Process for producing mixed alcohols from an octene-containing purge stream

Abstract

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

Description

[Background technology]

[0001] In the production of ethylene / octene copolymers, ethylene, octene comonomer, and a polymerization catalyst are introduced into a polymerization reactor under suitable reaction conditions (in the presence of a solvent and a chain transfer agent) to obtain a polymerization product stream of ethylene / octene copolymer. The product stream is removed from the reactor. The product stream contains the ethylene / octene copolymer and hydrocarbon species, including unreacted monomer (ethylene), unreacted comonomer (octene), and other related hydrocarbons (hydrogen, ethane, methane, propane, pentane, hexane, and butane). The ethylene / octene copolymer is separated from the solvent, unreacted monomer, and unreacted comonomer by devolatilization. The granular ethylene / octene copolymer is then recovered after pelletization and cooling. After the ethylene / octene copolymer is separated from the product stream, the hydrocarbon species are either recycled to the polymerization reactor or purged from the system.

[0002] Regeneration of purged hydrocarbon species is one of the biggest challenges facing large-scale polyolefin production. For example, the conversion of octene comonomer in the polymerization of ethylene / octene copolymers is typically very low, e.g., 10-20%. This means that 80-90% of the octene can pass through the reactor without being converted to polymer.

[0003] Ideally, the octene comonomer is recycled back to the polymerization reactor. While recycling volatile monomers such as ethylene is very efficient, recycling octene is difficult, especially when other saturated hydrocarbons are present in the product stream. The boiling point of octene is very close to that of other saturated and unsaturated species present in the product stream, making separation of octene difficult. Fresh octene streams also contain other isomers of octene (1% to 5% by weight of octene isomers, based on the total weight of octene). Octene isomers typically do not react with ethylene in the polymerization process. As a result, octene isomers aggregate or otherwise "build up" in the continuous recycling of the recycle stream, reducing the efficiency of recycling as a feed stream. In this way, octene isomers can accumulate to up to 70% of the total recycle stream.

[0004] Therefore, it has been recognized in the art that there is currently a need for a method to utilize the hydrocarbon species of the purge stream without simply discarding them. There is a further need to utilize the octene monomer present in the purge stream. Summary of the Invention

[0005] The present disclosure provides a process. In one embodiment, the process includes providing a purge stream comprised of octene isomers. The process includes subjecting the purge stream to hydroformylation conditions and forming a reaction product comprised of nonanal. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic diagram of a hydroformylation reactor system for providing hydroformylation conditions according to one embodiment of the present disclosure. [Figure 2] 1 is a temperature-time graph of an overhead fraction separation according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0007] definition Any reference to the Periodic Table of the Elements is to that published by CRC Press, Inc., 1990-1991. References to element groups in this table are by the new notation for numbering groups.

[0008] For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent United States version thereof is so incorporated by reference), particularly with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0009] Numerical ranges disclosed herein include all values ​​between and including the lower and upper limits. Ranges containing explicit values ​​(e.g., 1 or 2, or 3-5, or 6, or 7) include all subranges between any two explicit values ​​(e.g., the 1-7 range above includes subranges of 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0010] Unless specifically stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0011] An "alcohol" is a compound containing a hydroxyl group (-OH) attached to a hydrocarbon radical.

[0012] An "aldehyde" is a compound containing a hydrocarbon radical and a carbonyl functional group (C=O) bonded to a hydrogen atom.

[0013] An "alkene" is a hydrocarbon containing a carbon-carbon double bond.

[0014] As used herein, the terms "blend" or "polymer blend" refer to a blend of two or more polymers. Such blends may or may not be miscible (not phase separated at the molecular level). Such blends may or may not be phase separated. Such blends 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.

[0015] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0016] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless specifically stated to the contrary. In contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of any succeeding description, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not expressly delineated or listed. The term "or," unless otherwise stated, refers to the listed members individually as well as in any combination. The use of the singular includes the use of the plural, and vice versa.

[0017] An "enal" is an aldehyde compound containing a carbon-carbon double bond. Enals can be formed by aldol (or cross-aldol) condensation of an aldehyde, followed by dehydration of the resulting intermediate compound. A non-limiting example of an enal is 2-ethylhexenal, which results from the self-condensation of a C4 aldehyde, as shown below.

[0018] [ka]

[0019] An "enol" is an alcohol containing a carbon-carbon double bond. Enols can be formed by partial hydrogenation of an enal.

[0020] 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 may optionally 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" may be used interchangeably.

[0021] A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. A "hydrocarbonyl" (or "hydrocarbonyl group") is a hydrocarbon having a valence (typically monovalent).

[0022] As used herein, the term "1-octene" has the molecular formula CH 16 1-octene is an unsaturated hydrocarbon α-olefin having the following structure (A):

[0023] [ka]

[0024] As used herein, the term "octene isomers" refers to isomers of the molecular formula CH 16and the unsaturation (double bond) is not in the alpha position. In other words, the term "octene isomer" refers to any octene excluding 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.

[0025] As used herein, the term "linear internal octene isomer" refers to a straight-chain, unsaturated hydrocarbon composed of an eight-carbon chain, wherein the unsaturation (double bond) is not 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" refers to a hydrocarbon having the molecular formula CH 16 and a main chain length of 7 or less carbon atoms. In contrast to the linearity of Structure A, branched C8 olefins contain at least one hydrocarbon radical directly attached to the main chain. Non-limiting examples of branched C8 olefins include methylheptenes, such as 3-methyl-2-heptene, 3-methyl-3-heptene, 5-methyl-2-heptene, and 5-methyl-3-heptene. Additional non-limiting examples of branched C8 olefins include dimethylhexenes, such as 3,4-dimethyl-2-hexene, 3,4-dimethyl-3-hexene, and 2,3-dimethyl-3-hexene. Further non-limiting examples include ethylhexenes, such as 2-ethyl-1-hexene.

[0026] An "olefin" is an unsaturated aliphatic hydrocarbon containing a carbon-carbon double bond.

[0027] A "polymer" is a compound prepared by polymerizing monomers, whether of the same or different types, that provide multiple and / or repeating "units" or "mer units" that, in polymerized form, constitute the polymer. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to a polymer prepared from at least two types of monomer. Polymer also encompasses all forms of copolymers, e.g., random, block, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" refer to the aforementioned copolymers prepared by polymerizing ethylene or octene with one or more additional polymerizable α-olefin monomers, respectively. While polymers are often referred to as "made of" one or more specific monomers, "based on" a specific monomer or monomer type, "containing" a specific monomer content, etc., it should be noted that in this context, the term "monomer" is understood to refer to the polymerized residue of a specific monomer, and not to the unpolymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0028] Test Method Gas Chromatography (GC).

[0029] The composition of the spent solvent and hydroformylation reaction product is determined by gas chromatography (GC) using the following conditions:

[0030] [Table 1]

[0031] Quantifications in the data in Table 1 (in the Examples section below) and Section A of the Examples section are based on weight percent using response factors derived from standard solutions of known concentrations.

[0032] The compositions of the cross-aldol reaction products and crude alcohol products are determined by both GC and gas chromatography / mass spectrometry (GC / MS) using the following conditions:

[0033] [Table 2]

[0034] Quantification in Sections B-E of the Examples section is based on GC area percent (synonymously referred to as "GC area" or "GC%") from the FID signal. Confirmation of peak identity / component structure is based on Electron Ionization Mass Selective Detector signals matched to the National Institute of Standards and Testing library.

[0035] N:I Ratio. The hydroformylation reaction of olefins having three or more carbon atoms produces a mixture of both linear and branched isomers. As used herein, the term "N:I ratio" is the ratio of linear or normal (N) aldehyde isomers to branched or isoaldehyde (I) isomers. The N:I ratio is calculated by dividing the weight percent normal aldehyde concentration by the weight percent isoaldehyde concentration. The weight percent concentration of each aldehyde isomer is determined by gas chromatography (GC).

[0036] Detailed Description The present disclosure provides a process comprising providing a purge stream comprised of octene isomers and subjecting the purge stream to hydroformylation conditions to form a reaction product comprised of nonanal.

[0037] The process includes providing a purge stream. The purge stream comprises octene isomers. As used herein, a "purge stream" is one of several fractions separated or otherwise recovered from the effluent exiting the polymerization reactor after the polymerization reaction has occurred. The liquid effluent exiting the polymerization reactor contains a solid (particulate) polymer product, which is removed. A recycle stream is also removed from the effluent, which is 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 monomer, including octene isomers, and other hydrocarbons utilized in the polymerization reaction. It will be understood that the purge stream is free of, or substantially free of, solid polymer product.

[0038] In one embodiment, the purge stream is the effluent from a polymerization reactor in which ethylene is copolymerized with octene. The purge stream contains unreacted octene isomers and other hydrocarbons.

[0039] In one embodiment, the purge flow comprises: (i) 20% to 55% by weight, or 25% to 50% by weight, of 1-octene; (ii) 20% by weight to 60% by weight of linear internal octene isomers; (iii) 2 wt% to 8 wt% branched C8 olefins, and (iv) 5% to 60% by weight of a hydrocarbon solvent, where the weight percentages are based on the total weight of the purge stream, it being understood that components (i) through (iv) add up to 100% by weight of the purge stream.

[0040] In one embodiment, the process includes removing ethylene that may be present in the purge stream. The purge stream is sparged with nitrogen gas to eliminate the presence of ethylene in the purge stream. The purge stream is free or substantially free of ethylene monomer, i.e., ethylene is from 0 wt. % or from greater than 0 wt. % to less than 0.5 wt. % based on the total weight of the purge stream.

[0041] The process includes subjecting the purge stream to hydroformylation conditions. As used herein, "hydroformylation conditions" are the reactor conditions (including temperature and pressure) in one or more reactors, reactants (alkene, solvent, hydroformylation catalyst, and a supply of synthesis gas (also known as "syngas"), which is hydrogen (H) and carbon monoxide (CO) in a molar ratio of H:CO of 1:10 to 10:1 or 1:1), that promote the attachment of a formyl group (-CH=O) and a hydrogen atom to the carbon-carbon double bond of an alkene (i.e., an olefin) to produce an aldehyde. Hydroformylation can be carried out in the liquid state, the gas state, and in a continuous, semi-continuous, or batch process, and can include liquid recycle and / or gas recycle operations.

[0042] In one embodiment, the step of subjecting the purge stream to hydroformylation conditions comprises contacting the purge stream with a hydroformylation catalyst under hydroformylation conditions. The hydroformylation catalyst is a metal-organophosphite ligand complex catalyst. Non-limiting examples of suitable metals include rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (O), and mixtures thereof. In one embodiment, the metal is selected from rhodium, cobalt, and ruthenium, or is selected as rhodium. The ligand is an organomonophosphite ligand, an organopolyphosphite ligand, or a combination thereof.

[0043] In one embodiment, the ligand is an organopolyphosphite ligand. The organopolyphosphite ligand is composed of multiple phosphite groups, each of which contains one trivalent phosphorus atom bonded to three hydrocarbyloxy radicals. The hydrocarbyloxy radicals that connect and bridge two phosphite groups are referred to as "divalent hydrocarbyldioxy radicals." These bridging diradicals are not limited to any particular hydrocarbyl species. Meanwhile, the hydrocarbyloxy radicals that are pendant from the phosphorus atom and do not bridge two phosphite groups (i.e., terminal, non-bridging) must each consist essentially of an aryloxy radical. "Aryloxy" refers to either of two types of aryloxy radicals: (1) a monovalent aryl radical bonded to a single ether linkage, as in -O-aryl, where the aryl group contains either a single aromatic ring or multiple aromatic rings that are fused together and linked directly or indirectly (such that different aromatic groups are bonded to a common group such as methylene or ethylene moieties); or (2) a divalent arylene radical bonded to two ether linkages, as in -O-arylene-O- or -O-arylene-arylene-O-, where the arylene group contains either a single aromatic ring or multiple aromatic rings that are fused together and linked directly or indirectly (such that different aromatic groups are bonded to a common group such as methylene or ethylene moieties). In one embodiment, an aryloxy group contains one aromatic ring or two to four fused or linked aromatic rings having from 5 to 20 carbon atoms, e.g., phenoxy, naphthyloxy, or biphenoxy, as well as arylenedioxy radicals such as phenylenedioxy, naphthylenedioxy, and biphenylenedioxy. Any of these radicals and groups can be unsubstituted or substituted.

[0044] In one embodiment, the organopolyphosphite ligand contains two, three, or more phosphite groups. Mixtures of such ligands can be used if desired. Achiral organopolyphosphites are preferred. Representative organopolyphosphites include those of formula (I):

[0045] [ka] wherein X represents a substituted or unsubstituted n-valent organic bridging radical containing 2 to 40 carbon atoms, and each R 1 are the same or different and represent divalent organic radicals containing 4 to 40 carbon atoms, and each R 2 are the same or different and represent substituted or unsubstituted monovalent hydrocarbon radicals containing 1 to 24 carbon atoms, and a and b may be the same or different and each have a value from 0 to 6, provided that the sum of a+b is from 2 to 6 and n is equal to a+b. Of course, when a has a value of 2 or more, each R 1 The radicals may be the same or different, and when b has a value of 1 or greater, each R 2 It should be understood that the radicals can be the same or different.

[0046] In one embodiment, the ligand is [[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bi-s(oxy)]bis-dibenzo[d,f][1,3,2]-dioxaphosphepine, having the formula of Ligand A shown below:

[0047] [ka]

[0048] Subjecting the purge stream to hydroformylation conditions is accomplished by a hydroformylation process that includes feeding the purge stream along with syngas (carbon monoxide and hydrogen) and a hydroformylation catalyst into a series-connected multiple reactor system, i.e., the output of a first reaction zone is provided as the input to a subsequent reaction zone.

[0049] The H2:CO molar ratio of gaseous hydrogen to carbon monoxide is 1:10 to 10:1. The hydroformylation process is carried out at a reaction temperature of 50°C to 100°C, and the total gas pressure, consisting of the purge stream, carbon monoxide, and hydrogen, ranges from 1 psia (6.9 kPa) to 2,000 psia (13,800 kPa).

[0050] 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 paraffins including methylene chloride; and paraffinic hydrocarbons such as heptane. In one embodiment, the solvent is the aldehyde product and / or oligomers of the aldehyde product and the reactive olefin or olefins.

[0051] In one embodiment, the hydroformylation process is carried out continuously in a multistage reactor designed with internal physical barriers creating two or more theoretical reactive stages or zones per vessel. The hydroformylation process includes (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 suitable reaction temperature and pressure conditions for hydroformylating the purge stream, (c) supplying make-up amounts of the purge stream, carbon monoxide, and hydrogen to the reaction medium as those reactants are consumed, and (d) recovering the desired aldehyde hydroformylation product.

[0052] The continuous hydroformylation process may be carried out in a single pass mode in which the vaporous mixture, including the unreacted purge stream, and the vaporized aldehyde product are removed from the liquid reaction mixture from which the aldehyde product is recovered, and make-up olefinic starting material, carbon monoxide, and hydrogen are fed to the liquid reaction medium for a next single pass without recycle of unreacted olefinic starting material.

[0053] Subjecting the purge stream to the aforementioned hydroformylation conditions results in the formation of a reaction product comprised of nonanal. Because the purge stream contains octene isomers, subjecting the purge stream to hydroformylation conditions results in the formation of a reaction product comprised of nonanal. "Nonanal" is an aldehyde containing nine carbon atoms. The purge stream is a mixture of alkenes (primarily 1-octene and octene isomers) and alkanes, and as a result, the reaction product from the hydroformylation reaction contains 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.

[0054] The process includes adding an aldehyde selected from a C4 aldehyde, a C5 aldehyde, and combinations thereof (hereinafter, "C4 / C5 aldehyde") to a reaction product comprised of nonanal (hereinafter, "nonanal product") to form a mixture, Mixture A. The process includes cross-aldol condensing Mixture A and forming a cross-aldol product. The cross-aldol product is a C8 enal, C 10 Henard, C. 13 Henard, C. 14 Henard, C. 18 The cross-aldol product may also contain alcohol, solvent, water, unreacted aldehyde, and combinations thereof.

[0055] The crossed aldol condensation step involves combining the nonanal product with a C4 / C5 aldehyde using 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 between 30°C and 100°C, whereby the inorganic base catalyzes the aldol condensation reaction to form the crossed aldol product and a water by-product.

[0056] In one embodiment, the process includes adding a C4 aldehyde and adding the nonanal product to an inorganic base catalyst (such as sodium hydroxide) and an alcohol (such as isopropyl alcohol) to form a reaction mixture, Mixture A4. The process includes heating 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 to produce the C8 enal, C 13 Henard, C. 18 The crossed aldol product is formed from an enal selected from the group consisting of an alcohol solvent, water, unreacted aldehyde, other C8, C9, C10, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C30, C41, C50, C60, C71, C82, C93, C94, C95, C19, C18, C19, C21, C22, C30, C41, C50, C61, C72, C83, C94, C95, C96, C97, C98, C99, C19, C19, C21, C32, C43, C54, C65, C76, C87, C98, C99, C19, C19, C22, C33, C44, C 13 , and C 18 In one embodiment, the cross-aldol product may further comprise a majority of C enal, C 13 Enal, and C 18 Including enals, "major amount" is greater than 50% of the total GC area of ​​the cross-aldol reaction products.

[0057] In one embodiment, the process includes adding a C5 aldehyde and adding the nonanal product to an inorganic base catalyst (such as sodium hydroxide) and an alcohol (such as isopropyl alcohol) to form a reaction mixture, Mixture A5. The process includes heating 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 to form C5. 10 Henard, C. 14 Henard, C. 18 The crossed aldol product is formed by removing the alcohol solvent, water, optionally unreacted aldehyde, and other C 10 , C 14 , C 18 In one embodiment, the cross-aldol product may further comprise a majority of C 10 Henard, C. 14 Enal, and C 18 Including enal C, "major amount" is greater than 50% of the total GC area of ​​the cross-aldol reaction products.

[0058] The process involves hydrogenating the crossed aldol product, which is a C8 enal, C 10 Henard, C. 13 Henard, C. 14 Henard, C. 18 The process includes forming a crude alcohol product, which includes C8 alcohols, C8 enals, and combinations thereof. 10 Alcohol, C 13 Alcohol, C 14 Alcohol, C 18 The crude alcohol product also contains alkane components and other C, C 10 , C 13 , C 14 , C 18 In one embodiment, the crude alcohol product comprises a majority of C8 alcohols, C 10 Alcohol, C 13Alcohol, C 14 Alcohol, and C 18 Including alcohol, "major amount" is greater than 50% of the total GC area of ​​the crude alcohol product.

[0059] In one embodiment, the hydrogenation of the crossed 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 crossed aldol product is 0.1 h -1 (hr -1 )~8 hours -1 , or 0.5 hours -1 ~3 hours -1 The gas hourly space velocity (GHSV) of hydrogen is -1 , 10,000 hours -1 , or 200 hours -1 ~4,000 hours -1 The hydrogenation process is carried out 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.

[0060] In one embodiment, the process comprises the steps of: 13 Henard, C. 18 The process involves hydrogenating the cross-aldol products composed of C8 alcohols, C8 enals, and combinations thereof. 13 Alcohol, C 18 The crude alcohol product may also include forming a crude alcohol product comprising alkane components and other C, C, C 13 , C 18 In a further embodiment, the process separates the alkane components and other species to produce C8 alcohols, C 13 Alcohol, C 18In another embodiment, the bottoms product is further purified (e.g., via distillation) to obtain 2-ethylhexanol, C 2 -ethylhexanol, C 3 -methylhexanol, C 4 -methylhexanol, C 5 -methylhexanol, C 6 -methylhexanol, C 7 -methylhexanol, C 8 -methylhexanol, C 9 -methylhexanol, C 10 -methylhexanol, C 11 -methylhexanol, C 1 13 Alcohol, and C 18 providing a fraction comprised of one or more of the alcohols.

[0061] In one embodiment, the process comprises: 10 Henard, C. 14 Henard, C. 18 The process involves hydrogenating the cross-aldol products composed of enals, and combinations thereof. 10 Alcohol, C 14 Alcohol, C 18 The crude alcohol product may also include forming a crude alcohol product comprising alkane components and other C 10 , C 14 , C 18 In a further embodiment, the process separates the alkane components to form C 10 Alcohol, C 14 Alcohol, C 18 In another embodiment, the bottoms product is further purified (e.g., via distillation) to produce 2-propylheptanol, C 2 -propylheptanol, C 3 -propylheptanol, C 4 -propylheptanol, C 5 -propylheptanol, C 6 -propylheptanol, C 7 -propylheptanol, C 8 -propylheptanol, C 9 -propylheptanol, C 10 -propylheptanol, C 1 14 Alcohol, and C 18 providing a fraction comprised of one or more of the alcohols.

[0062] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples. [Example]

[0063] The compositions of the purge streams recovered from the ethylene / octene polymerization manufacturing process are provided below in Table 1. The weight percentages are based on the total weight of the purge stream.

[0064] [Table 3]

[0065] The hydroformylation catalyst ligands used in the inventive examples (IE) are provided in Table 2 below.

[0066] [Table 4]

[0067] A. Subjecting the Purge Stream to Hydroformylation Conditions Hydroformylation conditions are provided within the reactor system, as shown in Figure 1. The reactor system consists of three 1-liter stainless steel stirred-tank reactors (Rx1, Rx2, and Rx3) connected in series. Each reactor is equipped with a vertically mounted agitator and a circular tubular sparger near the bottom to feed olefins and / or synthesis gas into the reactor. The sparger contains multiple holes large enough to provide the desired gas flow within the liquid body. Each reactor has a silicone oil shell as a means of controlling the reactor temperature. Reactors 1 to 2 and 2 to 3 are further connected via lines to transfer any unreacted gas and to allow a portion of the liquid solution containing the aldehyde product and catalyst to flow (e.g., via a pressure differential or by pumping) from Reactor 1 to Reactor 2 and from Reactor 2 to Reactor 3. Thus, unreacted olefins in Reactor 1 are further hydroformylated in Reactor 2 and subsequently in Reactor 3. In an alternative configuration, reactor 3 (Rx3) can be bypassed so that only two reactors are used.

[0068] Each reactor also contains a pneumatic liquid level controller for maintaining a desired liquid level within the reactor. Reactor 1 further contains lines for introducing olefins, carbon monoxide, and hydrogen through a sparger, while makeup carbon monoxide and hydrogen are sent to reactors 2 and 3 via transfer lines that also carry unreacted gas from reactor 1 to reactor 2 and from reactor 2 to reactor 3. Each reactor also contains a blow-off vent, if desired, for controlled removal of unreacted gas. A portion of the liquid reaction solution is continuously pumped from the final reactor in series to a vaporizer, which consists of a heating zone that utilizes a flow of fluidizing gas (strip gas) to sweep a portion of the volatile components into a water-cooled condenser, where they can be collected as liquid in a product receiver (crude product). Non-volatile materials pass through an aqueous extraction zone, consisting of a contact region and a separation zone. The purpose of the aqueous extraction is to extract the acidic by-products, thereby preventing further hydrolysis of the phosphite ligand, as described in U.S. Patent No. 5,741,944. After the aqueous extraction, the organic non-volatile materials are pumped back to reactor 1 through a recycle line.

[0069] A purge stream is introduced into reactor 1 ("Olefins" in FIG. 1 represents the purge stream). The purge stream is from an ethylene-octene polymerization production process. The composition of the purge stream is provided in Table 1 above.

[0070] The hydroformylation reaction (i.e., subjecting the purge stream to hydroformylation conditions) is carried out using two reactors (Rx1 and Rx2, with Rx3 bypassed). Two liters of a catalyst solution composed of 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), tetraethylene glycol dimethyl ether (approximately 15 wt. %), and mixed C4 aldehydes (approximately 85 wt. % n-butyraldehyde to isobutyraldehyde ratio of approximately 30:1, based on the total weight of C4 aldehydes) is charged to the reactor system shown in Figure 1. The reactors are then heated to 70°C under flowing syngas (H2:CO ratio = 1:1). The pressures of Reactor 1 and Reactor 2 are maintained at 244 psig and 220 psig, respectively. Spent solvent is fed to reactor 1 at a rate of 138 grams / hour. The vaporizer system is operated at a flow rate of 790 sLph with strip gas composed of 1:1 syngas and vaporizer pressure is maintained at 7 psig with a catalyst temperature of 101°C.

[0071] After several days of continuous operation, butyraldehyde and tetraethylene glycol dimethyl ether are removed overhead, leaving a reactor process fluid composed of nonanal, aldehyde heavies (a by-product of the in situ dol condensation), unreacted olefins, and hydrocarbon solvent (continuously introduced as part of the spent solvent). A reaction product composed of nonanal (nonanal reaction product) is collected at a rate of 155 grams / hour. The composition of the purge stream hydroformylation reaction product (synonymously referred to as "nonanal product") is shown in Table 3 below.

[0072] Table 3. Composition of nonanal product. Weight percentages in Table 3 are based on the total weight of nonanal product.

[0073] [Table 5]

[0074] B. Crossed aldol condensation A solution of isopropanol (IPA, 37.5 g), water (4.7 g), and NaOH (1.2 g) was charged to a 300 mL Parr reactor, purged three times with nitrogen, and sealed. The solution was heated to 60°C with stirring. A mixture of (i) the C4 aldehyde (25.2 g, 0.35 mol) and (ii) the nonanal product (Table 3 above) (38.2 g, 0.175 mol of n-nonanal) was introduced into the Parr reactor with a small laboratory pump at a feed rate of 40 mL / min. After addition, the temperature was maintained at 60°C for 1 hour with stirring to complete the cross-aldol condensation reaction and produce the C8 enal, C 13 Henard, C. 18 A cross-aldol product composed of the enal and other species is formed, which is then cooled to 40° C. and quenched with 0.9 equivalents of acetic acid.

[0075] The crossed aldol product is transferred to a separatory funnel and allowed to separate for 30 minutes. The small aqueous phase (bottom phase) is removed. The crossed aldol condensation reaction (described in the paragraph above) is repeated three times, and the combined organic phase (320.5 g) is concentrated on a rotary evaporator at 50 °C and 146 mbar. The residue (208 g) is washed with water (104 g), leaving an organic phase with a water content of 3.58 wt. %. Additional IPA (60 g) is added to the organic phase to facilitate the azeotropic removal of water. The mixture is concentrated once more on a rotary evaporator at 50 °C and 146 mbar to obtain the crossed aldol product (187.8 g). The composition of the crossed aldol product is shown in Table 4 below.

[0076] [Table 6]

[0077] The conversions of the C4 aldehyde and crude C9 aldehyde products are 97.2% and 93.5%, respectively.

[0078] C. Hydrogenation of Cross-Aldol Products (Continuous) The hydrogenation reaction is carried out in a tube reactor containing an 8-inch piece of 3 / 8-inch stainless steel tubing packed with 8 mL of hydrogen-activated Ni-3288. Ni-3288 is a hydrogenation fixed-bed catalyst composed of 60 wt. % nickel-containing trilobe extrudates available from BASF. The cross-aldol product (from Table 4) is mixed with hydrogen and pumped as a hydrogen-saturated liquid phase through the Ni-3288 catalyst bed. The hydrogenation reaction is carried out at 140°C and 500 psig for 2.2 hours. -1 Liquid hourly space velocity (LHSV) and 600 hours -1 The feed is run at a gas hourly space velocity (GHSV) of 1000 psi to produce a mixed alcohol / alkane product. The crude mixed alcohol / alkane product is collected in a cooled catch pot. The feed and mixed alcohol / alkane product compositions are shown in Table 5 below.

[0079] Table 5. Cross-aldol product (feed) and crude alcohol product from continuous hydrogenation. The data in Table 5 show the effective single-pass conversion of aldehyde to alcohol in the continuous hydrogenation process.

[0080] [Table 7]

[0081] D.C8-C 18 Separation of alcohol mixtures The crude alcohol product (700 g) from Table 5 is charged to a 1 L round-bottom distillation kettle fitted with a heating mantle and connected to a spinning band distillation column. A magnetic stir bar is used to achieve good mixing and uniform boiling. To remove the light fraction ("light" synonymously refers to C1-C7 species) from the mixed alcohol / alkane product, the column pressure is set to 100 mmHg and an 8:1 reflux ratio is established. The temperature of the liquid in the kettle ranges from 59.7°C (beginning of distillation) to 154.9°C (end of light cut), and the overhead vapor temperature ranges from 34.4°C to 56.4°C during this same period. The light fraction (78.2 g) is collected as the overhead fraction and the C8-C7 species are collected as the bottoms product.18 A mixture of alcohols (621.0 g) remains. 18 The composition of the alcohol mixture is shown in Table 6 below.

[0082] [Table 8]

[0083] E. 2EH from the bottom mixture, C 13 , C 18 Separation of The bottom mixture (703 g) from Table 6 is charged to the 1 L kettle of a spinning band distillation apparatus. The distillation procedure described in Section D above is used to remove the light fraction. As the overhead vapor temperature increases (vapor temperature in Figure 2), 2-ethylhexanol (2-EH) begins to collect overhead. Three 2-ethylhexanol (2EH) fractions are removed, and then the distillation pressure is reduced to 20 mm Hg to separate the three C 13 Allow the distillates to collect. The reflux ratio is maintained at 8:1 throughout. Two additional distillates are removed to form C in the kettle. 18 The fractions are further concentrated (see Table 7 below).

[0084] [Table 9]

[0085] Both the overhead vapor temperature and the kettle liquid temperature are closely monitored and used as the basis for collecting the distillate fractions. The purity of 2EH ranges from 92 to 95%. 13 The purity of the product ranges from 67 to 88%.

[0086] The collected fractions can be further purified via distillation, if desired.

[0087] The present disclosure is not limited to the embodiments and examples contained herein, but is expressly intended to include portions of the embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims. (Aspect) (Aspect 1) A process comprising: providing a purge stream comprising octene isomers; subjecting said purge stream to hydroformylation conditions; forming a reaction product comprising nonanal. (Aspect 2) 20% to 55% by weight of 1-octene; 20% to 60% by weight of linear internal octene isomers; 2% to 8% by weight of branched C 8 an olefin; 2. The process of embodiment 1, comprising providing a purge stream consisting of: 5 wt.% to 60 wt.% solvent. (Aspect 3) 3. The process of any one of the preceding aspects, wherein the subjecting comprises contacting the purge stream with a hydroformylation catalyst under hydroformylation conditions, the hydroformylation catalyst comprising a metal and an organophosphite ligand. (Aspect 4) C 4 Aldehyde, C 5 adding an aldehyde selected from the group consisting of aldehydes, and combinations thereof, to the reaction product containing nonanal to form mixture A; introducing an inorganic base catalyst into mixture A; heating mixture A and crossed aldol condensation mixture A; C 8 Henard, C. 10 Henard, C. 13 Henard, C. 14 Enal, and C 18 and forming a crossed aldol product comprised of components selected from the group consisting of: enals, aldehydes, methyl aldehydes, methyl methyl ketones, ... (Aspect 5) The reaction product containing nonanal is 4 adding an aldehyde to form mixture A4; introducing an inorganic base catalyst into mixture A4; heating mixture A4 and crossed aldol condensation mixture A4; C 8 Henard, C. 13 Henard, C. 18 and forming a crossed aldol product comprised of components selected from the group consisting of: enals, and combinations thereof. (Aspect 6) The reaction product containing nonanal is 5 adding an aldehyde to form mixture A5; introducing an inorganic base catalyst into mixture A5; heating mixture A5 and crossed aldol condensation mixture A5; C 10 Henard, C. 14 Henard, C. 18 and forming a crossed aldol product comprised of components selected from the group consisting of: enals, and combinations thereof. (Aspect 7) Aspect 7. The process of any one of aspects 5 or 6, wherein the inorganic base catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof. (Aspect 8) hydrogenating the crossed aldol product; forming a crude alcohol product. (Aspect 9) C 8 Henard, C. 13 Henard, C. 18 hydrogenating a cross-aldol product comprised of a component selected from the group consisting of enals, and combinations thereof; C 8 Alcohol, C 13 Alcohol, C 18 forming a crude alcohol product comprised of the alcohol, the hydroxybenzoate ... (Aspect 10) 2-ethylhexanol, C 13 Alcohol, and C 18 10. The process of embodiment 9, comprising separating the alcohol selected from the group consisting of alcohols. (Aspect 11) C 10 Henard, C. 14 Henard, C. 18 hydrogenating a cross-aldol product comprised of a component selected from the group consisting of enals, and combinations thereof; C 10 Alcohol, C 14 Alcohol, C 18 forming a crude alcohol product comprised of the alcohol, the hydroxybenzoate ... (Aspect 12) From the crude alcohol product, 2-propylheptanol, C 14 Alcohol, and C 18 12. The process of embodiment 11, comprising separating the alcohol selected from the group consisting of alcohols.

Claims

1. A process comprising: providing a purge stream comprising octene isomers; subjecting said purge stream to hydroformylation conditions; forming a reaction product comprising nonanal; C ４ Aldehyde, C ５ adding an aldehyde selected from the group consisting of aldehydes, and combinations thereof, to the reaction product containing nonanal to form mixture A; introducing an inorganic base catalyst into mixture A; heating mixture A and subjecting it to a cross-aldol condensation; C ８ Enal, C. １０ Enal, C. １３ Enal, C. １４ Enal, and C １８ forming a cross-aldol product comprised of components selected from the group consisting of enals, and combinations thereof; The process includes: (i) 20% by weight to 55% by weight of 1-octene; (ii) 20% to 60% by weight of linear internal octene isomers; (iii) 2% to 8% by weight of branched C ８ an olefin; and (iv) 5 wt.% to 60 wt.% solvent, wherein the combined wt.% of components (i)-(iv) is 100 wt.%, based on the total weight of the purge stream.

3. 3. The process of claim 1 or 2, wherein said subjecting comprises contacting said purge stream with a hydroformylation catalyst under hydroformylation conditions, said hydroformylation catalyst comprising a metal and an organophosphite ligand.

4. The reaction product containing nonanal is ４ adding an aldehyde to form mixture A4; introducing an inorganic base catalyst into mixture A4; heating mixture A4 and subjecting it to a cross-aldol condensation; C ８ Enal, C. １３ Enal, C. １８ and forming a cross-aldol product comprised of components selected from the group consisting of: enals, aldehydes, methyl aldehydes, methyl methyl ester ...

5. The reaction product containing nonanal is ５ adding an aldehyde to form mixture A5; introducing an inorganic base catalyst into mixture A5; heating mixture A5 and subjecting it to a cross-aldol condensation; C １０ Enal, C. １４ Enal, C. １８ and forming a cross-aldol product comprised of components selected from the group consisting of: enals, aldehydes, methyl aldehydes, methyl methyl ester ...

6. 6. The process of claim 4, wherein the inorganic base catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.

7. hydrogenating the crossed aldol product; and forming a crude alcohol product.

8. C ８ Enal, C. １３ Enal, C. １８ hydrogenating a cross-aldol product comprised of a component selected from the group consisting of enals, and combinations thereof; C ８ Alcohol, C １３ Alcohol, C １８ and forming a crude alcohol product consisting of alcohols, and combinations thereof.

9. From the crude alcohol product, 2-ethylhexanol, C １３ Alcohol, and C １８ 9. The process of claim 8, comprising separating an alcohol selected from the group consisting of alcohols.

10. C １０ Enal, C. １４ Enal, C. １８ hydrogenating a cross-aldol product comprised of a component selected from the group consisting of enals, and combinations thereof; C １０ Alcohol, C １４ Alcohol, C １８ and forming a crude alcohol product consisting of alcohols, and combinations thereof.

11. From the crude alcohol product, 2-propylheptanol, C １４ Alcohol, and C １８ 11. The process of claim 10, comprising separating an alcohol selected from the group consisting of alcohols.

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