0026]

[0027] As used herein, the term "isomers of octene" refers to isomers of the molecular formula C8H 16and an unsaturated hydrocarbon in which the unsaturation (double bond) is not in the alpha position. In other words, the term "octene isomer" refers to any octene other than 1-octene. Non-limiting examples of octene isomers include cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, and combinations thereof, as well as cis-4-octene, trans-4-octene, branched octene isomers, and combinations thereof.

[0028] As used herein, the term "linear internal octene isomer" is a linear unsaturated hydrocarbon comprising an eight-carbon chain, with the unsaturation (double bond) not being in the alpha position. Linear internal octene isomers include cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, cis-4-octene, trans-4-octene, and combinations thereof. As used herein, the term "branched C8 olefin" is a branched C8 olefin having the molecular formula C8H 16 The non-limiting examples of branched C8 olefins include methylheptene, such as 3-methyl-2-heptene, 3-methyl-3-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene, etc. The non-limiting examples of branched C8 olefins include dimethyl hexene, such as 3,4-dimethyl-2-hexene, 3,4-dimethyl-3-hexene, 2,3-dimethyl-3-hexene, etc. Other non-limiting examples include ethyl hexene, such as 2-ethyl-1-hexene, etc.

[0029] "Olefin" is an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0030] "Polymer" is a compound prepared by polymerizing monomers of the same or different types, which monomers provide, in polymerized form, multiple and / or repeating "units" or "monomer units" that make up the polymer. Thus, the general term polymer encompasses the term homopolymer, which is generally used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is generally used to refer to polymers prepared from at least two types of monomers. It also encompasses all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" refer to copolymers prepared by polymerizing ethylene or octene, respectively, and one or more additional polymerizable α-olefin monomers, as described above. It should be noted that although polymers are often referred to as being "made from" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in the present context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than the unpolymerized species. Generally speaking, polymers are referred to herein as being based on "units" of the polymerized form of the corresponding monomer.

[0031] Test Method

[0032] Gas chromatography (GC).

[0033] The composition of the spent solvent and hydroformylation reaction products was determined by gas chromatography (GC) using the following conditions:

[0034]

[0035] Quantification of the data in Table 1 (in the Examples section below) and Section A of the Examples section is based on weight percent using response factors derived from standard solutions of known concentration.

[0036] The compositions of the cross-aldol reaction products and crude alcohol product were determined by GC and gas chromatography / mass spectrometry (GC / MS) using the following conditions:

[0037]

[0038] Quantitation in Sections B through E of the Examples section is based on the GC area percentage (interchangeably referred to as "GC area" or "GC %") of the FID signal. Peak identification / confirmation of component structure is based on electron ionization mass selective detector signals matched to a National Institute of Standards and Testing library.

[0039] N:I Ratio. The hydroformylation reaction of olefins having three or more carbon atoms produces a mixture of linear and branched isomers. As used herein, the term "N:I ratio" is the ratio of the linear or normal (N) aldehyde isomer to the branched or isoaldehyde (I) isomer. The N:I ratio is calculated by dividing the concentration (wt%) of the normal aldehyde by the concentration (wt%) of the isoaldehyde. The weight percent concentration of each aldehyde isomer is determined by gas chromatography (GC). DETAILED DESCRIPTION

[0040] The present disclosure provides a method. The method includes providing a purge stream comprising octene isomers and subjecting the purge stream to hydroformylation conditions. The method includes forming a reaction product comprising nonanal.

[0041] The present method includes providing a purge stream. The purge stream includes octene isomers. As used herein, a "purge stream" is one of several fractions that are separated or otherwise recovered from the effluent leaving the polymerization reactor after the polymerization reaction occurs. The liquid effluent leaving the polymerization reactor contains solid (granular) polymer product, which is removed. A recycle stream is also removed from the effluent, further processed and returned to the polymerization reactor. The purge stream is the stream remaining after (i) the polymer product has been recovered from the effluent and (ii) the recycle stream has been separated from the effluent. The purge stream contains unreacted olefin monomers, including octene isomers and other hydrocarbons used during the polymerization reaction. It should be understood that the purge stream does not contain or is substantially free of solid polymer product.

[0042] In one embodiment, the purge stream is the effluent from a polymerization reactor in which ethylene and octene are copolymerized. The purge stream includes unreacted octene isomers and other hydrocarbons.

[0043] In one embodiment, the sweep stream comprises

[0044] (i) 20 wt% to 55 wt%, or 25 wt% to 50 wt% of 1-octene,

[0045] (ii) 20 wt% to 60 wt% of linear internal octene isomers,

[0046] (iii) 2 wt% to 8 wt% of branched C8 olefins, and

[0047] (iv) 5 wt% to 60 wt% hydrocarbon solvent, wherein the weight percentages are based on the total weight of the sweep stream. It will be understood that components (i)-(iv) add up to 100 wt% of the sweep stream.

[0048] In one embodiment, the method includes removing any ethylene that may be present in the purge stream. The purge stream is sparged with nitrogen such that no ethylene is present in the purge stream. The purge stream contains no or substantially no ethylene monomer, i.e., 0 wt %, or greater than 0 wt % to less than 0.5 wt % ethylene, based on the total weight of the purge stream.

[0049] The method includes subjecting the purge stream to hydroformylation conditions. As used herein, "hydroformylation conditions" are reactor conditions (including temperature and pressure), reaction ingredients (olefin, solvent, hydroformylation catalyst, and synthesis gas (also known as "syngas," which is a feed of hydrogen (H2) and CO in a molar ratio of hydrogen (H2): carbon monoxide (CO) of 1:10 to 10:1 or 1:1) within one or more reactors that promote the formation of a formyl group (-CH=O) and a hydrogen atom with the carbon-carbon double bond of an alkene (i.e., olefin) to produce an aldehyde. Hydroformylation can be carried out in a liquid state, a gaseous state, and in a continuous process, a semi-continuous process, or a batch process, and can involve liquid recycle and / or gas recycle operations.

[0050] In one embodiment, the step of subjecting the purge stream to hydroformylation conditions is included in contacting the purge stream with a hydroformylation catalyst under the hydroformylation conditions. The hydroformylation catalyst is a metal-organic phosphite ligand complex catalyst. The non-limiting example of suitable metal includes rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and their mixture. In one embodiment, the metal is selected from rhodium, cobalt and ruthenium, or is selected as rhodium. The ligand is an organic monophosphite ligand, an organic polyphosphite ligand or their combination.

[0051] In one embodiment, the part is an organic polyphosphite ligand. The organic polyphosphite ligand comprises a plurality of phosphite groups, and each phosphite group contains a trivalent phosphorus atom bonded to three hydroxyl groups. The hydroxyl group connecting and bridging two phosphite groups is referred to as " divalent alkyl dioxy group ". These bridging diradicals are not limited to any specific alkyl species. On the other hand, the hydroxyl group that is side-hung in the phosphorus atom and does not bridge two phosphite groups (that is, end, non-bridging) needs to be basically composed of an aryloxy group separately. "Aryloxy" refers to either of two types of aryloxy groups: (1) a monovalent aromatic group bound to a single ether linkage, as in -O-aryl, wherein the aryl group comprises a single aromatic ring or multiple aromatic rings fused together, directly linked, or indirectly linked (such that the different aromatic groups are bound to a common group such as a methylene or ethylene moiety), or (2) a divalent arylene group bound to two ether linkages, as in -O-arylene-O- or -O-arylene-arylene-O-, wherein the arylene group comprises a divalent hydrocarbon group having a single aromatic ring or multiple aromatic rings fused together, directly linked, or indirectly linked (such that the different aromatic groups are bound to a common group such as a methylene or ethylene moiety). In one embodiment, the aryloxy group contains one aromatic ring or 2 to 4 fused or linked aromatic rings having 5 to 20 carbon atoms, for example, phenoxy, naphthyloxy, or biphenyloxy, as well as arylenedioxy groups such as phenylenedioxy, naphthylenedioxy, and biphenylenedioxy. Any of these groups may be unsubstituted or substituted.

[0052] In one embodiment, the organopolyphosphite ligand includes two, three or more phosphite groups. If desired, a mixture of such ligands can be used. Achiral organopolyphosphites are preferred. Representative organopolyphosphites include those of formula (I):

[0053]

[0054] wherein X represents a substituted or unsubstituted n-valent organic bridging group containing 2 to 40 carbon atoms, and each R 1 are the same or different and represent a divalent organic group containing 4 to 40 carbon atoms, each R 2 are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon radical containing 1 to 24 carbon atoms, a and b may be the same or different and each have a value of 0 to 6, provided that the sum of a+b is 2 to 6 and n is equal to a+b. Of course, it should be understood that when a has a value of 2 or greater, each R 1 The groups may be the same or different, and when b has a value of 1 or greater, each R 2 The groups may be the same or different.

[0055] In one embodiment, the ligand is [[3,3′,5,5′-tetrakis(1,1-dimethylethyl)-[1,1′-biphenyl]-2,2′-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]-dioxaphosphapin, which has the formula of Ligand A shown below:

[0056] Ligand A

[0057]

[0058] The purge stream is subjected to hydroformylation conditions by a hydroformylation process. The hydroformylation process comprises feeding the purge stream along with synthesis gas (carbon monoxide and hydrogen) and a hydroformylation catalyst to a multiple reactor system connected in series, i.e., the output of the first reaction zone is fed as input to a subsequent reaction zone.

[0059] The molar ratio of gaseous hydrogen to carbon monoxide (H2:CO) is in the range of 1:10 to 10:1. The hydroformylation process is conducted at a reaction temperature of 50°C to 100°C, and a total gas pressure consisting of the purge stream, carbon monoxide, and hydrogen in the range of 1 psia (6.9 kPa) to 2,000 psia (13,800 kPa).

[0060] An inert solvent can be used as a diluent for the hydroformylation reaction medium. A variety of solvents can be used, including ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and cyclohexanone; aromatic compounds such as benzene, toluene, and xylene; halogenated aromatic compounds including o-dichlorobenzene; ethers such as tetrahydrofuran, dimethoxyethane, and dioxane; halogenated alkanes including dichloromethane; alkanes such as heptane; and the like. In one embodiment, the solvent is the aldehyde product and / or oligomers of the aldehyde product and one or more reactive olefins.

[0061] In one embodiment, the hydroformylation process is carried out in a continuous manner in a multi-stage reactor designed with internal physical barriers that create more than one theoretical reactive stage or zone per vessel. The hydroformylation process comprises: (a) hydroformylating a purge stream with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a solvent and a hydroformylation catalyst; (b) maintaining reaction temperature and pressure conditions favorable for hydroformylation of the purge stream; (c) supplying make-up amounts of the purge stream, carbon monoxide, and hydrogen to the reaction medium as the reactants are depleted; and (d) recovering the desired aldehyde hydroformylation product.

[0062] The continuous hydroformylation process can be conducted in a single pass mode, wherein the vaporous mixture includes an unreacted purge stream and the vaporized aldehyde product is removed from the liquid reaction mixture, thereby recovering the aldehyde product, and supplying make-up olefin starting material, carbon monoxide, and hydrogen to the liquid reaction medium for the next single pass without recycling unreacted olefin starting material.

[0063] The purge stream is subjected to the aforementioned hydroformylation conditions to form a reaction product comprising nonanal. Since the purge stream comprises octene isomers, the purge stream is subjected to the hydroformylation conditions to form a reaction product comprising nonanal. "Nonanal" is an aldehyde containing nine carbon atoms. The purge stream is a mixture of olefins (primarily 1-octene and octene isomers) and alkanes, and thus the reaction product from the hydroformylation reaction includes other components in addition to nonanal. Non-limiting examples of other components in the hydroformylation reaction product include C8 olefins, C7-C9 alkanes, and combinations thereof.

[0064] The method comprises adding an aldehyde selected from C4 aldehydes, C5 aldehydes and combinations thereof (hereinafter referred to as "C4 / C5 aldehyde") to a reaction product comprising nonanal (hereinafter referred to as "nonanal product") to form a mixture, namely, mixture A. The method comprises cross-aldol condensing mixture A and forming a cross-aldol product. The cross-aldol product is selected from C8 alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal, C 18 The cross-aldol product may also include alcohol, solvent, water, unreacted aldehyde, and combinations thereof.

[0065] The cross-aldol condensation step comprises combining the nonanal product and the C4 / C5 aldehyde with an inorganic base catalyst, an alcohol, and optionally water to form a reaction mixture, mixture A. Non-limiting examples of suitable inorganic base catalysts include sodium hydroxide, potassium hydroxide, and combinations thereof. A non-limiting example of a suitable alcohol is isopropyl alcohol. Reaction mixture A is heated to a temperature of 30° C. to 100° C., whereby the inorganic base catalyzes the aldol condensation reaction to form the cross-aldol product and a water byproduct.

[0066] In one embodiment, the process comprises adding a C4 aldehyde and adding the nonanal product to an inorganic base catalyst (such as sodium hydroxide) and an alcohol (such as isopropanol) to form a reaction mixture, i.e., mixture A4. The process comprises heating the reaction mixture A4 to a temperature of 30°C to 100°C, or to a temperature of 40°C to 70°C, or to a temperature of 50°C to 60°C, whereby the inorganic base catalyzes the aldehyde-alcohol condensation and forms a nonanal selected from the group consisting of C8 alkenal, C 13 Alkenal, C 18The cross-aldol product may further include alcohol solvent, water, unreacted aldehyde, other C8, C 13 and C 18 In one embodiment, the cross-aldol product comprises a major amount of C8 alkenals, C 13 Alkenal and C 18 Alkenals, wherein the "major amount" is greater than 50% of the total GC area of the crossed aldol reaction products.

[0067] In one embodiment, the process comprises adding a C5 aldehyde and adding the nonanal product to an inorganic base catalyst (such as sodium hydroxide) and an alcohol (such as isopropanol) to form a reaction mixture, i.e., mixture A5. The process comprises heating the reaction mixture A5 to a temperature of 30°C to 100°C, or to a temperature of 40°C to 70°C, or to a temperature of 50°C to 60°C, whereby the inorganic base catalyzes the aldehyde-alcohol condensation and forms the C5 aldehyde. 10 Alkenal, C 14 Alkenal, C 18 The cross-aldol product may further include an alcohol solvent, water, optional unreacted aldehyde and other C 10 、C 14 、C 18 In one embodiment, the cross-aldol product comprises a major amount of C 10 Alkenal, C 14 Alkenal and C 18 Alkenals, wherein the "major amount" is greater than 50% of the total GC area of the crossed aldol reaction products.

[0068] The method comprises hydrogenating a cross-aldol product. The cross-aldol product comprises C8 alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal, C 18 Alkenal and their combination. The method comprises forming a crude alcohol product. The crude alcohol product is composed of C8 alcohol, C 10 Alcohol, C 13 Alcohol, C 14 Alcohol, C 18 Alcohols and their combination. The crude alcohol product also includes alkane components and other C8, C 10 、C 13 、C 14 、C 18 In one embodiment, the crude alcohol product includes a major amount of C8 alcohol, C 10 Alcohol, C 13 Alcohol, C 14 Alcohol and C 18Alcohol, wherein the "major amount" is greater than 50% of the total GC area of the crude alcohol product.

[0069] In one embodiment, the hydrogenation of the cross-aldol product is carried out under liquid phase hydrogenation conditions using a heterogeneous supported metal catalyst (nickel, palladium, copper, cobalt and / or platinum). The liquid hourly space velocity (LHSV) of the cross-aldol product is 0.1 h -1 (hr -1 ) to 8 hours -1 or 0.5 hours -1 Up to 3 hours -1 The gas hourly space velocity (GHSV) of hydrogen is 50 hr -1 Up to 10,000 hours -1 or 200 hours -1 Up to 4,000 hours -1 The hydrogenation process is conducted at a reaction temperature of 100°C to 200°C, or 120°C to 180°C, and a reaction pressure of 300 psig to 1,500 psig, or 400 psig to 1,000 psig.

[0070] In one embodiment, the process comprises hydrogenating a C8 alkenyl, a C 13 Alkenal, C 18 The method comprises forming a cross-aldol product composed of C8 alcohol, C 13 Alcohol, C 18 The crude alcohol product also includes alkane components and other C8, C 13 、C 18 In another embodiment, the method includes separating the alkane component and the other materials to leave a C8 alcohol, C 13 Alcohol, C 18 In another embodiment, the bottom product is further refined (e.g., via distillation) to provide a product consisting of 2-ethylhexanol, C 13 Alcohol and C 18 A fraction consisting of one or more alcohols.

[0071] In one embodiment, the method comprises hydrogenating 10 Alkenal, C 14 Alkenal, C 18 The method comprises forming a cross-aldol product consisting of C 10 Alcohol, C 14 Alcohol, C 18 The crude alcohol product also includes alkane components and other C 10 、C 14 、C 18In another embodiment, the method comprises separating the alkane component to leave a 10 Alcohol, C 14 Alcohol, C 18 In another embodiment, the bottom product is further refined (e.g., via distillation) to provide a product consisting of 2-propylheptanol, C 14 Alcohol and C 18 A fraction consisting of one or more alcohols.

[0072] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0073] Example

[0074] Table 1 below provides the composition of the purge stream recovered from an ethylene / octene polymerization production process. The weight percentages are based on the total weight of the purge stream.

[0075] Table 1

[0076] Purge flow (wt%) hydrocarbon solvents 6.1 <![CDATA[Branched C9 olefins]]> 4.8 1-octene 42.4 trans-4-octene 2.4 trans-3-octene and cis-4-octene (co-eluting) 9.9 cis-3-octene 2.0 Octane 0.6 trans-2-octene 17.0 cis-2-octene 14.8

[0077] The ligands used in the hydroformylation catalysts of Examples (IE) of the present invention are provided in Table 2 below.

[0078] Table 2

[0079]

[0080] A. Subjecting the Purge Stream to Hydroformylation Conditions

[0081] In such Figure 1 Hydroformylation conditions are provided in the reactor system shown. The reactor system is composed of three 1-liter stainless steel stirred tank reactors (Rx1, Rx2, Rx3) connected in series. Each reactor is equipped with a vertically mounted agitator and a circular tubular distributor near the bottom for feeding olefins and / or synthesis gas to the reactor. The ejector comprises a plurality of holes with sufficient size to provide the required airflow for entering the liquid body. Each reactor has a silicone oil shell as a way of controlling the reactor temperature. Reactors 1 to 2 and reactors 2 to 3 are also connected via pipelines to transfer any unreacted gas and allow a part of the liquid solution comprising aldehyde product and catalyst to flow to reactor 2 and from reactor 2 to reactor 3 (for example, via pressure difference or by pumping). Therefore, the unreacted olefins of reactor 1 are further hydroformylated in reactor 2 and subsequently in reactor 3. In an optional configuration, reactor 3 (Rx3) can be bypassed so that only two reactors are used.

[0082] Each reactor also includes a pneumatic level controller for maintaining the required liquid level in the reactor. Reactor 1 also includes a pipeline for introducing olefins, carbon monoxide and hydrogen through a distributor, while the supplementary carbon monoxide and hydrogen are transmitted to reactors 2 and 3 via a transfer line, which also transports unreacted gas from reactor 1 to reactor 2 and from reactor 2 to reactor 3. If necessary, each reactor also includes a vent for removing unreacted gas under controlled conditions. A portion of the liquid reaction solution is continuously pumped from the final reactor in series to a gasifier, which consists of a heating zone, wherein a portion of the volatile components is purged into a water-cooled condenser using a flowing gas (stripping gas) stream, where they can be collected as a liquid in a product receiver (crude product). Non-volatiles pass through an aqueous extraction zone consisting of a contact zone and a separation zone. The purpose of aqueous extraction is to extract acidic by-products, thereby preventing additional hydrolysis of the phosphite ligand, as described in US5741944. After aqueous extraction, the organic non-volatiles are pumped back to reactor 1 via a recirculation line.

[0083] The purge flow is introduced into the reactor 1 ( Figure 1 The "olefin" in the formula represents a purge stream. The purge stream is from an ethylene-octene polymerization process. The composition of the purge stream is provided in Table 1 above.

[0084] Two reactors (Rx1 and Rx2, with Rx3 bypassed) were used for the hydroformylation reaction (i.e., the purge stream was subjected to hydroformylation conditions). Two liters of a catalyst solution containing rhodium dicarbonyl acetylacetonate (394 ppm rhodium), Ligand A (Table 2 above) (0.7 wt%; 2.0 molar equivalents of Ligand A per mole of rhodium), tetraglyme (about 15 wt%), and mixed C4 aldehydes (about 85 wt%; based on the total weight of the C4 aldehydes, with a ratio of n-butyraldehyde to isobutyraldehyde of about 30:1) were charged to the reactor. Figure 1 The reactor system is shown. The reactors were then heated to 70°C under flowing syngas (H2:CO ratio = 1:1). The pressures in Reactor 1 and Reactor 2 were maintained at 244 psig and 220 psig, respectively. Spent solvent was fed to Reactor 1 at a rate of 138 g / hr. The gasifier system was operated with a stripping gas consisting of 1:1 syngas at a flow rate of 790 sLph; the gasifier pressure was maintained at 7 psig, and the catalyst temperature was 101°C.

[0085] After several days of continuous operation, butyraldehyde and tetraglyme were removed overhead, leaving a reactor process stream consisting of nonanal, aldehyde heavies (byproducts of the in-situ aldol condensation), unreacted olefins, and hydrocarbon solvent (continuously introduced as part of the spent solvent). A reaction product comprising nonanal (nonanal reaction product) was collected at a rate of 155 g / hr. The composition of the purge stream hydroformylation reaction product (interchangeably referred to as "nonanal product") is shown in Table 3 below.

[0086] Table 3. Composition of nonanal product. The weight percentages in Table 3 are based on the total weight of the nonanal product.

[0087] Table 3 - Nonanal Products

[0088] wt% <![CDATA[C9 aldehyde]]> 64.8 <![CDATA[Unreacted C8 olefins]]> 32.8 hydrocarbon solvents 2.4 N:I ratios of nonanal reaction products 13.8:1 (93.2% n-nonanal)

[0089] B. Cross-aldol condensation

[0090] A solution of isopropyl alcohol (IPA: 37.5 g), water (4.7 g) and NaOH (1.2 g) was charged into a 300 mL Parr reactor, purged three times with nitrogen, and sealed. The solution was heated to 60° C. under vigorous stirring. A mixture of (i) C4 aldehyde (25.2 g; 0.35 mol) and (ii) nonanal product (Table 3 above) (38.2 g; 0.175 mol n-nonanal) was introduced into the Parr reactor at a feed rate of 40 mL / min using a small laboratory pump. After the addition, the temperature was maintained at 60° C. for 1 hour under stirring to complete the cross-aldol condensation reaction and form a C8 alkenal, ... 13 Alkenal, C 18 The cross-aldol product is then cooled to 40°C and quenched with 0.9 equivalents of acetic acid.

[0091] The cross-aldol product was transferred to a separatory funnel and allowed to separate for 30 minutes. A small amount of aqueous phase (bottom phase) was removed. The cross-aldol condensation reaction (described in the above paragraph) was repeated three times and the combined organic phase (320.5 g) was concentrated on a rotary evaporator at 50° C. and 146 mbar. The residue (208 g) was washed with water (104 g), leaving an organic phase with a water content of 3.58 wt%. Additional IPA (60 g) was added to the organic phase to facilitate azeotropic drainage. The mixture was concentrated a second time on a rotary evaporator at 50° C. and 146 mbar to produce the cross-aldol product (187.8 g); the composition of the cross-aldol product is shown in Table 4 below.

[0092] Table 4. Composition of the crossed aldol products.

[0093] Table 4

[0094] Components Crossed aldol product (GC%) Isopropyl alcohol 2.69 <![CDATA[C4 aldehyde]]> 1.5 Octene 4.87 <![CDATA[C8 enal]]> 24.95 <![CDATA[C9 aldehyde]]> 3.03 <![CDATA[C 13 Alkenal]]> 15.82 <![CDATA[C 13 Alkenal]]> 20.67 <![CDATA[C 18 Alcohol]]> 0.68 <![CDATA[C 18 Alkenal]]> 6.76 Total Unknown 19.03

[0095] The conversions of the C4 aldehyde and crude C9 aldehyde products were 97.2% and 93.5%, respectively.

[0096] C. Hydrogenation of Crossed Aldol Products (Continuous)

[0097] The hydrogenation reaction was carried out in a tubular reactor comprising an 8-inch 3 / 8" stainless steel tube filled with 8 ml of Ni-3288 activated with hydrogen. Ni-3288 is a fixed bed hydrogenation catalyst comprising 60 wt% nickel-containing trilobal extrudates available from BASF. The cross-aldol product (from Table 4) was mixed with hydrogen and pumped through the Ni-3288 catalyst bed as a hydrogen-saturated liquid phase. The hydrogenation reaction was carried out at 140°C and 500 psig for 2.2 hours. -1 Liquid hourly space velocity (LHSV) and 600hr -1 The reaction was carried out at a gas hourly space velocity (GHSV) of 100 to produce a mixed alcohol / alkane product. The crude mixed alcohol / alkane product was collected in a cooled collection tank. The feed and mixed alcohol / alkane product compositions are shown in Table 5 below.

[0098] Table 5. Crossed Aldol Product (Feed) and Crude Alcohol Product from Continuous Hydrogenation The data in Table 5 demonstrate the efficient single pass conversion of aldehydes to alcohols during the continuous hydrogenation process.

[0099] Table 5

[0100]

[0101] D.C8-C 18 Separation of alcohol mixtures

[0102] The crude alcohol product (700 g) of Table 5 was charged into a 1 L round bottom still equipped with a heating jacket and connected to a rotating belt distillation column. A magnetic stirring bar was used to achieve good mixing and uniform boiling. In order to remove the light component fraction (wherein "light component" refers interchangeably to C1-C7 substances) from the mixed alcohol / alkane product, the column pressure was set to 100 mmHg and a reflux ratio of 8:1 was established. The temperature of the liquid in the still was in the range of 59.7°C (start of distillation) to 154.9°C (completion of light component fraction); during the same time period, the overhead vapor temperature was in the range of 34.4°C to 56.4°C. The light component fraction (78.2 g) was collected as the overhead distillate, leaving the C8-C7 as the bottom product. 18 Alcohol mixture (621.0 g). Light component fraction and C8-C 18 The composition of the alcohol mixture is shown in Table 6 below.

[0103] Table 6. Composition of light fraction and bottoms mixture

[0104] Components Light component fraction (GC%) Bottom mixture (GC%) Isopropyl alcohol 17.09 0.00 Mixed alkanes 11.25 0.00 Octane 53.35 0.00 <![CDATA[C8 aldehyde]]> 1.39 0.16 2EH 12.05 26.16 <![CDATA[C 13 Alcohol]]> 0.00 18.83 <![CDATA[C 13 Alcohol]]> 0.00 22.66 <![CDATA[C 18 Alcohol]]> 0.00 11.20 Total Unknown 4.82 19.67

[0105] E. Separate 2EH and C from the bottom mixture 13 、C 18

[0106] The bottom mixture (703 g) of Table 6 was charged to a 1 L kettle of a spinning belt distillation apparatus. The light fraction was removed using the distillation procedure described in Section D above. As the temperature of the overhead vapor increased ( Figure 2 The vapor temperature in the column is 0.04°C), 2-ethylhexanol (2-EH) begins to collect at the top of the column. Three 2-ethylhexanol (2EH) fractions are obtained, after which the distillation pressure is reduced to 20 mmHg to allow the collection of three C 13 The reflux ratio was always kept at 8:1. Two additional fractions were obtained to further concentrate the C 18 fractions (see Table 7 below).

[0107] Table 7 - Separation of alcohol from bottoms product

[0108]

[0109] The overhead vapor temperature and the kettle liquid temperature were closely monitored and used as the basis for collecting distillate fractions. 2EH purity was in the range of 92% to 95%, C 13 Product purity ranged from 67% to 88%.

[0110] If desired, the collected fractions can be further refined by distillation.

[0111] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but rather includes modifications of those embodiments including portions of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A method for reusing hydrocarbon materials purged during the production of ethylene / octene copolymers, the method comprising: providing a purge stream comprising octene isomers; wherein the purge stream comprises: (i) 20 wt% to 55 wt% of 1-octene, (ii) 20 wt% to 60 wt% of linear internal octene isomers, (iii) 2 wt% to 8 wt% of branched C8 olefins; as well as (iv) 5 wt% to 60 wt% of a solvent, wherein components (i)-(iv) total 100 wt% of the purge stream; contacting the purge stream with a hydroformylation catalyst under hydroformylation conditions, and The hydroformylation catalyst has a ligand A having the following structure: Ligand A wherein the hydroformylation catalyst further comprises a metal, and the metal is selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os), and combinations thereof; and A reaction product comprising nonanal is formed.

2. The method according to claim 1, comprising: adding an aldehyde selected from the group consisting of C4 aldehydes, C5 aldehydes, and combinations thereof to the reaction product comprising nonanal to form a mixture A; introducing an inorganic base catalyst into mixture A; heating mixture A and cross-aldol condensing mixture A; and Formed by a mixture selected from C8 alkenyl, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal and C 18 Crossed aldol products are composed of components of the group consisting of alkenals and combinations thereof.

3. The method according to claim 2, comprising: adding a C4 aldehyde to the reaction product comprising nonanal to form mixture A4; Introducing an inorganic base catalyst into mixture A4; heating mixture A4 and cross-aldol condensing mixture A4; and Formed by a mixture selected from C8 alkenyl, C 13 Alkenal, C 18 Crossed aldol products are composed of components of the group consisting of alkenals and combinations thereof.

4. The method according to claim 2, comprising: adding a C5 aldehyde to the reaction product comprising nonanal to form a mixture A5; Introducing an inorganic base catalyst into mixture A5; heating the mixture A5 and cross-aldol condensing the mixture A5; and Formed by selected from C 10 Alkenal, C 14 Alkenal, C 18 Crossed aldol products are composed of components of the group consisting of alkenals and combinations thereof.

5. The method according to any one of claims 3 to 4, wherein the inorganic base catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.

6. The method according to any one of claims 3 to 4, comprising: hydrogenating the crossed aldol product; and A crude alcohol product is formed.

7. The method according to claim 6, comprising: Hydrogenation is carried out by selecting from C8 alkenyl, C 13 Alkenal, C 18 Crossed aldol products consisting of members of the group consisting of alkenals and combinations thereof; and Formed by C8 alcohol, C 13 Alcohol, C 18 The crude alcohol product consists of alcohols and combinations thereof.

8. The method according to claim 7, comprising: Separate from the crude alcohol product 2-ethylhexanol, C 13 Alcohol and C 18 Alcohols constitute the group of alcohols.

9. The method according to claim 6, comprising: Hydrogenation is carried out by selecting C 10 Alkenal, C 14 Alkenal, C 18 Crossed aldol products consisting of members of the group consisting of alkenals and combinations thereof; and Formed by C 10 Alcohol, C 14 Alcohol, C 18 The crude alcohol product consists of alcohols and combinations thereof.

10. The method according to claim 9, comprising: Separate from the crude alcohol product 2-propylheptanol, C 14 Alcohol and C 18 Alcohols constitute the group of alcohols.

11. The method of claim 1 , wherein the metal is selected from the group consisting of rhodium, cobalt, and ruthenium.

12. The method of claim 1, wherein the metal is rhodium.

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