Process for the production of branched products

Abstract

To provide a method for producing an isomerized olefin, a branched aldehyde, a branched alcohol, a branched surfactant and other branched derivatives by isomerization, hydroformylation, hydrogenation, surfactant formation reaction and other derivative formation reaction using an inexpensive α - olefin as a raw material.SOLUTION: Providing a first catalyst comprising an organometallic complex comprising at least one of rhodium and cobalt and at least one organic phosphorus ligand, providing a mixture of one or more C4-C36 linear alpha olefins, providing a gaseous phase comprising carbon monoxide, and isomerizing the linear alpha olefins with the first catalyst at a first pressure in the presence of the carbon monoxide; The method for producing a branched product includes a step of producing an isomerized olefin and a step of hydroformylating the isomerized olefin with a first catalyst in the presence of carbon monoxide and hydrogen at a second pressure different from a first pressure to produce a branched aldehyde.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to branched aldehydes, branched alcohols, and methods for producing one or more branched products.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This patent application is a non-provisional PCT application of, and claims the benefit of the filing date of, co-pending U.S. Provisional Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (2020, Dec. 17; 17.12.20).

[0003] This patent application is a non-provisional PCT application of and claims the benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (2020, June 5; 05.06.20).

[0004] This patent application is a non-provisional PCT application of and claims the benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20).

[0005] This patent application is a non-provisional PCT application of and claims the benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (2020, June 5; 05.06.20).

[0006] This patent application is a non-provisional continuation-in-part PCT application of co-pending U.S. non-provisional patent application No. 17 / 246,580 entitled "Alcohols Production," filed on April 30, 2021 (April 30, 2021; 30.04.2021), which claims the benefit of the filing date of co-pending U.S. provisional patent application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20).

[0007] This patent application is a non-provisional continuation-in-part of and claims the benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on April 30, 2021 (April 30, 2021; 30.04.2021), which claims the benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20).

[0008] This patent application is a non-provisional continuation-in-part PCT application of co-pending U.S. non-provisional patent application Ser. No. 17 / 331,371 entitled "Branched Compounds," filed May 26, 2021 (2021, 5 / 26; 26.05.2021), which claims the benefit of the filing date of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Branched Compounds," filed on December 17, 2020 (2020, December 17; 17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (2020, 6 / 5; 05.06.20), which claims benefit to U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on April 30, 2021 (2021, 4 / 30; 30.04.2021), which claims benefit to U.S. Patent Application No. 17 / 246,580 entitled "Alcohols Production," filed on June 5, 2020 (2020, 6 / 5; 05.06.20), which claims benefit to U.S. Patent Application No. International application PCT / US21 / 30341, entitled "Alcohols Production," filed April 30, 2021 (2021, April 30; 30.04.2021), claims benefit to U.S. patent application Ser. No. 63 / 035,073, entitled "Alcohols Production."

[0009] This patent application is a non-provisional continuation-in-part PCT application of co-pending International Application No. PCT / US2021 / 034189 entitled "Branched Compounds," filed May 26, 2021 (2021, 5 / 26 / 2021; 26.05.2021), which claims the benefit of the filing date of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Branched Compounds," filed on December 17, 2020 (2020, December 17; 17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20), which claims the benefit of priority to U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on April 30, 2021 (2021, April 30; 30.04.2021), which claims the benefit of priority to U.S. Patent Application No. 17 / 246,580 entitled "Alcohols Production," filed on June 5, 2020 (2020, June 5; 05.06.20), which claims the benefit of priority to U.S. Patent Application No. International application PCT / US21 / 30341, entitled "Alcohols Production," filed April 30, 2021 (2021, April 30; 30.04.2021), claims the benefit of priority to U.S. patent application Ser. No. 63 / 035,073, entitled "Alcohols Production."

[0010] This patent application is a non-provisional continuation-in-part PCT application of co-pending U.S. non-provisional patent application Ser. No. 17 / 336,099 entitled "Branched Alcohols," filed June 1, 2021 (2021, 6 / 1; 01.06.2021), and claims the benefit of the filing date thereof. U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.2020); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed April 30, 2021 (30.04.2021), claims benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073, entitled "Alcohols Production," and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed April 30, 2021 (30.04.2021), claims benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed June 5, 2020 (05.06.20).

[0011] This patent application is a non-provisional continuation-in-part PCT application of co-pending U.S. non-provisional patent application No. 17 / 336,099 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), which claims the benefit of the filing date of U.S. patent application No. 17 / 331,371 entitled "Branched Compounds," filed May 26, 2021 (26.05.2021), which claims the benefit of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20), and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20).

[0012] This patent application is a non-provisional continuation-in-part PCT application of co-pending U.S. non-provisional patent application Ser. No. 17 / 336,099 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), which claims the benefit of the filing date of international application PCT / US2021 / 034189 entitled "Branched Compounds," filed May 26, 2021 (26.05.2021), which claims the benefit of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20), and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20).

[0013] This patent application is a non-provisional continuation-in-part PCT application of co-pending International Application No. PCT / US2021 / 035169 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), and claims the benefit of the filing date thereof. U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.2020); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.2020); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed April 30, 2021 (30.04.2021), claims benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073, entitled "Alcohols Production," and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed April 30, 2021 (30.04.2021), claims benefit of the filing date of co-pending U.S. Provisional Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed June 5, 2020 (05.06.20).

[0014] This patent application is a non-provisional continuation-in-part of co-pending International Application No. PCT / US2021 / 035169 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), which claims the benefit of the filing date of U.S. Patent Application No. 17 / 331,371 entitled "Branched Compounds," filed May 26, 2021 (26.05.2021), which claims the benefit of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20), and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20).

[0015] This patent application is a non-provisional continuation-in-part of co-pending International Application No. PCT / US2021 / 035169 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), which claims the benefit of the filing date of International Application PCT / US2021 / 034189 entitled "Branched Compounds," filed May 26, 2021 (26.05.2021), which claims the benefit of each of the following priorities: U.S. Patent Application No. 63 / 035,280 entitled "Branched Compounds," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,479 entitled "Branched Alcohols," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 035,073 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 63 / 126,780 entitled "Branched Products," filed on December 17, 2020 (17.12.20); U.S. Patent Application No. 63 / 126,780 entitled "Alcohols Production," filed on June 5, 2020 (05.06.20); U.S. Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20), and International Application PCT / US2021 / 030341, entitled "Alcohols Production," filed on April 30, 2021 (30.04.2021), which claims benefit to U.S. Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed on June 5, 2020 (05.06.20).

[0016] Accordingly, this non-provisional PCT application is a continuation of U.S. patent application Ser. No. 63 / 035,280 entitled "Branched Compounds," U.S. patent application Ser. No. 63 / 035,479 entitled "Branched Alcohols," U.S. patent application Ser. No. 63 / 035,073 entitled "Alcohols Production," International application PCT / US2021 / 030341 entitled "Alcohols Production," U.S. patent application Ser. No. 17 / 246,580 entitled "Alcohols Production," U.S. patent application Ser. No. 17 / 331,371 entitled "Branched Compounds," and International application PCT / US2021 / 034189 entitled "Branched Compounds," all filed on June 1, 2021 (June 1, 2021; 01.06.2021). This application claims priority to U.S. patent application Ser. No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), and international application PCT / US2021 / 035169, entitled "Branched Alcohols," filed June 5, 2020 (2020, June 5; 05.06.20).

[0017] Accordingly, this non-provisional PCT application is a continuation of U.S. Provisional Patent Application No. 63 / 126,780, entitled "Branched Products," U.S. Patent Application No. 17 / 331,371, entitled "Branched Compounds," International Application No. PCT / US2021 / 034189, entitled "Branched Compounds," U.S. Patent Application No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, 6 / 1; 01.06.2021), and U.S. Patent Application No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, 6 / 1; 01.06.2021). Priority is claimed through the application of international patent application PCT / US2021 / 035169 entitled "Potentially Induced Alcohols" dated December 17, 2020 (2020, December 17; 17.12.20).

[0018] Accordingly, this non-provisional PCT application is a continuation of U.S. patent application Ser. No. 17 / 246,580, entitled "Alcohols Production," International application PCT / US2021 / 030341, entitled "Alcohols Production," U.S. patent application Ser. No. 17 / 331,371, entitled "Branched Compounds," International application PCT / US2021 / 034189, entitled "Branched Compounds," filed June 1, 2021 (2021, 6 / 1; 01.06.2021), U.S. patent application Ser. No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, 6 / 1; 01.06.2021), and U.S. patent application Ser. No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, 6 / 1; 01.06.2021). Priority is claimed through the international application PCT / US2021 / 035169 entitled "Alcohols" dated April 30, 2021 (2021, April 30; 30.04.2021).

[0019] This non-provisional PCT application therefore claims priority to U.S. patent application Ser. No. 17 / 331,371, entitled "Branched Compounds," International application PCT / US2021 / 034189, entitled "Branched Compounds," U.S. patent application Ser. No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), and International application PCT / US2021 / 035169, entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021), filed May 26, 2021 (2021, May 26; 26.05.2021).

[0020] This non-provisional PCT application therefore claims priority to U.S. patent application Ser. No. 17 / 336,099, entitled "Branched Alcohols," filed on June 1, 2021 (2021, June 1; 01.06.2021), and international application PCT / US2021 / 035169, entitled "Branched Alcohols," filed on June 1, 2021 (2021, June 1; 01.06.2021).

[0021] (Incorporated by reference) This patent application incorporates by reference in its entirety co-pending U.S. Provisional Patent Application No. 63 / 035,280, entitled "Branched Compounds," filed June 5, 2020 (2020, June 5; 05.06.20).

[0022] This patent application incorporates by reference in its entirety co-pending U.S. Provisional Patent Application No. 63 / 035,479, entitled "Branched Alcohols," filed June 5, 2020 (2020, June 5; 05.06.20).

[0023] This patent application incorporates by reference in its entirety co-pending U.S. Provisional Patent Application No. 63 / 035,073, entitled "Alcohols Production," filed June 5, 2020 (2020, June 5; 05.06.20).

[0024] This patent application incorporates by reference in its entirety co-pending U.S. Provisional Patent Application No. 63 / 126,780, entitled "Branched Products," filed December 7, 2020 (2020, Dec 7; 17.12.20).

[0025] This patent application incorporates by reference in its entirety co-pending U.S. Non-Provisional Patent Application No. 17 / 246,580, entitled "Alcohols Production," filed on April 30, 2021 (2021, April 30; 30.04.2021).

[0026] This patent application incorporates by reference in its entirety the co-pending international application PCT / US2021 / 030341 entitled "Alcohols Production," filed on April 30, 2021 (2021, April 30; 30.04.2021).

[0027] This patent application incorporates by reference in its entirety co-pending U.S. Non-Provisional Patent Application No. 17 / 331,371, entitled "Branched Compounds," filed on May 26, 2021 (2021, May 26; 26.05.2021).

[0028] This patent application incorporates by reference in its entirety the co-pending international application PCT / US2021 / 034189 entitled "Branched Compounds," filed on May 26, 2021 (2021, May 26; 26.05.2021).

[0029] This patent application incorporates by reference in its entirety co-pending U.S. Non-Provisional Patent Application No. 17 / 336,099, entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021).

[0030] This patent application incorporates by reference in its entirety co-pending international application PCT / US2021 / 035169 entitled "Branched Alcohols," filed June 1, 2021 (2021, June 1; 01.06.2021). [Background technology]

[0031] The chemical industry has long felt the need for cost-effective production of branched aldehydes, branched alcohols, and branched products derived from branched aldehydes and branched alcohols. Inexpensive alpha-olefins are available in large quantities. However, no method is known for efficiently and cost-effectively producing branched aldehydes, branched alcohols, and branched products on an industrial scale using alpha-olefins as a feedstock. Summary of the Invention

[0032] Alpha olefins are supplied in large quantities worldwide and are inexpensive. Alpha olefins are typically produced from economically priced ethylene via an ethylene oligomerization process. However, these alpha olefins are mostly linear, and a major problem is that no method is known for efficiently and cost-effectively producing branched products from linear alpha olefins. Specifically, no method is known for efficiently producing valuable products such as branched aldehydes and branched alcohols on an industrial scale using alpha olefins as a feedstock. Various embodiments of the present specification enable the simultaneous production of multiple branched aldehyde products from an alpha olefin feedstock. In embodiments of the present specification, multiple branched alcohol products can be simultaneously produced from an alpha olefin feedstock.

[0033] It is well known that α-olefins can be hydroformylated to produce aldehyde products. However, these products are predominantly linear because the olefin functionality (i.e., the double bond) is in the α-position (i.e., between the first and second carbons), resulting in the formation of linear aldehydes. For example, hydroformylation of the C12 α-olefin 1-dodecene produces a C13 aldehyde product consisting essentially of the linear aldehyde 1-tridecanal. To produce branched products, a first step involves isomerizing the olefin functionality from the α-position to an internal olefinic position, followed by a second step of hydroformylating the olefin to the aldehyde. Thus, a two-step process, consisting of a first isomerization and a second hydroformylation, can produce branched aldehyde products from linear α-olefin starting materials. The use of the same catalyst for both the isomerization and hydroformylation steps offers significant advantages in terms of the efficiency and economic viability of this two-step process. The branched aldehydes produced from α-olefins via this two-step process are predominantly "2-alkyl" branched aldehydes, where the branching occurs at the second carbon atom from the aldehyde functional group. These 2-alkyl branched aldehydes can be efficiently hydrogenated to produce 2-alkyl branched alcohol products, which can then be further reacted to produce other 2-alkyl derivatives such as surfactants. It is known that the position and length of the alkyl branching are important for the properties of the final product.

[0034] In one embodiment, a two-stage process for producing 25% to 98%+ branched, greater than 20% branched aldehyde products from an alpha-olefin feedstock is disclosed. The disclosed two-stage process also employs a rhodium organophosphorus catalyst in both the first isomerization step and the second hydroformylation step. In one embodiment, the disclosed two-stage process employs a cobalt organophosphorus catalyst in both the first isomerization step and the second hydroformylation step. In one embodiment, the disclosed two-stage process employs a cobalt-rhodium mixed organophosphorus catalyst in both the first isomerization step and the second hydroformylation step.

[0035] In one embodiment, the method disclosed herein can have a first process step and a second process step. The first process step can be a reaction of isomerizing α-olefins under a carbon monoxide (CO) and hydrogen (H) (also referred to as "CO / H") atmosphere at a first pressure. The isomerization step can be catalyzed by a first catalyst including an organometallic complex of rhodium and one type of organophosphorus ligand, or an organometallic complex of rhodium and two or more types of organophosphorus ligands, to produce isomerized olefins. The second step of this embodiment can be a reaction of hydroformylating the isomerized olefins under a CO / H atmosphere at a second pressure higher than the first pressure. The hydroformylation step can be catalyzed by the first catalyst to produce branched aldehydes by hydroformylation.

[0036] In one embodiment, the catalyst used in the isomerization step can be the same catalyst as the catalyst used in the hydroformylation step. In one embodiment, the second pressure can be lower than the first pressure. In another embodiment, the first pressure and the second pressure are different. Thus, optionally, the second pressure can be higher or lower than the first pressure.

[0037] In one embodiment, the organophosphorus ligand can be a phosphine. A non-limiting example of a phosphine ligand is triphenylphosphine. In another embodiment, the organophosphorus ligand can be a phosphite. A non-limiting example of a phosphite ligand is tris(2,4-di-t-butylphenyl)phosphite. In yet another embodiment, a mixture of different organophosphorus ligands can be used, such as a mixture of phosphines and phosphites. A non-limiting example of a mixture of organophosphorus ligands is a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the α-olefin can be a C4 to C36 α-olefin. In one embodiment, the first catalyst can be formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1.

[0038] In one embodiment, the molar ratio of CO to H2 in the isomerization step can be in the range of 10:1 to 1:10. In one embodiment, the molar ratio of CO to H2 in the hydroformylation step can be in the range of 10:1 to 1:10. In one embodiment, the molar ratio of CO to H2 in the isomerization step can be the same as the molar ratio of CO to H2 in the hydroformylation step. In one embodiment, the molar ratio of CO to H2 in the isomerization step can be different from the molar ratio of CO to H2 in the hydroformylation step.

[0039] In one embodiment, the α-olefins may include at least one of short-chain α-olefins, medium-chain α-olefins, and long-chain α-olefins. In one embodiment, the α-olefins may include at least one of C4 or higher α-olefins. In one embodiment, the α-olefins may include at least one of C4 or higher α-olefins, C6 or higher α-olefins, C10 or higher α-olefins, C16 or higher α-olefins, C20 or higher α-olefins, C30 or higher α-olefins, and C36 or higher α-olefins.

[0040] In one embodiment, the isomerization produces a reaction product comprising at least 20 wt% isomerized olefins.

[0041] In one embodiment, the isomerization step produces a reaction product comprising 5 wt% or more isomerized olefins, or 10 wt% or more isomerized olefins, or 15 wt% or more isomerized olefins, or 20 wt% or more isomerized olefins, or 30 wt% or more isomerized olefins, or 40 wt% or more isomerized olefins, or 50 wt% or more isomerized olefins, or 60 wt% or more isomerized olefins, or 70 wt% or more isomerized olefins, or 80 wt% or more isomerized olefins, or 90 wt% or more isomerized olefins, or 95 wt% or more isomerized olefins, or 99 wt% or more isomerized olefins.

[0042] In one embodiment, the hydroformylation step produces a reaction product comprising 25 wt% or more branched aldehydes, or 30 wt% or more branched aldehydes, or 40 wt% or more branched aldehydes, or 50 wt% or more branched aldehydes, or 60 wt% or more branched aldehydes, or 70 wt% or more branched aldehydes, or 80 wt% or more branched aldehydes, or 90 wt% or more branched aldehydes, or 95 wt% or more branched aldehydes, or 99 wt% or more branched aldehydes.

[0043] In one embodiment, the method includes providing a first catalyst, the first catalyst being an organometallic complex of rhodium and one organophosphorus ligand, or an organometallic complex of rhodium and two or more organophosphorus ligands; activating the first catalyst with CO to obtain an activated first catalyst; isomerizing α-olefins over the activated first catalyst at a first pressure to produce isomerized olefins; providing hydrogen; and hydroformylating the isomerized olefins by reaction with CO and H at a second pressure to produce branched aldehydes. In one embodiment, the isomerization step is carried out under an atmosphere containing 10-100 mol% CO and 0-90 mol% hydrogen. In one embodiment, the isomerization step is carried out under an atmosphere containing both CO and H. In one embodiment, the molar ratio of CO to H in the isomerization step can be in the range of 10:1 to 1:10. In one embodiment, the molar ratio of CO to H in the hydroformylation step can be in the range of 10:1 to 1:10. In one embodiment, the α-olefin is a linear α-olefin having a carbon number ranging from C4 to C36. In one embodiment, the α-olefin can be a C4 to C36 α-olefin. In one embodiment, the organophosphorus ligand can be a phosphine. A non-limiting example of a phosphine ligand is triphenylphosphine. In another embodiment, the organophosphorus ligand can be a phosphite. A non-limiting example of a phosphite ligand is tris(2,4-di-t-butylphenyl)phosphite. In yet another embodiment, a mixture of different organophosphorus ligands can be used, such as a mixture of phosphines and phosphites. A non-limiting example of a mixture of organophosphorus ligands is a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the first catalyst can be formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1.

[0044] In one embodiment, the method includes providing CO and H2, providing a first catalyst that is an organometallic complex of rhodium and one organophosphorus ligand or an organometallic complex of rhodium and two or more organophosphorus ligands, providing a linear alpha olefin, isomerizing the linear alpha olefin (also referred to as a normal alpha olefin) with the first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin, and hydroformylating the isomerized olefin with the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce a branched aldehyde. In one embodiment, the branched aldehyde is a 2-alkyl branched aldehyde. In one embodiment, the linear alpha olefin is a C4-C36 linear alpha olefin. In one embodiment, the branched aldehyde produced from the C4-C36 linear alpha olefin is a C5-C37 branched aldehyde. In one embodiment, the linear alpha olefin is 1-butene and the branched aldehyde can be branched pentanal. In one embodiment, the linear alpha olefin is 1-hexene and the branched aldehyde can be branched heptanal. In one embodiment, the linear alpha olefin is 1-octene and the branched aldehyde can be branched nonanal. In one embodiment, the linear alpha olefin is 1-decene and the branched aldehyde can be branched undecanal. In one embodiment, the linear alpha olefin is 1-dodecene and the branched aldehyde can be branched tridecanal. In one embodiment, the linear alpha olefin is 1-tetradecene and the branched aldehyde can be branched pentadecanal.

[0045] In one embodiment, the linear alpha olefin can be 1-hexadecene, and the branched aldehyde can be branched heptadecanal. In one embodiment, the linear alpha olefin can be 1-octadecene, and the branched aldehyde can be branched nonadecanal. In one embodiment, the organophosphorus ligand can be a phosphine. A non-limiting example of a phosphine ligand is triphenylphosphine. In another embodiment, the organophosphorus ligand can be a phosphite. A non-limiting example of a phosphite ligand is tris(2,4-di-t-butylphenyl)phosphite. In yet another embodiment, a mixture of different organophosphorus ligands can be used, such as a mixture of a phosphine and a phosphite. A non-limiting example of a mixture of organophosphorus ligands is triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite.

[0046] In one embodiment, the first catalyst is formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1. In one embodiment, the first catalyst is formed when the molar ratio of phosphorus to rhodium in the isomerization step and / or reactor is in the range of 1:1 to 1000:1. In one embodiment, the first catalyst is formed when the molar ratio of phosphorus to rhodium in the hydroformylation step and / or reactor is in the range of 1:1 to 1000:1.

[0047] In one embodiment, the method includes providing CO and H2, providing a first catalyst that is an organometallic complex of rhodium and one organophosphorus ligand, or an organometallic complex of rhodium and two or more organophosphorus ligands, providing an α-olefin, isomerizing the α-olefin with the first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin, and hydroformylating the isomerized olefin with the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce a branched aldehyde. In one embodiment, the α-olefin can be a C4-C36 α-olefin. In one embodiment, the organophosphorus ligand can be a phosphine. A non-limiting example of a phosphine ligand is triphenylphosphine. In another embodiment, the organophosphorus ligand can be a phosphite. A non-limiting example of a phosphite ligand is tris(2,4-di-t-butylphenyl)phosphite. In yet another embodiment, a mixture of different types of organophosphorus ligands can be used, such as a mixture of phosphines and phosphites. A non-limiting example of a mixture of organophosphorus ligands is a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the first catalyst can be formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1.

[0048] In one embodiment, the method includes providing CO and H2, providing a first catalyst that is an organometallic complex of rhodium and one organophosphorus ligand, or an organometallic complex of rhodium and two or more organophosphorus ligands, providing an α-olefin, isomerizing the α-olefin with the first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin, hydroformylating the isomerized olefin with the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce a branched aldehyde, and hydrogenating the branched aldehyde to produce a branched alcohol. In one embodiment, the isomerization step produces a reaction product comprising at least 5 wt% isomerized olefin, or at least 10 wt% isomerized olefin, or at least 20 wt% isomerized olefin, or at least 40 wt% isomerized olefin. In one embodiment, the hydroformylation step produces a reaction product comprising at least 25 wt% branched aldehydes, or at least 50 wt% branched aldehydes. In one embodiment, the hydrogenation step produces a reaction product comprising at least 25 wt% branched alcohols, or at least 50 wt% branched alcohols.

[0049] In one embodiment, a method for producing a branched aldehyde may include providing an α-olefin, providing a first catalyst, isomerizing an alkene catalyzed by the first catalyst under an atmosphere comprising CO and H at a first pressure, producing an intermediate isomerized olefin product composition with an internal olefin, and hydroformylating the intermediate isomerized olefin product catalyzed by the first catalyst under an atmosphere comprising CO and H at a second pressure higher than the first pressure, producing a branched aldehyde product. Also, in one embodiment, the method may include separating the branched aldehyde product from the first catalyst stream by a distillation process. Also, in one embodiment, the method may include hydrogenating the branched aldehyde in the presence of a hydrogenation catalyst, producing a branched alcohol product composition. In one embodiment, the α-olefin is a C4 to C36 or higher α-olefin. In one embodiment, the catalyst is a rhodium catalyst. In one embodiment, the catalyst is a homogeneous rhodium catalyst. In one embodiment, the catalyst is a homogeneous rhodium catalyst with an organophosphorus ligand. In one embodiment, the first pressure can range from 0.01 bar (absolute) to 20 bar (absolute) (gauge pressure: -0.99 bar(g) (negative value, vacuum) to 19 bar(g)). In one embodiment, the intermediate isomerized olefin product can comprise at least 10 wt. % internal olefins, or at least 20 wt. % internal olefins. In one embodiment, the second pressure can range from 1 bar(g) to 400 bar(g). The branched aldehyde product can comprise at least 25 wt. % branched aldehydes.

[0050] In one embodiment, the method includes providing CO and H2, providing a first catalyst that is an organometallic complex of rhodium and one organophosphorus ligand or an organometallic complex of rhodium and two or more organophosphorus ligands, providing an α-olefin, isomerizing the α-olefin over the first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin, hydroformylating the isomerized olefin over the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce a branched aldehyde, hydrogenating the branched aldehyde to produce a branched alcohol, and producing a branched surfactant from the branched alcohol. In one embodiment, the producing step includes sulfated the branched alcohol to produce a branched alcohol sulfate. In one embodiment, the producing step includes alkoxylated the branched alcohol to produce a branched alkoxylated alcohol. In one embodiment, the alkoxylating agent can be ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide. In one embodiment, the alkoxylating agent can be ethylene oxide and propylene oxide, added simultaneously or in stages (i.e., block oxide). In one embodiment, the alkoxylating agent can be ethylene oxide, propylene oxide, butylene oxide, or a mixture of ethylene oxide, propylene oxide, and butylene oxide. In one embodiment, the alkoxylated alcohol can be sulfated to produce a branched, sulfated alkoxylated alcohol. In one embodiment, the isomerization step can produce a reaction product comprising 20 wt.% or more internal olefins. In one embodiment, the isomerization can produce a reaction product comprising 50 wt.% or more internal olefins. In one embodiment, the hydroformylation can produce a reaction product comprising 25 wt.% or more branched aldehydes. In one embodiment, the hydroformylation can produce a reaction product comprising 50 wt.% or more branched aldehydes. In one embodiment, the hydrogenation can produce a reaction product comprising 40 wt.% or more branched alcohols.In one embodiment, the hydrogenation step can produce a reaction product comprising 50 wt% or more of a branched alcohol. In one embodiment, the surfactant can comprise 40 wt% or more of a branched surfactant. In one embodiment, the surfactant can comprise 50 wt% or more of a branched surfactant.

[0051] (Downstream products of branched alcohols)

[0052] The branched alcohol products produced by the methods of the various embodiments disclosed herein can be used to make a myriad of different products.

[0053] In one embodiment, the branched alcohol products of the methods disclosed herein can be used to make fuels, lubricity additives, food additives, solvents, emulsifiers, emollients, thickeners, coatings, elastomers, adhesives, antioxidants, polymer stabilizers, cosmetics, and the like.

[0054] (Carboxylation product)

[0055] In one embodiment, the branched alcohol products of the presently disclosed methods can be carboxylated by reaction with a carboxylic acid, dicarboxylic acid, or polyacid to form an ester. Applications for such esters produced by the presently disclosed methods include lubricants, plasticizers, solvents, coatings, inks, cleaners, binders, paint strippers, and / or oil field chemicals.

[0056] (branched aldehyde, amine, carboxylic acid product)

[0057] In various embodiments, numerous downstream products can be produced as a product of the methods disclosed herein. The branched aldehydes produced by the present embodiments can be reacted to produce numerous branched aldehyde products. The branched aldehydes can be further reacted to produce branched amine products. In other embodiments, the branched aldehydes can be reacted to produce branched carboxylic acid products.

[0058] (branched aldehyde product)

[0059] In one embodiment, examples of branched aldehyde products of the presently disclosed methods include, but are not limited to, perfume molecules, flavorings, solvents, intermediates in plastics manufacturing, dyes, and pharmaceuticals.

[0060] In one embodiment, the branched aldehydes produced by the methods disclosed herein can be reacted with ammonia and hydrogen to produce branched primary amines.

[0061] In one embodiment, the branched aldehydes produced by the methods disclosed herein can be reacted with an amine and hydrogen to produce a branched secondary amine.

[0062] In one embodiment, the branched aldehydes produced by the methods disclosed herein can be reacted with secondary amines to produce branched tertiary amines.

[0063] (Branched Amine Product)

[0064] In one embodiment, examples of branched amine products of the presently disclosed methods include, but are not limited to, chemical catalysts, corrosion inhibitors, emulsifiers, flotation aids, ion exchange resins, rubber chemicals, antioxidants, stabilizers, antistatic agents, plasticizers, dyes, gasoline and lubrication additives, curing agents for epoxy resins, solvents, metal extractants, photographic developers, anticaking agents, and the like.

[0065] In one embodiment, the branched amine products of the methods disclosed herein can be intermediates for the synthesis of pharmaceuticals, herbicides, fungicides, and insecticides.

[0066] In one embodiment, the branched amine product of the methods disclosed herein can be alkoxylated to produce an alkoxylated amine surfactant.

[0067] In one embodiment, the branched amine product of the presently disclosed method embodiments can be oxidized to produce an amine oxide surfactant.

[0068] (Branched Carboxylic Acid Product)

[0069] In one embodiment, the branched aldehyde product of the methods disclosed herein can be oxidized with oxygen or other oxidizing agent to produce a branched carboxylic acid.

[0070] In one embodiment, the branched carboxylic acid products of the methods disclosed herein can be corrosion inhibitors, emulsifiers, ion exchange resins, food additives, flavor molecules, plastic additives, lubricants, solvents, coatings, dyes, rubber chemicals, and plasticizers.

[0071] In one embodiment, the method may include providing a feed having α-olefins, providing a catalyst, catalyzing the isomerization of the α-olefins with the catalyst, isomerizing the α-olefins to produce isomerized olefins, catalyzing the hydroformylation of the isomerized olefins with the catalyst, and hydroformylating the isomerized olefins to produce branched aldehydes. Also, in one embodiment, the method may include reacting the branched aldehyde with hydrogen and reacting the branched aldehyde to produce branched alcohols.

[0072] In one embodiment, the method may also include providing a feed having one or more internal olefins. In one embodiment, the method may also include providing a feed having one or more internal olefins, wherein the internal olefins are C4 to C36 internal olefins. In one embodiment, the method may include providing a feed having one or more internal olefins, providing a catalyst, catalyzing the isomerization of the internal olefins with the catalyst, producing an isomerized olefin mixture by isomerization of the internal olefins, catalyzing the hydroformylation of the isomerized olefin mixture with the catalyst, and producing a branched aldehyde mixture by hydroformylation of the isomerized olefin mixture. In one embodiment, the method may also include reacting the branched aldehyde mixture with hydrogen and producing a branched alcohol mixture by reacting the branched aldehyde mixture.

[0073] In one embodiment, the method may also include providing a mixed olefin feed that is a mixture of internal olefins and α-olefins. In one embodiment, the method may also include providing a mixed olefin feed that is a mixture of one or more C4-C36 internal olefins and one or more C4-C36 α-olefins. In one embodiment, the method may include providing the mixed olefin feed, providing a catalyst, catalyzing the isomerization of the mixed olefins with the catalyst, isomerizing the mixed olefins to produce an isomerized olefin mixture, catalyzing the hydroformylation of the mixed olefins with the catalyst, and hydroformylating the mixed olefins to produce a branched aldehyde mixture. In one embodiment, the method may also include reacting the branched aldehyde mixture with hydrogen and reacting the branched aldehyde mixture to produce a branched alcohol mixture.

[0074] In one embodiment, the method may include providing a C4 to C36 alkene, providing a first catalyst, isomerizing the C4 to C36 alkene catalyzed by the first catalyst, producing an intermediate product composition having a plurality of isomerized alkenes, the intermediate product composition comprising at least 60 wt% of the plurality of isomerized alkenes, and hydroformylating the plurality of isomerized alkenes. In one embodiment, the method may further include producing a branched aldehyde. In one embodiment, the method may further include producing a branched aldehyde product composition comprising at least 60 wt% of the plurality of branched aldehydes by hydroformylation.

[0075] In one embodiment, the composition may comprise a mixture of C8-C36 alcohols, wherein less than 60% of the mixture of C8-C36 alcohols are straight chain alcohols, greater than 25% of the mixture of C8-C36 alcohols are 2-methyl branched alcohols, and greater than 8% of the mixture of C8-C36 alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may comprise a mixture of C8-C36 alcohols where greater than 10% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 12% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 14% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 16% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 18% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 20% of the alcohols are 2-ethyl branched alcohols.

[0076] In another embodiment, the composition comprises a mixture of C8-C36 alcohols, wherein less than 50% of the C8-C36 alcohols are straight chain alcohols, greater than 30% of the C8-C36 alcohols are 2-methyl branched alcohols, and greater than 8% of the C8-C36 alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 10% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 12% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 14% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 16% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8-C36 alcohols where greater than 18% of the alcohols are 2-ethyl branched alcohols. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 20% of the alcohols are 2-ethyl branched alcohols.

[0077] In one embodiment, the composition comprises a mixture of C8-C36 alcohols, wherein less than 60% of the mixture of C8-C36 alcohols are linear alcohols, greater than 25% of the mixture of C8-C36 alcohols are 2-methyl branched alcohols, and greater than 8% of the mixture of C8-C36 alcohols are 2-ethyl branched alcohols; the alcohol mixture comprises about 90% or more C13 alcohols (i.e., tridecanol), wherein less than 60% of the mixture of alcohols is linear 1-tridecanol, greater than 25% of the mixture of alcohols is 2-methyldodecanol, and greater than 8% of the mixture of alcohols is 2-ethylundecanol. In one embodiment, the composition can have a mixture of C8-C36 alcohols, wherein more than 10% of the mixture of alcohols is 2-ethylundecanol. In one embodiment, the composition can have a mixture of C8-C36 alcohols, wherein more than 12% of the mixture of alcohols is 2-ethylundecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 14% of the alcohol mixture is 2-ethylundecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 16% of the alcohol mixture is 2-ethylundecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 18% of the alcohol mixture is 2-ethylundecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 20% of the alcohol mixture is 2-ethylundecanol.

[0078] The composition can include a mixture of C8-C36 alcohols, wherein less than 60% of the mixture of C8-C36 alcohols are linear alcohols, greater than 25% of the mixture of C8-C36 alcohols are 2-methyl branched alcohols, and greater than 8% of the mixture of C8-C36 alcohols are 2-ethyl branched alcohols; the mixture of alcohols can include about 90% or more C15 alcohols (i.e., pentadecanol), wherein less than 60% of the mixture of alcohols is linear 1-pentadecanol, greater than 25% of the mixture of alcohols is 2-methyltetradecanol, and greater than 8% of the mixture of alcohols is 2-ethyltridecanol. In one embodiment, the composition can have a mixture of C8-C36 alcohols, wherein more than 10% of the mixture of alcohols is 2-ethyltridecanol. In one embodiment, the composition can have a mixture of C8-C36 alcohols, wherein more than 12% of the mixture of alcohols is 2-ethyltridecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 14% of the alcohol mixture is 2-ethyltridecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 16% of the alcohol mixture is 2-ethyltridecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 18% of the alcohol mixture is 2-ethyltridecanol. In one embodiment, the composition may have a mixture of C8 to C36 alcohols, where greater than 20% of the alcohol mixture is 2-ethyltridecanol.

[0079] The composition may comprise a mixture of C8-C36 aldehydes, wherein less than 60% of the mixture of C8-C36 aldehydes are linear aldehydes, greater than 25% of the mixture of C8-C36 aldehydes are 2-methyl branched aldehydes, and greater than 8% of the mixture of C8-C36 aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 10% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 12% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 14% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 16% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 18% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 20% of the aldehydes are 2-ethyl branched aldehydes.

[0080] In one embodiment, the composition comprises a mixture of C8-C36 aldehydes, wherein less than 50% of the mixture of C8-C36 aldehydes are linear aldehydes, greater than 30% of the mixture of C8-C36 aldehydes are 2-methyl branched aldehydes, and greater than 8% of the mixture of C8-C36 aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 10% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 12% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes where greater than 14% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 16% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 18% of the aldehydes are 2-ethyl branched aldehydes. In one embodiment, the composition may have a mixture of C8-C36 aldehydes, where greater than 20% of the aldehydes are 2-ethyl branched aldehydes.

[0081] In one embodiment, the composition can include a mixture of C8-C36 aldehydes, wherein less than 60% of the mixture of C8-C36 aldehydes are linear aldehydes, greater than 25% of the mixture of C8-C36 aldehydes are 2-methyl branched aldehydes, greater than 8% of the mixture of C8-C36 aldehydes are 2-ethyl branched aldehydes, the aldehyde mixture can include about 90% or more C13 aldehydes (i.e., tridecanal), wherein less than 60% of the mixture of aldehydes are linear 1-tridecanal, greater than 25% of the mixture of aldehydes is 2-methyldodecanal, and greater than 8% of the mixture of aldehydes is 2-ethylundecanal. In one embodiment, the composition can have a mixture of C8-C36 aldehydes, wherein greater than 10% of the mixture of aldehydes is 2-ethylundecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 12% of the aldehyde mixture is 2-ethylundecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 14% of the aldehyde mixture is 2-ethylundecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 16% of the aldehyde mixture is 2-ethylundecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 18% of the aldehyde mixture is 2-ethylundecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 20% of the aldehyde mixture is 2-ethylundecanal.

[0082] In one embodiment, the composition can include a mixture of C8-C36 aldehydes, wherein less than 60% of the mixture of C8-C36 aldehydes are linear aldehydes, greater than 25% of the mixture of C8-C36 aldehydes are 2-methyl branched aldehydes, greater than 8% of the mixture of C8-C36 aldehydes are 2-ethyl branched aldehydes, the aldehyde mixture can include about 90% or more C15 aldehydes (i.e., pentadecanal), wherein less than 60% of the mixture of aldehydes is linear 1-pentadecanal, greater than 25% of the mixture of aldehydes is 2-methyltetradecanal, and greater than 8% of the mixture of aldehydes is 2-ethyltridecanal. In one embodiment, the composition can have a mixture of C8-C36 aldehydes, wherein greater than 10% of the mixture of aldehydes is 2-ethyltridecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 12% of the aldehyde mixture is 2-ethyltridecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 14% of the aldehyde mixture is 2-ethyltridecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 16% of the aldehyde mixture is 2-ethyltridecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 18% of the aldehyde mixture is 2-ethyltridecanal. In one embodiment, the composition may have a mixture of C8 to C36 aldehydes, where greater than 20% of the aldehyde mixture is 2-ethyltridecanal.

[0083] A product composition is provided that is produced as the product of a process comprising the steps of: reacting a mixture of C8 to C36 aldehydes, wherein less than 60% of the mixture of C8 to C36 aldehydes are linear aldehydes, more than 25% of the mixture of C8 to C36 aldehydes are 2-methyl branched aldehydes, and more than 8% of the mixture of C8 to C36 aldehydes are 2-ethyl branched aldehydes, with an amine and hydrogen to produce a mixture of C8 to C36 amines, wherein less than 60% of the amines are linear amines, more than 25% of the amines are 2-methyl branched amines, and more than 8% of the amines are 2-ethyl branched amines; and producing an amine composition. The product composition can be produced by a reaction step in which the amine reacted is ammonia and the amine composition produced is a mixture of primary amines. The product composition can be produced by a reaction step in which the amine reacted is a primary amine and the amine composition produced is a mixture of secondary amines. The product composition can be produced by a reaction step in which the amine reacted is a secondary amine and the product amine composition is a mixture of tertiary amines.

[0084] reacting a mixture of C8 to C36 aldehydes, wherein less than 60% of the mixture of C8 to C36 aldehydes are linear aldehydes, greater than 25% of the mixture of C8 to C36 aldehydes are 2-methyl branched aldehydes, and greater than 8% of the mixture of C8 to C36 aldehydes are 2-ethyl branched aldehydes, with amines and hydrogen to produce a mixture of C8 to C36 amines, wherein less than 60% of the amines are linear amines, greater than 25% of the amines are 2-methyl branched amines, and greater than 8% of the amines are 2-ethyl branched amines; and producing an amine composition, wherein greater than 5% of the amines are 2-methyl branched amines and greater than 8% of the amines are 2-ethyl branched amines; and further comprising reacting the amine composition with oxygen or other oxidizing agent to produce an amine oxide mixture comprising a mixture of C8 to C36 amine oxides, wherein less than 60% of the amine oxides are linear amine oxides, greater than 25% of the amine oxides are 2-methyl branched amine oxides, and greater than 8% of the amine oxides are 2-ethyl branched amine oxides. In one embodiment, the method can produce at least one amine oxide, or multiple amine oxides, each of which is a surfactant. In one embodiment, the amine oxide mixture produced by the method comprises a surfactant. In one embodiment, the amine oxide mixture produced by the method is a surfactant composition.

[0085] A product carboxylic acid composition is provided, the product of a process comprising: reacting a mixture of C8-C36 aldehydes, wherein less than 60% of the mixture of C8-C36 aldehydes are linear aldehydes, more than 25% of the mixture of C8-C36 aldehydes are 2-methyl branched aldehydes, and more than 8% of the mixture of C8-C36 aldehydes are 2-ethyl branched aldehydes, with oxygen or other oxidizing agent to produce a mixture of C8-C36 carboxylic acids, wherein less than 60% of the carboxylic acids are linear carboxylic acids, more than 25% of the carboxylic acids are 2-methyl branched carboxylic acids, and more than 8% of the carboxylic acids are 2-ethyl branched carboxylic acids; and producing a product carboxylic acid composition. In one embodiment, the carboxylic acid produced by the process is a corrosion inhibitor. In one embodiment, the product ester composition produced by the process is a lubricant or lubricant additive. In one embodiment, the product ester composition produced by the process is a plasticizer.

[0086] Provided is a product ester composition produced by a process comprising reacting a mixture of C8 to C36 alcohols, wherein less than 60% of the mixture of C8 to C36 alcohols are linear alcohols, more than 25% of the mixture of C8 to C36 alcohols are 2-methyl branched alcohols, and more than 8% of the mixture of C8 to C36 alcohols are 2-ethyl branched alcohols, with a compound having one or more carboxylic acid functional groups. In the product ester composition of the process, the compound having one or more carboxylic acid functional groups can be a monocarboxylic acid, and the resulting ester composition can be a mixture of monoesters. In the product ester composition of the process, the compound having one or more carboxylic acid functional groups can be a dicarboxylic acid, and the resulting ester composition can be a mixture of diesters. In the product ester composition of the process, the compound having one or more carboxylic acid functional groups can be a polyacid, and the resulting ester composition can be a mixture of polyesters.

[0087] A product ester composition is provided that is produced by a process comprising the steps of: reacting a mixture of C8 to C36 aldehydes, wherein less than 60% of the mixture of C8 to C36 aldehydes are linear aldehydes, more than 25% of the mixture of C8 to C36 aldehydes are 2-methyl branched aldehydes, and more than 8% of the mixture of C8 to C36 aldehydes are 2-ethyl branched aldehydes, with oxygen or other oxidizing agent to produce a mixture of C8 to C36 carboxylic acids, wherein less than 60% of the carboxylic acids are linear carboxylic acids, more than 25% of the carboxylic acids are 2-methyl branched carboxylic acids, and more than 8% of the carboxylic acids are 2-ethyl branched carboxylic acids; producing a product carboxylic acid composition; and reacting the product carboxylic acid composition with a compound having one or more alcohol functional groups to produce a product ester composition. The product ester composition of this process can be a mixture of mono-esters, where the compound having one or more alcohol functional groups is a mono-alcohol. In the product ester composition of the present method, the compound having one or more alcohol functional groups is a diol (glycol), and the resulting ester composition can be a mixture of diesters. In the product ester composition of the present method, the compound having one or more alcohol functional groups is a polyol, and the resulting ester composition can be a mixture of polyesters. In one embodiment, the product ester composition produced by the present method is a lubricant or lubricant additive. In one embodiment, the product ester composition produced by the present method is a plasticizer.

[0088] Provided is a resultant alkyl sulfate composition produced by a method comprising reacting a mixture of C8-C36 alcohols, wherein less than 60% of the mixture of C8-C36 alcohols are linear alcohols, more than 25% of the mixture of C8-C36 alcohols are 2-methyl branched alcohols, and more than 8% of the mixture of C8-C36 alcohols are 2-ethyl branched alcohols, with a sulfating agent to produce a mixture of C8-C36 alcohol sulfates, wherein less than 60% of the alcohol sulfates are linear alcohol sulfates, more than 25% of the alkyl sulfates are 2-methyl branched alkyl sulfates, and more than 8% of the alkyl sulfates are 2-ethyl branched alkyl sulfates. In one embodiment, the method can produce at least one alkyl sulfate, or multiple alkyl sulfates, each of which is a surfactant. The resultant alkyl sulfate composition of the method can include a surfactant in the alkyl sulfate mixture. The resultant alkyl sulfate composition of the method can be a surfactant composition in the alkyl sulfate mixture.

[0089] Provided is a resultant alcohol alkoxylate composition produced by a method comprising: reacting a mixture of C8 to C36 alcohols, wherein less than 60% of the mixture of C8 to C36 alcohols are linear alcohols, more than 25% of the mixture of C8 to C36 alcohols are 2-methyl branched alcohols, and more than 8% of the mixture of C8 to C36 alcohols are 2-ethyl branched alcohols, with an alkoxylating agent to produce a resultant alcohol alkoxylate composition comprising a mixture of C8 to C36 alcohol alkoxylates, wherein less than 60% of the alcohol alkoxylates are linear alcohol alkoxylates, more than 25% of the alcohol alkoxylates are 2-methyl branched alcohol alkoxylates, and more than 8% of the alcohol alkoxylates are 2-ethyl branched alcohol alkoxylates. In one embodiment, the method can produce at least one alcohol alkoxylate, or multiple alcohol alkoxylates, each of which is a surfactant. The resultant alcohol alkoxylate composition produced by the method can include a surfactant in the alcohol alkoxylate mixture. The resultant alcohol alkoxylate composition produced by the method can be a surfactant composition. The product alcohol alkoxylate composition produced by the present method can be one in which the alkoxylating agent is ethylene oxide, propylene oxide, butylene oxide, or a mixture of epoxides comprising ethylene oxide, propylene oxide, butylene oxide.

[0090] Reacting a mixture of C8 to C36 alcohols, wherein less than 60% of the mixture of C8 to C36 alcohols are linear alcohols, greater than 25% of the mixture of C8 to C36 alcohols are 2-methyl branched alcohols, and greater than 8% of the mixture of C8 to C36 alcohols are 2-ethyl branched alcohols, with an alkoxylating agent to produce a resultant alcohol alkoxylate composition comprising a mixture of C8 to C36 alcohol alkoxylates, wherein less than 60% of the alcohol alkoxylates are linear alcohol alkoxylates, greater than 25% of the alcohol alkoxylates are 2-methyl branched alcohol alkoxylates, and greater than 8% of the alcohol alkoxylates are 2-ethyl branched alcohol alkoxylates. A product alcohol alkoxylate sulfate (i.e., alkyl ether sulfate) is provided by producing a product alcohol alkoxylate composition by a method comprising the steps of: reacting the product alcohol alkoxylate composition with a sulfating agent to produce a product alcohol alkoxylate sulfate mixture comprising C8 to C36 alcohol alkoxylate sulfates, in which less than 60% of the alcohol alkoxylate sulfates are linear alcohol alkoxylate sulfates, more than 25% of the alcohol alkoxylate sulfates are 2-methyl-branched alcohol alkoxylate sulfates, and more than 8% of the alcohol alkoxylate sulfates are 2-ethyl-branched alcohol alkoxylate sulfates. In one embodiment, the method can produce at least one alcohol alkoxylate sulfate (i.e., alkyl ether sulfate) or multiple alcohol alkoxylate sulfates (i.e., alkyl ether sulfates), each of which is a surfactant. The product alcohol alkoxylate sulfate (i.e., alkyl ether sulfate) produced by the method can include a surfactant in the alcohol alkoxylate sulfate mixture. The product alcohol alkoxylate sulfate (i.e., alkyl ether sulfate) produced by the method can be a surfactant composition in the alcohol alkoxylate sulfate mixture.

[0091] A method for producing a product aldehyde composition comprising a mixture of two or more branched aldehydes is provided, the method comprising the steps of: providing C4 to C36 α-olefins of at least two different chain lengths; providing a first catalyst; isomerizing the α-olefin mixture catalyzed by the first catalyst under an atmosphere comprising CO and H at a first pressure; producing an intermediate isomerized olefin product composition comprising a mixture of α-olefins and internal olefins; hydroformylating the intermediate isomerized olefin product catalyzed by the first catalyst under an atmosphere comprising CO and H at a second pressure higher than the first pressure; and producing a product aldehyde composition that is a mixture of C5 to C37 branched aldehydes of at least two different chain lengths. The method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes may further comprise separating the mixture of C5 to C37 branched aldehydes from the first catalyst stream by a distillation process. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the catalyst can be a rhodium catalyst. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the catalyst can be a homogeneous rhodium catalyst. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the catalyst can be an organometallic complex of rhodium and one organophosphorus ligand, or an organometallic complex of rhodium and two or more organophosphorus ligands. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the first pressure can be in the range of 0.01 bar (absolute) to 20 bar (absolute). In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the intermediate isomerized olefin product can contain at least 20 wt% internal olefins. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the second pressure can be in the range of 1 bar(g) to 400 bar(g). In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the product branched aldehyde can be a 2-alkyl branched aldehyde.In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the product aldehyde composition may comprise at least 25 wt% branched aldehydes. In the method for producing a product aldehyde composition comprising a mixture of C5 to C37 branched aldehydes, the product aldehyde composition has at least two different C5 to C37 chain lengths, and the method may further comprise separating the product aldehyde composition comprising a mixture of at least two different C5 to C37 branched aldehydes into individual purified branched aldehyde products via a series of distillation processes. Each distilled purified branched aldehyde product consists essentially of products with a single carbon chain length in the C5 to C37 carbon number range.

[0092] A method for producing a mixture of two or more branched alcohols, comprising the steps of: providing at least two C4 to C36 α-olefins of different chain lengths; providing a first catalyst; isomerizing the α-olefin mixture catalyzed by the first catalyst under an atmosphere containing CO and H2 at a first pressure; producing an intermediate isomerized olefin product composition comprising a mixture of α-olefins and internal olefins; and isomerizing the intermediate isomerized olefin product catalyzed by the first catalyst under an atmosphere containing CO and H2 at a second pressure higher than the first pressure. The present invention provides a method for producing a mixture of branched aldehydes having at least two different carbon chain lengths from C5 to C37, comprising the steps of: distilling a rhodium-containing catalyst stream to produce a mixture of branched aldehydes having at least two different carbon chain lengths from C5 to C37; separating the mixture of C5 to C37 branched aldehydes from a rhodium-containing catalyst stream via a distillation process; and hydrogenating the mixture of C5 to C37 branched aldehydes at elevated hydrogen pressure in the presence of hydrogen and a hydrogenation catalyst to produce a product that is a mixture of branched alcohols having at least two different carbon chain lengths in the C5 to C37 carbon number range (also referred to as two different C5 to C37 chain lengths). In the method for producing a mixture of C5 to C37 branched alcohols, the catalyst can be a rhodium catalyst. In the method for producing a mixture of C5 to C37 branched alcohols, the catalyst can be a homogeneous rhodium catalyst. In the method for producing a mixture of C5 to C37 branched alcohols, the catalyst can be an organometallic complex of rhodium and one organophosphorus ligand, or an organometallic complex of rhodium and two or more organophosphorus ligands. In the method for producing a mixture of C5 to C37 branched alcohols, the first pressure can be in the range of 0.01 bar (absolute) to 20 bar (absolute). In the method for producing a mixture of C5 to C37 branched alcohols, the intermediate isomerization olefin product can contain at least 20 wt% internal olefins. In the method for producing a mixture of C5 to C37 branched alcohols, the second pressure can be in the range of 1 bar (g) to 400 bar (g). In the method for producing a mixture of C5 to C37 branched alcohols, the mixture of C5 to C37 branched alcohols can be 2-alkyl branched alcohols.In the method for producing a mixture of C5 to C37 branched alcohols, the mixture of C5 to C37 branched alcohols may contain at least 25 wt% branched alcohols. In the method for producing a mixture of C5 to C37 branched alcohols, the mixture has at least two different C5 to C37 chain lengths, and the method may further include separating the mixture of at least two C5 to C37 branched alcohols into individual purified branched alcohol products via a series of distillation processes. Each distilled purified branched alcohol product consists essentially of a single carbon chain length product in the C5 to C37 carbon number range. The method for producing a mixture of C5 to C37 branched alcohols may further include providing two α-olefins, a first α-olefin being a C12 α-olefin (i.e., 1-dodecene) and a second α-olefin being a C14 α-olefin (i.e., 1-tetradecene); producing a mixture of branched C13 aldehydes and branched C15 aldehydes; and producing a mixture of branched C13 alcohols and branched C15 alcohols. The method for producing a mixture of C13 branched alcohols may further include separating the mixture of C13 branched alcohols and C15 branched alcohols, purifying the C13 branched alcohol product by a first distillation step, and purifying the branched C15 alcohol product by a second distillation step.

[0093] A method is provided that includes the steps of: providing a first catalyst including an organometallic complex having at least one of rhodium and cobalt and at least one organophosphorus ligand; providing a mixture of one or more C4 to C36 linear alpha olefins; providing a gas phase including CO; isomerizing the linear alpha olefins with the first catalyst in the presence of CO at a first pressure to produce isomerized olefins; and hydroformylating the isomerized olefins with the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce branched aldehydes. In one embodiment, the branched aldehyde can be a 2-alkyl branched aldehyde. In one embodiment, the organophosphorus ligand can be a phosphite ligand. In one embodiment, the organophosphorus ligand can be tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the at least one organophosphorus ligand may be a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the method may further include providing a hydrogenation catalyst, providing hydrogen, and hydrogenating the branched aldehyde in the presence of the hydrogenation catalyst and hydrogen to produce a branched alcohol.

[0094] A method is provided that includes the steps of: providing a first catalyst including an organometallic complex having at least one of rhodium and cobalt and at least one organophosphorus ligand; providing a mixture of one or more C4 to C36 linear alpha olefins; providing a gas phase including CO; isomerizing the linear alpha olefins with the first catalyst in the presence of CO at a first pressure to produce isomerized olefins; and hydroformylating the isomerized olefins with the first catalyst in the presence of CO and H2 at a second pressure different from the first pressure to produce branched aldehydes. In one embodiment, the branched aldehyde can be a 2-alkyl branched aldehyde. In one embodiment, the organophosphorus ligand can be a phosphite ligand. In one embodiment, the organophosphorus ligand can be tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the method can further include a first organophosphorus ligand that is triphenylphosphine and a second organophosphorus ligand that is tris(2,4-di-t-butylphenyl)phosphite. In one embodiment, the method can further include providing a hydrogenation catalyst, providing hydrogen, and hydrogenating the branched aldehyde in the presence of the hydrogenation catalyst and hydrogen to produce a branched alcohol. [Brief explanation of the drawings]

[0095] Some aspects and embodiments of the present invention solve the problems discussed above and provide significant advances in the art of branched compounds and the creation and manufacture of branched compounds. The present invention can be more fully understood from the detailed description and accompanying drawings below.

[0096] [Figure 1] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor and a hydroformylation reactor. [Figure 2] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor and a hydroformylation reactor with an isomerization reactor bypass. [Figure 3]FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, and catalyst recovery. [Figure 4] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, catalyst recovery, and aldehyde distillation. [Figure 5] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, a catalyst recovery reactor, and an aldehyde hydrogenation reactor. [Figure 6] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, a catalyst recovery, an aldehyde distillation, and an aldehyde hydrogenation reactor. [Figure 7] Sales details 1 is shown. [Figure 8] Sales details 2 is shown. [Figure 9A] Page 1 of sales statement 3 is shown. [Figure 9B] Page 2 of sales statement 3 is shown. [Figure 10] Sales details 4 is shown. [Figure 11A] Page 1 of sales statement 5 is shown. [Figure 11B] Page 2 of sales statement 5 is shown. [Figure 12] Sales details 6 is shown. [Figure 13] FIG. 1 illustrates one embodiment of a chemical manufacturing process for producing n branched alcohol products via an isomerization reactor, a hydroformylation reactor, catalyst recovery, aldehyde distillation, n alpha olefin feeds to an aldehyde hydrogenation reactor, and n alcohol distillation unit operations. [Figure 14] FIG. 1 illustrates one embodiment of a chemical manufacturing process showing an isomerization reactor, a hydroformylation reactor, catalyst recovery, aldehyde distillation, C12 and C14 alpha olefin feed streams to an aldehyde hydrogenation reactor, and a branched C13 alcohol distillation unit operation and a branched C15 alcohol distillation unit operation. [Figure 15]FIG. 1 illustrates one embodiment of a chemical manufacturing process including an isomerization reactor, a hydroformylation reactor, a catalyst recovery reactor, an aldehyde hydrogenation reactor, and branched C13 and C15 alcohol distillation unit operations. [Figure 16] FIG. 1 illustrates one embodiment of a chemical manufacturing process for producing n branched aldehyde products through an isomerization reactor, a hydroformylation reactor, catalyst recovery, n alpha olefin feed to aldehyde distillation, and n aldehyde distillation unit operations.

[0097] The same reference numbers in one figure correspond to the same reference numbers in another figure. DETAILED DESCRIPTION OF THE INVENTION

[0098] In one embodiment, a two-stage process for producing a branched aldehyde product, with 25% to 98% or more branching, from an alpha-olefin feedstock is disclosed. The disclosed two-stage process employs an organometallic complex of rhodium and at least one organophosphorus ligand in both the first isomerization step and the second hydroformylation step. The disclosed two-stage process may also employ an organometallic complex of cobalt and at least one organophosphorus ligand in both the first isomerization step and the second hydroformylation step. The disclosed two-stage process may also employ a mixed organometallic complex comprising cobalt, rhodium, and at least one organophosphorus ligand in both the first isomerization step and the second hydroformylation step.

[0099] Numerical values ​​and ranges herein are intended to have tolerances and to account for design and manufacturing variations, unless otherwise noted. Thus, numerical values ​​may include "about" values ​​for that value. For example, a value X is intended to be understood as "about X." Similarly, a range Y to Z is intended to be understood as being within the range "about Y to about Z." Unless otherwise noted, significant digits disclosed for numerical values ​​are not intended to precisely limit the numerical value. Variations and tolerances are inherent in mechanical design, and numerical values ​​disclosed herein are intended to be interpreted to account for such factors (as a non-limiting example, ±10% of the given value). Similarly, the claims should be interpreted broadly with respect to numerical values ​​and ranges.

[0100] Every numerical range given herein includes every narrower numerical range that falls within that broader numerical range, as if all such narrower numerical ranges were expressly written herein. With respect to ranges and endpoints, every maximum numerical limit given herein includes every lower numerical limit, as if such lower numerical limit were expressly written herein. Every minimum numerical limit given herein includes every higher numerical limit, as if such higher numerical limits were expressly written herein.

[0101] As used herein, the term "reactor" refers to one or more physical reactors used individually or in combination to accomplish a reactive step in a chemical process. "Reaction step" and "reactive step" are used interchangeably. A "reactor" may be a single vessel or, optionally, multiple vessels. A "reactor" may optionally be configured so that a reactive step occurs in one or more reaction vessels. When there are multiple reaction vessels, these reaction vessels can be operated in series, parallel, or any combination thereof. The term "reactor" refers to a unit operation that performs a chemical reaction processing step, also referred to as a reaction step or reactive step.

[0102] For example, as shown in Figures 1-6, reactor expressions and / or reactor descriptions should not be construed as being limited to a single physical reactor. Optionally, a reaction step may be accomplished using a single physical reactor, or multiple physical reactors may be used to accomplish the reaction step. Herein, the term "reactor" should be construed to mean a reaction step that may actually be carried out in one or more reactors operating in series, parallel, or any combination thereof. Thus, an "isomerization reactor" should be construed to mean an isomerization step (isomerization reaction step) occurring in one or more reactors operating in series, parallel, or any combination thereof. Similarly, a "hydroformylation reactor" should be construed to mean a hydroformylation step (hydroformylation reaction step) occurring in one or more reactors operating in series, parallel, or any combination thereof. Furthermore, a "hydrogenation reactor" should be construed to mean a hydrogenation step (hydrogenation reaction step) occurring in one or more reactors operating in series, parallel, or any combination thereof.

[0103] Unless otherwise specified, temperatures given herein are in degrees Celsius (°C).

[0104] Unless otherwise specified, pressures given herein are in bar (g), i.e., bar gauge, where 0 bar (g) is atmospheric pressure, e.g., 14.70 psia (or 0 psig).

[0105] Pressure can also be expressed in absolute terms, which is written as bar(a) or bar (absolute).

[0106] Pressure can also be expressed in millibars, and is written as mbar, mbar(a), mbar absolute, or mbar (absolute), which all refer to pressure in units of millibar absolute pressure and are all equivalent and used interchangeably.

[0107] Unless otherwise specified, composition percentages given herein are by weight and are disclosed as weight percent (wt%).

[0108] Alternatively, concentrations are expressed herein in parts per million (ppm).

[0109] As used herein, the number of carbon atoms in a molecule is represented by a capital "C" followed by an integer representing the number of carbon atoms in the molecule. For example, "C12" is a molecule with 12 carbon atoms (e.g., 1-dodecene).

[0110] As used herein, the term "olefin" is used synonymously with the term "alkene" to refer to a molecule containing a carbon-carbon double bond.

[0111] As used herein, "linear" is defined as a molecule, compound, or chemical structure that has no branches along its carbon backbone (ie, a straight chain).

[0112] As used herein, "branched" is defined as a molecule, compound, or chemical structure that has one or more alkyl groups attached along its carbon backbone. A "branched" molecule is an isomer of a linear (i.e., straight-chain) molecule with the same number of carbon atoms.

[0113] As used herein, the term "percent linear" is defined to have its ordinary and accustomed meaning, as well as to mean the weight percent of linear molecules in a composition.

[0114] As used herein, the term "percent branched" is defined to have its ordinary and accustomed meaning, as well as to mean the weight percent of branched molecules in a composition. The term "percent branching" is used synonymously with "percent branched" and has the same meaning. As an example, in the case of an aldehyde composition, the "branching percentage" of aldehydes (also referred to as "% branching") means the weight percent of branched aldehyde isomers relative to the total weight percent of aldehydes present, as follows: Branching rate (%) = 100 * (weight % of branched aldehyde) ÷ (weight % of branched aldehyde + weight % of linear aldehyde)

[0115] As an example, the branched C6 aldehyde composition is 25wt% 1-hexanal (linear molecule) 40wt% 2-methylpentanal (branched molecule) 35wt% 2-ethylbutanal (branched molecule) and the branching rate is 75%.

[0116] As another example, the branched C13 aldehyde composition may be 25wt% 1-tridecanal (linear molecule) 40wt% 2-methyldodecanal (branched molecule) 20wt% 2-ethylundecanal (branched molecule) 15wt% 2-propyldecanal (branched molecule) and the branching rate is 75%.

[0117] In this example, the branching of the C13 aldehyde occurs at the second carbon position from the aldehyde carbon and is defined as a "2-alkyl" branching.

[0118] Here, the percentage of "2-methyl branched" is defined as the weight percent of the compound having a methyl group branch at carbon 2. In this example of a C13 aldehyde, the percentage of 2-methyl branched aldehyde = 40 wt% (i.e., the weight percent of 2-methyldodecanal).

[0119] Here, the percentage of "2-ethyl branched" is defined as the weight percent of the compound having an ethyl group branch at carbon 2. In this C13 aldehyde example, the percentage of 2-ethyl branched aldehyde = 20 wt% (i.e., the weight percent of 2-ethylundecanal).

[0120] Unless otherwise specified, the branched and linear percentages given herein are weight percent (wt%) calculated based on the weight of the reactants and products excluding non-participating compounds.

[0121] As used herein, the term "isomerization ratio" is defined in addition to its ordinary and accustomed meaning to mean the weight percent of olefin molecules in which the olefins are isomerized from the alpha position to the internal olefin position. Specifically, "isomerization ratio" means the weight percent of internal olefins in the olefin composition, as follows:

[0122] 100*(weight percent of internal olefin) ÷ (weight percent of α-olefin + weight percent of internal olefin)

[0123] As an example, a composition obtained by isomerizing a C12 alpha olefin may be 25wt% 1-dodecene (alpha olefin) 40wt% 2-dodecene (internal olefin) 35wt% 3-dodecene (internal olefin) The isomerization rate is 75%.

[0124] As used herein, the term "internal olefin" means, unless otherwise specified, an olefin in which the double bond is in a position other than the alpha position.

[0125] Unless otherwise specified, the isomerization percentages given herein are weight percent (wt%) calculated based on the weight of reactants and products excluding non-participating compounds.

[0126] In one embodiment, the branched alcohols can be produced by a process having the following method steps: 1) Provides C4 to C36 α-olefins. 2) To provide a homogeneous rhodium organophosphorus ligand catalyst. 3) Isomerization of C4 to C36 olefins catalyzed by a rhodium catalyst under a CO / H2 atmosphere at a pressure of 0.01 bar (absolute) to 20 bar (absolute). 4) Producing an intermediate isomerized olefin product composition containing at least 20 wt% internal (non-alpha) olefins. 5) Hydroformylation of the intermediate isomerized olefin product catalyzed by a rhodium catalyst under a CO / H2 atmosphere at a pressure of 1 bar(g) to 400 bar(g). 6) Producing a branched aldehyde product composition comprising at least 25 wt% branched aldehydes. 7) Separating the branched aldehyde product from the rhodium-containing catalyst stream by a distillation process. 8) The branched aldehyde is hydrogenated under elevated hydrogen pressure in the presence of a hydrogenation catalyst. 9) Producing a branched alcohol product composition comprising at least 40 wt% branched alcohol.

[0127] In one embodiment, the branched alcohols can be produced by a process having the following method steps: 1) Provides C4 to C36 α-olefins. 2) To provide a homogeneous rhodium organophosphorus ligand catalyst. 3) Isomerization of C4 to C36 olefins catalyzed by a rhodium catalyst under a CO / H2 atmosphere at a pressure of 0.01 bar (absolute) to 20 bar (absolute) and a CO / H2 molar ratio ranging from 10:1 to 1:10. 4) Producing an intermediate isomerized olefin product composition containing at least 20 wt% internal (non-alpha) olefins. 5) Hydroformylation of the intermediate isomerized olefin product catalyzed by a rhodium catalyst under a CO / H2 atmosphere at a pressure of 1 bar(g) to 400 bar(g) and a CO / H2 molar ratio ranging from 10:1 to 1:10. 6) Producing a branched aldehyde product composition comprising at least 25 wt% branched aldehydes. 7) Separating the branched aldehyde product from the rhodium-containing catalyst stream by a distillation process. 8) The branched aldehyde is hydrogenated under elevated hydrogen pressure in the presence of a hydrogenation catalyst. 9) Producing a branched alcohol product composition comprising at least 40 wt% branched alcohol.

[0128] FIG. 1 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor and a hydroformylation reactor.

[0129] FIG. 1 shows a two-stage process in which stream 1 having alpha olefins is fed to an isomerization reactor 100 to produce stream 2 having isomerized olefins, and stream 2 is fed to a hydroformylation reactor 200 to produce stream 3 having branched aldehydes.

[0130] (Catalyst specifications and composition)

[0131] In one embodiment, the same catalyst may be used in each of the first and second stages of the two-stage process. In one embodiment, the same catalyst may be used in isomerization reactor 100 and hydroformylation reactor 200.

[0132] In one embodiment, the isomerization and hydroformylation reactions can be catalyzed by a rhodium organophosphorus ligand catalyst. The organophosphorus ligand catalyst can be activated by the presence of CO. In one embodiment, the isomerization and hydroformylation reactions can be catalyzed by a cobalt organophosphorus ligand catalyst. In one embodiment, the isomerization and hydroformylation reactions can be catalyzed by a cobalt-rhodium organophosphorus ligand catalyst.

[0133] In one embodiment, a rhodium (-PPh3) catalyst system can be used as the catalyst.

[0134] For example, a triphenylphosphine rhodium (-PPh3) catalyst system can exist in different states and / or configurations to enable its use in different reactions, such as isomerization and hydroformylation reactions. As shown in Sequence 1 below, the leftmost position shows the catalyst in an inactive state because no CO is present and the three attached -PPh3 groups "block" the catalytically active sites. However, upon addition of CO, the -PPh3 groups on the rhodium are gradually replaced with CO groups, "opening" and activating the catalyst so that it can catalyze the isomerization and hydroformylation reactions of the presently disclosed embodiments. (Sequence 1: Triphenylphosphine rhodium activation sequence) [ka]

[0135] (Catalyst Composition)

[0136] In one embodiment, the molar ratio of phosphorus (“P”) to rhodium (“Rh”) (P:Rh) in the isomerization or hydroformylation reaction can be in the range of 1:1 to 1000:1, or 3:1 to 200:1, or 5:1 to 50:1, as non-limiting examples, 1:1, 3:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 100:1, 200:1, 500:1, or 1000:1.

[0137] In one embodiment, the concentration of Rh in the isomerization or hydroformylation reaction can be in the range of 1 to 10,000 ppm, 10 to 1,000 ppm, or 20 to 200 ppm, with non-limiting examples being 1 ppm, 20 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 1,000 ppm, 2,000 ppm, 5,000 ppm, 7,500 ppm, or 10,000 ppm.

[0138] In one embodiment, the catalyst used in the isomerization and hydroformylation reactions is an organometallic rhodium ligand complex consisting of Rh(CO)ACAC ((acetylacetonato)dicarbonylrhodium(I)) and tris(2,4-di-t-butylphenyl)phosphite ligand.

[0139] (isomerization)

[0140] The first stage occurs in isomerization reactor 100, and the stream 1 feed to isomerization reactor 100 may have a composition including: C4 to C36 α-olefins (or mixtures thereof), Rhodium catalyst A, Carbon monoxide (CO), and ·hydrogen

[0141] Optionally, stream 1 may contain a high boiling inert solvent, such as a polyalphaolefin.

[0142] Rhodium catalyst A is an organometallic complex of rhodium and at least one organophosphorus ligand. The isomerization reaction can be carried out in the presence of CO and H2 at a pressure of 0.01 bar (absolute) to 20 bar (absolute) and a temperature of 30 to 300°C, for example, 90°C. The isomerization reaction conditions can be described as proceeding under a CO / H2 atmosphere at a pressure of 0.01 bar (absolute) to 20 bar (absolute) and a temperature of 30 to 300°C, for example, 90°C. The isomerization reaction can be carried out at a CO:H2 molar ratio of 10:1 to 1:10.

[0143] The isomerization process can be run batchwise or continuously. All reactions and unit operations disclosed herein can be run batchwise or continuously.

[0144] In one embodiment, the catalyst used in the isomerization and hydroformylation reactions is a rhodium ligand complex consisting of Rh(CO)ACAC ((acetylacetonato)dicarbonylrhodium(I)) and tris(2,4-di-t-butylphenyl)phosphite ligand in a PAO-4 (polyalphaolefin) high-boiling inert solvent.

[0145] In a non-limiting example, stream 1 may have one or more of the ingredients identified in the sales specifications of Figures 7-12.

[0146] In one embodiment, a feed having alpha olefins or having a mixture of linear olefins can be isomerized at a temperature ranging from 30°C to 500°C, 40°C to 200°C, or 50°C to 120°C, non-limiting examples being 30°C, 50°C, 80°C, 90°C, 100°C, 120°C, 150°C, 180°C, 200°C, 250°C, 300°C, 400°C, or 500°C.

[0147] In one embodiment, a feed having alpha olefins or having a mixture of linear olefins can be isomerized at a pressure ranging from 0.0 bar(g) to 20 bar(g), 0.1 bar(g) to 10 bar(g), or 0.5 bar(g) to 5 bar(g), as non-limiting examples, 0.01 bar(g), 1 bar(g), 5 bar(g), 7.5 bar(g), 9 bar(g), 10 bar(g), 12 bar(g), 15 bar(g), 18 bar(g), or 20 bar(g).

[0148] In one embodiment, the isomerization of a linear alpha olefin, or a mixture of linear alpha olefins, can be carried out at a pressure ranging from 0 bar(g) to 20 bar(g), for example, at a pressure of 0 bar(g), 0.1 bar(g), 0.5 bar(g), 1 bar(g), 2 bar(g), 5 bar(g), 10 bar(g), or 20 bar(g).

[0149] In one embodiment, isomerization of a linear alpha olefin, or a mixture of linear alpha olefins, can be carried out at a CO / H molar ratio ranging from 10:1 to 1:10, for example, a CO / H molar ratio of 5:1, 2:1, 1.5:1, 1.1:1, 1.05:1, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, 1:1.3, 1:1.5, 1:2, 1:3, 1:5, or 1:10.

[0150] In one embodiment, the isomerization of a linear alpha olefin, or a mixture of linear alpha olefins, can be carried out at a CO / H2 molar ratio ranging from 1.2:1 to 1:1.2.

[0151] In one embodiment, the isomerization of a linear alpha olefin, or a mixture of linear alpha olefins, can be carried out at up to 20 bar(g) and up to 100° C., for example, 1 bar(g) and 90° C. In one embodiment, the isomerization of a linear alpha olefin, or a mixture of linear alpha olefins, can be carried out at a pressure of up to 20 bar(g), up to 100° C., and a CO:H molar ratio of up to 1:1, for example, 1 bar(g), 90° C., and a CO:H ratio of 1:1.15.

[0152] (Stream 1: Alpha Olefin Feed Composition)

[0153] In one embodiment, Stream 1 can be a C4 to C36 linear alpha olefin. For example, the Stream 1 feed can be a 1-dodecene feedstock that is substantially a C12 linear alpha olefin, such as AlphaPlus® 1-Dodecene (Chevron Phillips Chemical Co., P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260), shown in Sales Specification 1 in Figure 7.

[0154] In one embodiment, the feed in Stream 1 can be a 1-dodecene feedstock that is substantially a C12 linear alpha olefin, such as NEODENE® 12 (Shell Global Solutions, One Shell Plaza, 910 Louisiana, Houston, TX 77002-4916, USA, phone number (832) 337-2000) shown in Sales Specification 3 in Figures 9A and 9B.

[0155] In another embodiment, the Stream 1 feed can be a 1-dodecene feedstock that is a substantially C12 linear alpha olefin, such as AlphaOlefin C12 (dodecane-1) from Ineos Oligomers, Inc. (2600 South Shore Blvd., No. 400, League City, Texas 77573, phone number (281) 535-4266), shown in Sales Specification 4 in Figure 10.

[0156] In one embodiment, the feed in Stream 1 can be a 1-tetradecene feedstock that is substantially a C14 linear alpha olefin, such as AlphaPlus® 1-tetradecene (Chevron Phillips Chemical Co., P.O. Box 4910, The Woodlands, TX 77387-4910, USA, phone number (800) 231-3260), shown in Sales Specification 2 in FIG.

[0157] In one embodiment, the feed in Stream 1 can be a 1-tetradecene feedstock that is substantially a C14 linear alpha olefin, such as NEODENE® 14 (Shell Global Solutions, One Shell Plaza, 910 Louisiana, Houston, TX 77002-4916, USA, phone number (832) 337-2000) shown in Sales Specification 5 in Figures 11A and 11B.

[0158] In another embodiment, the Stream 1 feed can be a 1-tetradecene feedstock that is a substantially C14 linear alpha olefin, such as AlphaOlefin C14 (Tetradecan-1) from Ineos Oligomers, Inc. (2600 South Shore Blvd., No. 400, League City, Texas 77573, phone number (281) 535-4266), shown in Sales Specification 12 in Figure 6.

[0159] In one embodiment, the Stream 1 feed can be a composition having one or more alpha olefins. The alpha olefins in the Stream 1 feed can be the same or different and can have the same or different carbon chain lengths. For example, the alpha olefins in Stream 1 provided as reactants for isomerization can be one or more alpha olefins from the group C4 to C36 alpha olefins.

[0160] In one embodiment, the C12 linear alpha olefins supplied as reactants for isomerization can be 90.0 wt% or greater, e.g., 94.0 wt% or greater C12 linear alpha olefins, 94.6 wt% C12 linear alpha olefins, 99 wt% C12 linear alpha olefins, or greater.

[0161] In one embodiment, the C14 alpha olefins supplied as reactants for isomerization can be 90.0 wt% or more, e.g., 93.0 wt% or more C14 linear alpha olefins, or 93.4 wt% C14 linear alpha olefins, or 99 wt% or more C14 linear alpha olefins, or more.

[0162] In one embodiment, the alpha olefin feed to the isomerization reactor has a vinylidene concentration of 10 wt% or less, such as 4 wt% or less.

[0163] (Stream 2: Isomerization Reactor Product Stream Composition)

[0164] The isomerization reaction in isomerization reactor 100 produces an isomerization product stream that is fed to hydroformylation reactor 200. Stream 2 can have a composition that includes internal olefin products obtained from the isomerization reaction. As a non-limiting example, a portion of the starting alpha olefins can be isomerized to produce an olefin mixture that includes: more than 20 wt. % internal olefins, i.e. olefins in which the double bond is isomerized from the α position to the interior of the molecule, and Less than 80% by weight of alpha olefins

[0165] Stream 2 is an isomerization reactor product stream containing isomerized olefins that can have an isomerization rate ranging from 5 wt% to 99% or more, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or 99 wt%. In one embodiment, the isomerization reactor product stream, Stream 2, can have internal olefins at a composition of 20 wt% or more.

[0166] (Stream 3: Hydroformylation Product Composition)

[0167] In one embodiment, the hydroformylation product stream, Stream 3, may have a composition that includes greater than 25 wt% branched aldehydes.

[0168] (hydroformylation)

[0169] The second stage of the two-stage process illustrated in Figure 1 occurs in hydroformylation reactor 200. In this step, the feed (Stream 2) has a composition including: a C4-C36 olefin mixture containing more than 20 wt. % linear internal olefins and less than 80 wt. % linear alpha olefins, Rhodium catalyst A, Carbon monoxide (CO), Hydrogen, and C5 to C37 aldehydes (trace components)

[0170] Optionally, stream 2 may contain a high boiling inert solvent.

[0171] The reaction in hydroformylation reactor 200 proceeds using the same rhodium catalyst A at a temperature between 30 and 300°C. Because higher pressures favor the production of the desired branched aldehydes, the reaction in hydroformylation reactor 200 is carried out under a CO / H2 atmosphere at a pressure higher than that in isomerization reactor (100). In this step, the olefin mixture (or a portion of the olefin mixture) is hydroformylated to produce an aldehyde mixture containing: more than 25 wt% branched aldehydes, and Less than 75% by weight of linear aldehydes

[0172] In one embodiment, the feed to the hydroformylation having internal olefins or a mixture of alpha olefins and internal olefins can be hydroformylated at temperatures ranging from 30°C to 500°C, 40°C to 200°C, or 50°C to 120°C, non-limiting examples being 30°C, 50°C, 80°C, 90°C, 100°C, 120°C, 150°C, 180°C, 200°C, 250°C, 300°C, 400°C, or 500°C.

[0173] In one embodiment, the feed to the hydroformylation having internal olefins or having a mixture of alpha and internal olefins can be hydroformylated at a pressure ranging from 0 bar(g) to 500 bar(g), 5 bar(g) to 100 bar(g), or 7 bar(g) to 30 bar(g), as non-limiting examples, 0 bar(g), 1 bar(g), 5 bar(g), 7 bar(g), 10 bar(g), 15 bar(g), 30 bar(g), 50 bar(g), 100 bar(g), 150 bar(g), 200 bar(g), 250 bar(g), 300 bar(g), 350 bar(g), 400 bar(g), or 500 bar(g).

[0174] In one embodiment, a feed to a hydroformylation having an internal olefin, or having a mixture of alpha and internal olefins, can be hydroformylated at a CO / H molar ratio ranging from 10:1 to 1:10, for example, 5:1, 2:1, 1.5:1, 1.1:1, 1.05:1, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, 1:1.3, 1:1.5, 1:2, 1:3, 1:5, or 1:10.

[0175] In one embodiment, the feed to the hydroformylation having internal olefins or a mixture of alpha and internal olefins can be hydroformylated at a CO / H molar ratio ranging from 1.2:1 to 1:1.2.

[0176] In one embodiment, a feed having alpha olefins or having a mixture of linear olefins can be hydroformylated at a pressure of 15 bar(g) and 90°C.

[0177] Stream 2 may also contain small amounts of mixed aldehydes with carbon numbers C5 to C37 produced from the hydroformylation of C4 to C36 alpha olefins and C4 to C36 internal olefins. While not an intended purpose, aldehyde production in the isomerization reactor (100) is expected to occur at low rates. Because the aldehydes produced in this step tend to be linear aldehydes rather than the desired branched aldehydes, aldehyde production in this step should be controlled to a low level.

[0178] Figure 2 shows an embodiment of a chemical manufacturing process having an isomerization reactor 100 and using an optional isomerization reactor bypass, Stream 4, used to control the feed composition to a hydroformylation reactor 200. In the embodiment of Figure 2, the isomerization reactor product, Stream 2, is combined with the isomerization reactor bypass stream, Stream 4, to produce Stream 6, the hydroformylation reactor feed stream of the embodiment of Figure 2.

[0179] FIG. 2 illustrates the two-stage process of FIG. 1 in an embodiment with an optional olefin bypass stream, Stream 4, bypassing the isomerization reactor (100). In this embodiment, a portion of Stream 1 can be bypassed as Stream 4 around the isomerization reactor (100), and a portion of Stream 1 can be fed to the isomerization reactor (100) as Stream 5. Stream 2 is the isomerized product of the isomerization reactor (100) and is combined with Stream 4 to provide Stream 6, which is the feed to the hydroformylation reactor 200. The bypass function of Stream 4 provides a convenient and effective means for controlling the degree of olefin isomerization in the process. By adjusting the portion of Stream 1 that is isomerized (Stream 5) and the portion of Stream 1 that is not isomerized (Stream 4), the degree of olefin isomerization can be controlled to a desired value. The degree of olefin isomerization is a key variable that determines the degree of aldehyde branching. Therefore, by controlling the degree of olefin isomerization, the degree of aldehyde branching obtained in Stream 3 can be controlled to a desired value.

[0180] In the embodiment of Figure 2, the compositions of Stream 1, Stream 4, which is the isomerization reactor bypass stream, and Stream 5 can be the same. As shown in Figure 2, Stream 4 and Stream 5 are streams branched off from Stream 1.

[0181] Stream 1: Alpha Olefin Feed Composition

[0182] Stream 2: Isomerization reactor product (>20% internal olefins) composition

[0183] Stream 3: Hydroformylation product (>25% branching rate) composition

[0184] Stream 4: Isomerization reactor bypass (optional) composition

[0185] Stream 5: Isomerization reactor feed composition

[0186] Stream 6: Hydroformylation reactor feed composition

[0187] Figure 3 shows one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, and catalyst recovery. In this non-limiting embodiment, the process of Figure 2 is modified by adding a catalyst recovery step, catalyst recovery 300, to recover the rhodium catalyst and produce a recovered rhodium catalyst stream, Stream 7, which is recycled to the isomerization reactor 100, and Stream 8, which has a composition of branched aldehydes and unreacted olefins. Stream 8 is a product stream of branched aldehydes and unreacted olefins.

[0188] Figure 3 adds catalyst recovery 300 to the process of Figure 2. Stream 3 is the reactor product of hydroformylation reactor 200, with a composition of Stream 3 including: C5-C37 aldehyde mixture, more than 25 wt% branched aldehydes, and Less than 75% by weight of linear aldehydes, Unreacted C4 to C36 olefins Unreacted CO / H2, and Rhodium catalyst A

[0189] In one embodiment, the composition of stream 3 may optionally include a high boiling inert solvent.

[0190] In the catalyst recovery 300 step, unreacted CO / H gas is vented, and the aldehyde mixture and unreacted olefins are distilled overhead at reduced pressure, e.g., less than 0.1 bar (absolute), and elevated temperature, e.g., 100-200°C, to produce overhead liquid stream 8. In one embodiment, the olefins fed to hydroformylation reactor 200 are completely (or nearly completely) converted to aldehydes in hydroformylation reactor 200, and stream 8 is a mixed aldehyde product stream that does not require further purification.

[0191] In the embodiment of FIG. 3 , the non-volatile liquid residue from catalyst recovery 300 is shown as Stream 7. This stream contains recovered rhodium catalyst A and, optionally, a high-boiling inert solvent, if one is used. The recovered rhodium catalyst stream, Stream 7, is then recycled to isomerization reactor 100 for reuse in the process. While not essential to the present invention, it is often useful to include a high-boiling inert solvent in the system as a useful liquid carrier for the recovered rhodium catalyst. An example of such a high-boiling inert solvent is polyalphaolefin (PAO). In one embodiment, rhodium catalyst A can be an organometallic complex of rhodium and a water-soluble organophosphorus ligand. In this embodiment, the catalyst recovery 300 step can optionally separate the catalyst from the aldehyde product via an aqueous / organic extraction step rather than via a distillation step. In one embodiment, one or more of an extraction step and / or a distillation step can be optionally used. In these embodiments, the rhodium catalyst can be recovered in the aqueous phase and returned to the isomerization reactor 100 for reuse in the process to form a recycle, and the aldehyde product and unreacted olefins can be recovered as an organic phase resulting from the extraction step.

[0192] Stream 1: Alpha Olefin Feed Composition

[0193] Stream 2: Isomerization reactor product composition

[0194] Stream 3: Hydroformylation product composition

[0195] Stream 4: Isomerization reactor bypass composition

[0196] Stream 5: Isomerization reactor feed composition

[0197] Stream 6: Hydroformylation reactor feed composition

[0198] Stream 7: Recovered rhodium catalyst stream composition

[0199] Stream 8: Branched aldehyde / unreacted olefin composition

[0200] Figure 4 adds an aldehyde distillation unit 400 to the process of Figure 3. Figure 4 shows one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, catalyst recovery, and aldehyde distillation.

[0201] Figure 4 shows the process of Figure 3 with the addition of an aldehyde distillation step, shown as aldehyde distillation 400. In this embodiment, stream 8 is the feed stream to aldehyde distillation (400) and, in one embodiment, has, for example, the following composition: 1) A C5 to C37 aldehyde mixture containing more than 25 wt% branched aldehydes and less than 75 wt% linear aldehydes. 2) Unreacted C4 to C36 olefins

[0202] In the embodiment of Figure 4, in the distillation process of aldehyde distillation 400, unreacted C4 to C36 olefins that were not converted to aldehydes in hydroformylation reactor 200 are distilled overhead as a light product shown as Stream 9 with unreacted olefins. The unreacted olefins in Stream 9 are recycled back to the beginning of the process and, in the embodiment of Figure 4, are mixed with Stream 1. As shown, the unreacted olefins in Stream 9 are combined with alpha olefin feed stream 1 to produce stream 10, which is the mixed olefins feed to isomerization reactor 100.

[0203] In the embodiment of FIG. 4, the C5 to C37 aldehyde mixture in stream 8 produced by catalyst recovery 300 is further purified and cleaned by distillation in aldehyde distillation 400 to produce a distilled high purity C5 to C37 branched aldehyde product stream, shown in one embodiment as stream 11, which is free or nearly free of unreacted C4 to C36 olefins.

[0204] Stream 1: Alpha Olefin Feed Composition

[0205] Stream 2: Isomerization reactor product composition

[0206] Stream 3: Hydroformylation product composition

[0207] Stream 4: Isomerization reactor bypass composition

[0208] Stream 5: Isomerization reactor feed composition

[0209] Stream 6: Hydroformylation reactor feed composition

[0210] Stream 7: Recovered rhodium catalyst stream composition

[0211] Stream 8: Branched aldehyde / unreacted olefin composition

[0212] Stream 9: Unreacted olefin composition

[0213] Stream 10: Mixed Olefin Feed Composition

[0214] Stream 11: Branched aldehyde product composition

[0215] FIG. 5 illustrates one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, a catalyst recovery reactor, and an aldehyde hydrogenation reactor.

[0216] FIG. 5 shows a different embodiment in which the process of FIG. 3 is modified to feed stream 8 to an aldehyde hydrogenation reactor 500 to produce branched alcohols as stream 9, a branched alcohol product stream.

[0217] Figure 5 shows the process of Figure 3 with the addition of an aldehyde hydrogenation step, shown as aldehyde hydrogenation reactor 500. In one embodiment, stream 8 is the feed stream to aldehyde hydrogenation reactor (500) and has, for example, the following composition: 1) A C5 to C37 aldehyde mixture containing (a) more than 25 wt% branched aldehydes and (b) less than 75 wt% linear aldehydes. 2) Unreacted C4 to C36 olefins

[0218] In the embodiment of FIG. 5, C5-C37 aldehydes are hydrogenated in the presence of hydrogen and a hydrogenation catalyst, such as catalyst A, in aldehyde hydrogenation reactor (500) to produce stream 12.

[0219] Suitable examples of hydrogenation catalysts include base metal catalysts supported on high surface area supports such as ceramic, carbon, alumina, silica, titania, and zirconia, with the primary base metal component being nickel, cobalt, copper, manganese, molybdenum, zinc, and / or iron, or various combinations thereof, deposited and dispersed on the surface of the support. Examples of base metal nickel include alumina-supported nickel catalysts, silica-supported nickel catalysts, titania-supported nickel catalysts, zirconia-supported nickel catalysts, and carbon-supported nickel catalysts. Similar supported metal catalysts can be found for other base metals. Noble metal catalysts supported on high surface area supports such as ceramic, carbon, alumina, silica, titania, and zirconia are also suitable, with the metals including platinum, palladium, gold, silver, iridium, ruthenium, or various combinations thereof. Examples of noble metal platinum include carbon-supported platinum, silica-supported platinum, titania-supported platinum, zirconia-supported platinum, or alumina-supported platinum catalysts. Similar supported metal catalysts can be found for other noble metals. Raney® nickel and Raney® cobalt catalysts, manufactured by W.R. Grace & Company (7500 Grace Drive, Columbia, MD 21044, USA, phone number 1-410-531-4000), are also suitable hydrotreating catalysts. Suitable hydrotreating catalysts can be either finely divided slurry catalysts for use in stirred batch or continuous stirred tank reactors (i.e., CSTRs), or fixed-bed catalysts for use in reactors such as trickle-bed reactors.

[0220] Stream 12 is a branched alcohol product and, in one embodiment, may have a composition including: 1) A C5 to C37 alcohol mixture containing (a) more than 30 wt% branched alcohols and (b) less than 70 wt% linear alcohols. 2) C4 to C36 paraffins (alkanes)

[0221] In the embodiment of FIG. 5, C5 to C37 alcohols are produced in aldehyde hydrogenation reactor 500 by hydrogenation of the corresponding aldehydes, and C4 to C36 paraffins are also produced in aldehyde hydrogenation reactor 500 by hydrogenation of unreacted C4 to C36 olefins contained in stream 8.

[0222] Optionally, a distillation step can be used after aldehyde hydrogenation reactor 500 to remove low boiling C4-C36 paraffins to produce a distilled high purity C5-C37 branched alcohol product that is free or nearly free of C4-C36 paraffins, thereby increasing the C5-C37 alcohol content in stream 12 as the C4-C36 paraffin content decreases.

[0223] Stream 1: Alpha Olefin Feed Composition

[0224] Stream 2: Isomerization reactor product composition

[0225] Stream 3: Hydroformylation product composition

[0226] Stream 4: Isomerization reactor bypass composition

[0227] Stream 5: Isomerization reactor feed composition

[0228] Stream 6: Hydroformylation reactor feed composition

[0229] Stream 7: Recovered rhodium catalyst stream composition

[0230] Stream 8: Branched aldehyde / unreacted olefin composition

[0231] Stream 12: Branched Alcohol Products

[0232] In one embodiment, stream 12 may be a composition of branched alcohol products having a branching percentage greater than 25%.

[0233] Figure 6 shows one embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, catalyst recovery, aldehyde distillation, and an aldehyde hydrogenation reactor. Figure 6 shows the process of Figure 4 with the addition of an aldehyde hydrogenation reactor 500. In the embodiment of Figure 6, the branched aldehyde product stream, stream 11, is the feed stream to the aldehyde hydrogenation reactor (500) and may have, for example, a C5 to C37 aldehyde mixture including: 1) More than 25 wt% branched aldehydes 2) Less than 75 wt% linear aldehyde

[0234] In the embodiment of Figure 6, C5-C37 aldehydes are hydrogenated in aldehyde hydrogenation reactor (500) in the presence of hydrogen and a hydrogenation catalyst, such as catalyst A, to produce stream 12. Stream 12 is a branched alcohol product stream and may have a C5-C37 alcohol composition including, for example: 1) More than 30 wt% branched alcohol 2) Less than 70 wt% straight-chain alcohol

[0235] In the embodiment of FIG. 6, C5-C37 alcohols are produced by hydrogenation of the corresponding aldehydes, which are the reaction products of hydroformylation reactor 200.

[0236] Optionally, a distillation step can be added after aldehyde hydrogenation reactor 500 to remove undesirable impurities, such as low levels of C4-C36 paraffins, and purify the distilled C5-C37 branched alcohol product to increase the C5-C37 alcohol content (purity) in stream 12.

[0237] Stream 1: Alpha Olefin Feed Composition

[0238] Stream 2: Isomerization reactor product composition

[0239] Stream 3: Hydroformylation product composition

[0240] Stream 4: Isomerization reactor bypass composition

[0241] Stream 5: Isomerization reactor feed composition

[0242] Stream 6: Hydroformylation reactor feed composition

[0243] Stream 7: Recovered rhodium catalyst stream composition

[0244] Stream 8: Branched aldehyde / unreacted olefin composition

[0245] Stream 9: Unreacted olefin composition

[0246] Stream 10: Mixed Olefin Feed Composition

[0247] Stream 11: Branched aldehyde product composition

[0248] Stream 12: Branched alcohol products (>30% branching)

[0249] Example 1: Preparation of branched C13 aldehyde products

[0250] (introduction)

[0251] In one embodiment, the isomerization, hydroformylation, and hydrogenation reactions produce two branched alcohol products from two starting alpha olefins. Optionally, a mixture of multiple alpha olefins can be used.

[0252] In one embodiment, a first alpha olefin, 1-dodecene, can be converted to a mixture of branched tridecanols by the chemical processes described herein, and a second alpha olefin, 1-tetradecene, can be converted to a mixture of branched pentadecanols by a similar chemical process.

[0253] The process can be carried out batchwise or continuously.

[0254] (Batch Process Embodiment)

[0255] In one embodiment, the first stage of the process is a batchwise isomerization of individual α-olefins using a homogeneous rhodium organophosphorus ligand catalyst system at moderate temperature and pressure. The second stage is a hydroformylation reaction using the same rhodium organophosphorus ligand catalyst system, which can provide the corresponding branched tridecanals and branched pentadecanals in high yield and selectivity. For example, the branched tridecanal product obtained from such an isomerization and hydroformylation process can yield a composition containing a mixture of linear 1-tridecanal and 2-alkyl branched tridecanal isomers. [ka]

[0256] In one embodiment, the catalyst used in the isomerization and hydroformylation reactions is an organometallic rhodium ligand complex consisting of Rh(CO)ACAC ((acetylacetonato)dicarbonylrhodium(I)) and tris(2,4-di-t-butylphenyl)phosphite ligand.

[0257] After the completion of the hydroformylation batch chemical process, the crude aldehyde can be flash distilled to remove the expensive catalyst-ligand complex and recycled. The flashed aldehyde vapor can be directly fed to distillation to obtain high purity branched aldehyde intermediates.

[0258] In this embodiment, the branched tridecanol and pentadecanol can be hydrogenated batchwise in the presence of a hydrogenation catalyst, such as a base metal catalyst, for example, a supported nickel catalyst such as Raney® (WR Grace & Company, 7500 Grace Drive, Columbia, MD 21044, USA, phone number 1-410-531-4000), or a noble metal catalyst, at elevated pressure and moderate temperature. During hydrogenation, the aldehyde functionality is converted to the corresponding alcohol, producing the desired branched tridecanol and the desired branched pentadecanol, respectively.

[0259] In a batch reaction embodiment, the isomerization reaction and the hydroformylation reaction can be carried out in the same or different reactors.

[0260] When the same reactor is used for both the isomerization reaction and the hydroformylation reaction, the isomerization can be carried out under one set of reaction conditions and the hydroformylation can be carried out under a different set of reaction conditions. The reaction temperatures for the isomerization reaction and the hydroformylation reaction can be the same or different. The reaction pressures for the isomerization reaction and the hydroformylation reaction can be the same or different. The molar ratios of CO:H for the isomerization reaction and the hydroformylation reaction can be the same or different. In one embodiment, the hydroformylation reaction is carried out at a higher pressure than the isomerization reaction.

[0261] In one embodiment, the batch hydroformylation reaction is carried out at a moderate temperature of 80°C to 100°C and a moderate pressure of 15 to 20 bar(g). In this embodiment, flash removal of the branched aldehyde can be carried out in a flash unit operation, such as a flash drum, optionally in combination with a distillation column. In another embodiment, flash removal of the branched aldehyde can be carried out in an evaporation unit operation, such as a wiped film evaporator or a falling film evaporator, optionally in combination with a distillation column. The optional distillation can be carried out at pressures including variable vacuums from 1 mbar absolute to 999 mbar absolute, including, by non-limiting example, 5 mbar absolute, 10 mbar absolute, 20 mbar absolute, 50 mbar absolute, 100 mbar absolute, 500 mbar absolute, or higher.

[0262] In one embodiment, the hydrogenation of the branched aldehyde intermediate is carried out in a batch reactor at a hydrogen pressure of 10 bar(g) to 100 bar(g), e.g., 20 bar(g), 30 bar(g), 40 bar(g), 50 bar(g), 60 bar(g), 70 bar(g), 80 bar(g), 90 bar(g), or more. The hydrogenation can be carried out at a temperature of 50°C to 300°C, e.g., 50°C, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, or 450°C.

[0263] In one embodiment, the reaction of the reactants is considered complete when less than 1% of the branched aldehyde intermediate remains. In one embodiment, the reaction of the reactants is considered complete when less than 0.1% of the branched aldehyde intermediate remains. In this embodiment, the filtered crude branched alcohol is nearly colorless and is a highly pure (>97%) and highly branched (>80%) product.

[0264] In one embodiment, a branched alcohol product can be produced from an alpha olefin feed through a batch isomerization process, a batch hydroformylation process, and then flash distillation to produce a branched aldehyde intermediate, which is then batch hydrogenated to produce the final branched alcohol product, which is then filtered to remove the hydrogenation catalyst.

[0265] Example 2: Preparation of branched C13 alcohol product

[0266] The C12 linear alpha olefin feedstock (1-dodecene) was obtained from Chevron Phillips Chemical Company under the trade name AlphaPlus® 1-dodecene (Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, telephone number (800) 231-3260). The homogeneous rhodium organophosphorus catalyst used in this example was prepared in a high-pressure stainless steel stirred autoclave. An autoclave was charged with 0.027 wt% Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)), 1.36 wt% tris(2,4-di-t-butylphenyl)phosphite ligand, and 98.62 wt% Synfluid® PAO4cSt (Chevron Phillips Chemical Co., P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260) inert solvent. This mixture was heated at 80°C under a CO / H2 atmosphere at 2 bar (g) pressure for 4 hours to produce an activated rhodium catalyst solution (109 ppm rhodium, P:Rh molar ratio = 20). 1-Dodecene linear alpha olefin was added to the rhodium catalyst solution in the autoclave to produce a starting reaction mixture with a rhodium concentration of 35 ppm. This α-olefin feed was isomerized at 80°C under a CO / H atmosphere at 1 bar(g) for 10 hours. The isomerized olefins were then hydroformylated at 70°C under a CO / H atmosphere at 20 bar(g) for 8 hours. The molar ratio of CO to H in both the isomerization and hydroformylation steps was 1:1.15. The resulting hydroformylation reaction product was flash distilled at 140-150°C and 25 mbar absolute pressure to recover the rhodium catalyst solution as the bottom product and a branched C13 aldehyde overhead product with the following composition: weight% 1-Tridecanal 13.9% 2-Methyldodecanal 28.3% 2-Ethylundecanal 15.2% 2-Propyldecanal 14.5% 2-Butylnonanal 13.6% 2-Pentyloctanal 12.6% Total 98.0%

[0267] The weight percent branching of the branched C13 aldehyde product was 86.2%. The weight percent of linear aldehydes was 14.2%. The weight percent of 2-methyl branched aldehydes was 28.9%. The weight percent of 2-ethyl branched aldehydes was 15.5%.

[0268] The branched C13 aldehyde product was hydrogenated in a high-pressure Inconel 625 stirred autoclave at 150 °C and 20 bar(g) hydrogen pressure. The hydrogenation catalyst was Raney® Nickel 3111 (WR Grace & Company, 7500 Grace Drive, Columbia, MD 21044, USA, tel. 1-410-531-4000) catalyst with a 0.25 wt% loading. The aldehyde was hydrogenated for 10 hours, and the resulting reaction mixture was filtered to yield the branched C13 alcohol product, which contained: weight% 1-Tridecanol 13.2% 2-Methyldodecanol 29.1% 2-Ethylundecanol 15.5% 2-Propyldecanol 14.4% 2-Butylnonanol 13.2% 2-Pentyloctanol 12.9% Total 98.4%

[0269] The weight percent branching of the branched C13 alcohol product was 86.6%. The weight percent of linear alcohols was 13.4%. The weight percent of 2-methyl branched alcohols was 29.6%. The weight percent of 2-ethyl branched alcohols was 15.8%.

[0270] Example 3: Preparation of branched C15 alcohol product

[0271] The recovered rhodium catalyst stream from Example 2 was charged to a high-pressure stainless steel stirred autoclave, and a Chevron Phillips Chemical Company C14 linear alpha olefin feedstock (1-tetradecene) (AlphaPlus® 1-tetradecene, Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260) was added. The resulting mixture had a rhodium concentration of approximately 30 ppm. The 1-tetradecene linear alpha olefin was isomerized at 1 bar(g) pressure under a CO / H atmosphere at 80°C for 12 hours. The isomerized olefin was then hydroformylated at 20 bar(g) pressure under a CO / H atmosphere at 70°C for 8 hours. The resulting reaction product was flash distilled at 150-160°C and 25 mbar absolute pressure, recovering the rhodium catalyst solution as the bottom product and the branched C15 aldehyde overhead product. The recovered rhodium catalyst solution was then reused to complete a second batch isomerization (4 hours) and hydroformylation (6 hours) of 1-tetradecene. The C15 aldehyde products from the two batches were combined to obtain the branched C15 aldehyde product, which contained the following: weight% 1-Pentadecanal 12.1% 2-Methyltetradecanal 34.1% 2-Ethyltridecanal 21.9% 2-Propyl-dodecanal 14.0% 2-Butylundecanal 8.6% 2-Pentyldecanal + 2-Hexylnonanal 9.0% Total 99.6%

[0272] The weight percent branching of the branched C15 aldehyde product was 87.8%. The weight percent of linear aldehydes was 12.1%. The weight percent of 2-methyl branched aldehydes was 34.2%. The weight percent of 2-ethyl branched aldehydes was 22.0%.

[0273] The branched C15 aldehyde product was hydrogenated in a high-pressure Inconel 625 stirred autoclave at 150 °C and 20 bar(g) hydrogen pressure. The hydrogenation catalyst used was Raney® Nickel 3111 (WR Grace & Company, 7500 Grace Drive, Columbia, MD 21044, USA, tel. 1-410-531-4000) catalyst with a 0.25 wt% loading. The aldehyde was hydrogenated for 10 hours, and the resulting reaction mixture was filtered to yield the branched C15 alcohol product, which contained the following: weight% 1-Pentadecanol 13.7% 2-Methyltetradecanol 33.8% 2-Ethyltridecanol 21.4% 2-Propyl-dodecanol 12.4% 2-Butylundecanol 8.0% 2-Pentyldecanol + 2-Hexylnonanal 9.2% Total 98.4%

[0274] The weight percent branching of the branched C15 alcohol product was 86.1%. The weight percent of linear alcohols was 13.9%. The weight percent of 2-methyl branched alcohols was 34.3%. The weight percent of 2-ethyl branched alcohols was 21.7%.

[0275] Example 4: Preparation of branched C15 aldehyde product

[0276] The C14 linear alpha olefin feedstock (1-tetradecene) was obtained under the product name AlphaPlus® 1-tetradecene from Chevron Phillips Chemical Company (Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260). The homogeneous rhodium organophosphorus catalyst used in this example is an organometallic complex of Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)) and a triphenylphosphine ligand. The 1-tetradecene linear alpha olefin was added to the rhodium catalyst solution in a stainless steel autoclave to produce a starting reaction mixture with a rhodium concentration of 35 ppm and a P:Rh molar ratio of 20. This alpha olefin feed was isomerized at 80°C under a CO / H2 atmosphere at 1.5 bar (g) pressure for 3.5 hours. The isomerized olefins were then hydroformylated at 95°C under a CO / H atmosphere at 14 bar(g) for 9 hours. The molar ratio of CO to H in both the isomerization and hydroformylation steps was 1:1.15. The resulting hydroformylation reaction product was flash distilled at 140-150°C and 5 mbar absolute pressure to recover a branched C15 aldehyde overhead product with the following aldehyde composition: weight% 1-Pentadecanal 52.5% 2-Methyltetradecanal 33.1% 2-Ethyltridecanal 10.8% 2-Propyl-dodecanal 1.6% 2-Butylundecanal 0.6% 2-Pentyldecanal + 2-Hexylnonanal 0.9% Total 99.4%

[0277] The weight percent branching of the branched C15 aldehyde product was 47.2%. The weight percent of linear aldehydes was 52.8%. The weight percent of 2-methyl branched aldehydes was 33.3%. The weight percent of 2-ethyl branched aldehydes was 10.9%.

[0278] Figure 13 illustrates one embodiment of a chemical manufacturing process that produces n branched alcohol products through n alpha olefin feeds to an isomerization reactor, a hydroformylation reactor, catalyst recovery, aldehyde distillation, and an aldehyde hydrogenation reactor, as well as n alcohol distillation unit operations. In the embodiment of Figure 13, F1, F2, ..., F n n alpha-olefin feed, designated as α-olefins, is fed to isomerization reactor 100 to produce isomerization reactor product stream 3 containing n isomerized olefins. Stream 3 is fed to hydroformylation reactor 200 to produce stream 4, a mixture of n branched aldehydes. In catalyst recovery 300, the mixture of n branched aldehydes and unreacted olefins is distilled overhead to produce overhead stream 5, and the rhodium catalyst stream is recovered as bottoms product stream 6 and returned to isomerization reactor 100 for reuse in the process. In aldehyde distillation 400, unreacted olefins not converted to aldehydes in hydroformylation reactor 200 are distilled overhead and recovered as a light product, designated as stream 7, containing unreacted olefins. These unreacted olefins are recycled to the beginning of the process for further reaction to produce additional aldehyde products. In the embodiment of FIG. 13, stream 8 produced in the aldehyde distillation 400 step comprises a high purity mixture of distilled n branched aldehydes, and in one embodiment, is free or nearly free of unreacted olefins.

[0279] 13, the mixture of n-branched aldehydes is hydrogenated in aldehyde hydrogenation reactor (500) in the presence of hydrogen and a hydrogenation catalyst to produce a reaction product stream comprising a mixture of n-branched alcohols, Stream 9. In one embodiment, each of the n-branched alcohols produced from the hydrogenation of the corresponding n-branched aldehydes has, for example, the following alcohol isomer composition: 1) More than 30 wt% branched alcohol 2) Less than 70 wt% straight-chain alcohol

[0280] 13 , the mixture of n branched alcohols (Stream 9) from aldehyde hydrogenation reactor 500 is fed to an alcohol 1 distillation unit operation D-1, where low-boiling impurities are removed as a light stream L1, and branched alcohol 1 is recovered as a purified branched alcohol product P1; a bottoms stream (Stream B1) from the alcohol 1 distillation unit operation D-1 is fed to an alcohol 2 distillation unit operation D-2, where low-boiling impurities are removed as a light stream L2, and branched alcohol 2 is recovered as a purified branched alcohol product P2; and a bottoms stream from the alcohol 2 distillation unit operation D-2 is recovered as a stream B2. Similarly, each of the n branched alcohols contained in the mixture of branched alcohol products (Stream 9) from aldehyde hydrogenation reactor 500 is purified in a distillation unit operation to produce n purified branched alcohol products.

[0281] Figure 13 shows the following stream:

[0282] Stream F1: Alpha Olefin Feed 1

[0283] Stream F2: Alpha Olefin Feed 2

[0284] Stream F n : α-olefin feed n

[0285] Stream 3: Isomerization reactor product

[0286] Stream 4: Hydroformylation products (branched aldehydes)

[0287] Stream 5: Branched aldehydes / unreacted olefins

[0288] Stream 6: Recovered rhodium catalyst stream

[0289] Stream 7: Unreacted olefins

[0290] Stream 8: Branched Aldehydes

[0291] Stream 9: Crude branched alcohols

[0292] Stream L1: Light Stream 1

[0293] Stream P1: Branched Alcohol 1 Product

[0294] Stream B1: Bottom stream from Alcohol 1 distillation

[0295] Stream L2: Light Stream 2

[0296] Stream P2: Branched alcohol 2 product

[0297] Stream B2: Bottom stream from Alcohol 2 distillation

[0298] Stream L n :Light Stream n

[0299] Stream P n : Branched alcohol n product

[0300] Stream B n : Bottom stream from alcohol distillation

[0301] Figure 14 illustrates an embodiment of the chemical production process shown in Figure 13, in which the number of alpha-olefin feeds, n, is 2. Specifically, the first alpha-olefin feed, F1, is a C12 alpha-olefin (i.e., 1-dodecene), and the second alpha-olefin feed, F2, is a C14 alpha-olefin (i.e., 1-tetradecene). These two alpha-olefin feeds are fed to an isomerization reactor 100, which produces an isomerization reactor product stream 3 containing isomerized C12 olefins and isomerized C14 olefins. Stream 3 is fed to a hydroformylation reactor 200, which produces a mixture of C13 and C15 branched aldehydes, stream 4. In a catalyst recovery step 300, the mixture of C13 and C15 branched aldehydes and unreacted olefins is distilled overhead to produce overhead stream 5, and the rhodium catalyst stream is recovered as bottoms product stream 6 and returned to the isomerization reactor 100 for reuse in the process. In the aldehyde distillation 400 step, unreacted C12 / C14 olefins are distilled overhead and recovered as a light product shown as Stream 7 containing unreacted C12 / C14 olefins. These unreacted C12 / C14 olefins are recycled to the beginning of the process for further reaction processes to produce additional branched C13 and C15 aldehydes. In the embodiment of Figure 14, Stream 8 produced in the aldehyde distillation 400 step contains a high purity mixture of distilled C13 and C15 branched aldehydes, and in one embodiment, is free or nearly free of unreacted C12 / C14 olefins.

[0302] In the embodiment of Figure 14, a mixture of branched C13 aldehydes and branched C15 aldehydes is hydrogenated in the presence of hydrogen and a hydrogenation catalyst in aldehyde hydrogenation reactor (500) to produce a reaction product stream, Stream 9, comprising a mixture of C13 branched alcohols and C15 branched alcohols. In one embodiment, the C13 branched alcohols produced from the hydrogenation of the corresponding branched C13 aldehydes have, for example, the following C13 alcohol isomer composition: 1) More than 30 wt% branched C13 alcohol 2) Less than 70 wt% linear C13 alcohol

[0303] In one embodiment, the C15 branched alcohol produced from the hydrogenation of the corresponding branched C15 aldehyde has, for example, the following C15 alcohol isomer composition: 3) More than 30 wt% branched C15 alcohol 4) Less than 70 wt% linear C15 alcohol

[0304] 14, the mixture of C13 branched alcohols and C15 branched alcohols (Stream 9) from aldehyde hydrogenation reactor 500 is fed to a C13 alcohol distillation unit operation D-1, where low-boiling impurities are removed as lights stream 10, the branched C13 alcohols are recovered as purified and cleaned branched C13 alcohol product stream 11, and a bottoms stream (Stream 12) from C13 alcohol distillation unit operation D-1 is fed to a C15 alcohol distillation unit operation D-2, where low-boiling impurities are removed as lights stream 13, the branched C15 alcohols are recovered as purified and cleaned branched C15 alcohol product stream 14, and the bottoms stream from C15 alcohol distillation unit operation D-2 is recovered as stream 15.

[0305] Figure 14 shows the following stream:

[0306] Stream F1: C12 alpha olefin feed

[0307] Stream F2: C14 alpha olefin feed

[0308] Stream 3: Isomerization reactor product (C12 / C14 isomerized olefins)

[0309] Stream 4: Hydroformylation products (branched C13 / C15 aldehydes)

[0310] Stream 5: Branched C13 / C15 aldehydes / unreacted C12 / C14 olefins

[0311] Stream 6: Recovered rhodium catalyst stream

[0312] Stream 7: Unreacted C12 / C14 olefins

[0313] Stream 8: Branched C13 / C15 aldehydes

[0314] Stream 9: Branched C13 / C15 alcohols

[0315] Stream 10: C12 / C14 Light Stream

[0316] Stream 11: Branched C13 alcohol products

[0317] Stream 12: Crude branched C15 alcohols

[0318] Stream 13: Light stream from C15 alcohol distillation

[0319] Stream 14: Branched C15 alcohol products

[0320] Stream 15: Bottom stream from C15 alcohol distillation

[0321] FIG. 15 illustrates one embodiment of the chemical manufacturing process shown in FIG. 14, including an isomerization reactor, a hydroformylation reactor, catalyst recovery, an aldehyde hydrogenation reactor, a C13 alcohol distillation unit operation, and a C15 alcohol distillation unit operation. However, in this embodiment, there is no aldehyde distillation unit, and therefore no recovery or recycle of unreacted C12 / C14 olefins. In this embodiment, the hydroformylation reactor 200 is operated so that the hydroformylation reaction, which converts isomerized C12 / C14 olefins to branched C13 aldehydes and branched C15 aldehydes, occurs at a very high chemical conversion of the C12 / C14 olefins, e.g., 90% or greater, 95% or greater, or 98% or greater. This leaves only a low concentration of unreacted C12 / C14 olefins in the hydroformylation product (Stream 4), eliminating the aldehyde distillation step. In the catalyst recovery step 300, the rhodium catalyst stream is recovered as bottoms product stream 6, and a mixture of C13 and C15 branched aldehydes and low levels of unreacted C12 / C14 olefins is distilled overhead as stream 5. In the embodiment of FIG. 15, the mixture of branched C13 aldehydes, branched C15 aldehydes, and low levels of unreacted C12 / C14 olefins is hydrogenated in the presence of hydrogen and a hydrogenation catalyst in an aldehyde hydrogenation reactor (500) to produce stream 7, a reaction product stream containing a mixture of C13 branched alcohols, C15 branched alcohols, and low levels of C12 alkanes (dodecane) and C14 alkanes (tetradecane). These C12 alkanes and C14 alkanes are formed from the hydrogenation of the corresponding C12 and C14 alkenes. In one embodiment, the C13 branched alcohols in stream 7 produced from the hydrogenation of the corresponding branched C13 aldehydes have, for example, the following C13 alcohol isomer composition: 5) More than 30 wt% branched C13 alcohol 6) Less than 70 wt% linear C13 alcohol

[0322] In one embodiment, the C15 branched alcohol in stream 7 produced from the hydrogenation of the corresponding branched C15 aldehyde has, for example, the following C15 alcohol isomer composition: 7) More than 30 wt% branched C15 alcohol 8) Less than 70 wt% linear C15 alcohol

[0323] In the embodiment of Figure 15, the mixture of C13 branched alcohols, C15 branched alcohols, and low levels of C12 and C14 alkanes (Stream 7) from aldehyde hydrogenation reactor 500 is fed to a C13 alcohol distillation unit operation D-1. In this unit operation step, C12 alkanes and C14 alkanes are removed as low-boiling impurities in light stream 8, branched C13 alcohols are recovered as purified and cleaned branched C13 alcohol product stream 9, and a bottoms stream (Stream 10) from the C13 alcohol distillation unit operation D-1 is fed to a C15 alcohol distillation unit operation D-2. In the C15 alcohol distillation unit operation D-2, low-boiling impurities are removed as light stream 11, branched C15 alcohols are recovered as purified and cleaned branched C15 alcohol product stream 12, and a bottoms stream from the C15 alcohol distillation unit operation D-2 is recovered as stream 13.

[0324] Figure 15 shows the following stream:

[0325] Stream F1: C12 alpha olefin feed

[0326] Stream F2: C14 alpha olefin feed

[0327] Stream 3: Isomerization reactor product (C12 / C14 isomerized olefins)

[0328] Stream 4: Hydroformylation products (branched C13 / C15 aldehydes)

[0329] Stream 5: Branched C13 / C15 aldehydes / unreacted C12 / C14 olefins

[0330] Stream 6: Recovered rhodium catalyst stream

[0331] Stream 7: Branched C13 / C15 alcohols

[0332] Stream 8: C12 alkane / C14 alkane light stream

[0333] Stream 9: Branched C13 alcohol products

[0334] Stream 10: Crude branched C15 alcohol

[0335] Stream 11: Light stream from C15 alcohol distillation

[0336] Stream 12: Branched C15 alcohol products

[0337] Stream 13: Bottom stream from C15 alcohol distillation

[0338] FIG. 16 illustrates an embodiment of the chemical manufacturing process shown in FIG. 13 , except that in this embodiment, the end product of the process is an n-branched aldehyde product rather than an n-branched alcohol product as shown in FIG. 13 . This embodiment is preferred when a branched aldehyde is desired as the product. This is advantageous when a purified branched aldehyde is desired as the end product to be used (e.g., in fragrance applications) or when a purified branched aldehyde is desired as an intermediate for producing other useful derivatives, such as branched amines or branched carboxylic acids. The embodiment shown in FIG. 16 illustrates a chemical manufacturing process for producing an n-branched aldehyde product through an isomerization reactor, a hydroformylation reactor, catalyst recovery, an n-alpha olefin feed to aldehyde distillation, and an n-aldehyde distillation unit operation. This process can produce a distilled, high-purity mixture of n-branched aldehydes as stream 8 from aldehyde distillation 400 in a manner directly analogous to the process shown in FIG. 13 . In one embodiment, Stream 8 is free or substantially free of unreacted olefins. In the embodiment of FIG. 16, Stream 8 is fed directly to a series of aldehyde distillation unit operations rather than being hydrogenated to alcohols. In the embodiment of FIG. 16, the mixture of n branched aldehydes (Stream 8) is fed to an aldehyde 1 distillation unit operation D-1, where low-boiling impurities are removed as a light stream L1, branched aldehyde 1 is recovered as a purified and cleaned branched aldehyde product P1, and a bottoms stream (Stream B1) from the aldehyde 1 distillation unit operation D-1 is fed to an aldehyde 2 distillation unit operation D-2, where low-boiling impurities are removed as a light stream L2, branched aldehyde 2 is recovered as a purified and cleaned branched aldehyde product P2, and a bottoms stream from the aldehyde 2 distillation unit operation D-2 is recovered as a stream B2. Similarly, each of the n branched aldehydes contained in branched aldehyde mixture stream 8 is purified in a distillation unit operation to produce n purified branched aldehyde products.

[0339] Figure 16 shows the following stream:

[0340] Stream F1: Alpha Olefin Feed 1

[0341] Stream F2: Alpha Olefin Feed 2

[0342] Stream F n : α-olefin feed n

[0343] Stream 3: Isomerization reactor product

[0344] Stream 4: Hydroformylation products (branched aldehydes)

[0345] Stream 5: Branched aldehydes / unreacted olefins

[0346] Stream 6: Recovered rhodium catalyst stream

[0347] Stream 7: Unreacted olefins

[0348] Stream 8: Branched Aldehydes

[0349] Stream L1: Light Stream 1

[0350] Stream P1: Branched aldehyde 1 product

[0351] Stream B1: Bottom stream from aldehyde 1 distillation

[0352] Stream L2: Light Stream 2

[0353] Stream P2: Branched aldehyde 2 product

[0354] Stream B2: Bottom stream from aldehyde 2 distillation

[0355] Stream L n :Light Stream n

[0356] Stream P n : Branched aldehyde product

[0357] Stream B n : Bottom stream from aldehyde distillation

[0358] (Introduction of Examples 5 to 7)

[0359] Examples 5-7 demonstrate the simultaneous production of branched C13 aldehydes and branched C15 aldehydes, as well as the simultaneous production of branched C13 alcohols and branched C15 alcohols. Example 5 provides the first example of a two-stage process for the simultaneous production of branched C13 aldehydes and branched C15 aldehydes from a starting α-olefin feed containing a 50:50 mixture of 1-dodecene and 1-tetradecene. Example 6 provides a second example of a two-stage process for the simultaneous production of branched C13 aldehydes and branched C15 aldehydes from a 50:50 mixture of 1-dodecene and 1-tetradecene, which results in an increased degree of isomerization and an aldehyde product with increased branching. In Example 7, the branched C13 aldehydes and branched C15 aldehydes produced in Examples 5 and 6 were hydrogenated to produce a mixture of branched C13 alcohols and branched C15 alcohols.

[0360] Example 5: Preparation of branched C13 aldehyde and branched C15 aldehyde

[0361] The C12 linear alpha olefin feedstock (1-dodecene) and the C14 linear alpha olefin feedstock (1-tetradecene) were obtained from Chevron Phillips Chemical Company under the product names AlphaPlus® 1-dodecene and AlphaPlus® 1-tetradecene, respectively (Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260). The homogeneous rhodium organophosphorus catalyst solution in Example 5 was a mixture containing 0.040 wt% Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)), 2.51 wt% tris(2,4-di-t-butylphenyl)phosphite ligand, and 97.45 wt% Synfluid® PAO4cSt (Chevron Phillips Chemical Co., P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260) inert solvent. This mixture was heated at 110°C for 2 hours with stirring under a nitrogen atmosphere to produce an active rhodium catalyst solution (160 ppm rhodium, P:Rh molar ratio = 25). The starting reaction mixture contained 37.5 wt% C12 linear alpha olefin feed, 37.5 wt% C14 linear alpha olefin feed, and 25 wt% active rhodium catalyst solution.

[0362] The reaction was carried out in a batch process using a starting reaction mixture containing 40 ppm rhodium. The mixture was placed in a high-pressure stainless steel autoclave. The C12 / C14 α-olefin feed mixture was isomerized at 70°C under a CO / H2 atmosphere at 1.4 bar(g) for 2.0 hours. The isomerized olefin mixture was then hydroformylated at 70°C under a CO / H2 atmosphere at 15 bar(g) for 4 hours. The molar ratio of CO to H2 in both the isomerization and hydroformylation steps was 1:1.15. The conversion of the starting olefin to the aldehyde product was 97%. The resulting hydroformylation reaction product had a composition of 39.1 wt% C13 aldehyde and 39.4 wt% C15 aldehyde. The isomer distribution of the C13 aldehyde and C15 aldehyde produced was as follows: weight% C13 aldehyde 1-Tridecanal 8.3% 2-Methyldodecanal 16.8% 2-Ethylundecanal 9.1% 2-Propyldecanal 3.0% 2-Butylnonanal 1.4% 2-Pentyloctanal 0.5% Total C13 aldehydes: 39.1% C15 aldehyde 1-Pentadecanal 8.3% 2-Methyltetradecanal 16.8% 2-Ethyltridecanal 9.1% 2-Propyl-dodecanal 3.0% 2-Butylundecanal 1.5% 2-Pentyldecanal + 2-Hexylnonanal 0.7% Total C15 aldehydes: 39.4%

[0363] The weight percent branching of the branched C13 aldehyde product was 78.8%. The weight percent branching of the branched C15 aldehyde product was 78.9%.

[0364] Example 6: Production of branched C13 aldehyde and branched C15 aldehyde

[0365] The batch C12 / C14 α-olefin isomerization / hydroformylation process detailed in Example 5 was repeated, but the time for the isomerization step was increased from 2.0 hours to 3.0 hours and the time for the hydroformylation step was decreased from 4.0 hours to 3.0 hours. The conversion of the starting olefin to the aldehyde product in this example was 94%. The resulting hydroformylation reaction product had a composition of 38.0 wt% C13 aldehyde and 37.9 wt% C15 aldehyde. The isomer distribution of the C13 aldehyde and C15 aldehyde produced was as follows: weight% C13 aldehyde 1-Tridecanal 4.3% 2-Methyldodecanal 10.5% 2-Ethylundecanal 8.1% 2-Propyldecanal 6.3% 2-Butylnonanal 8.4% 2-pentyl octanal 0.4% Total C13 aldehydes: 38.0% C15 aldehyde 1-Pentadecanal 4.2% 2-Methyltetradecanal 10.4% 2-Ethyltridecanal 8.0% 2-Propyl-dodecanal 6.1% 2-Butylundecanal 8.7% 2-Pentyldecanal + 2-Hexylnonanal 0.5% Total C15 aldehydes: 37.9%

[0366] The weight percent branching of the branched C13 aldehyde product was 88.7%. The weight percent branching of the branched C15 aldehyde product was 88.9%.

[0367] Example 7: Production of branched C13 alcohol and branched C15 alcohol

[0368] The hydroformylation reaction products of Examples 5 and 6 were combined and flash distilled at 150-160°C and 5 mbar absolute pressure. The rhodium catalyst solution was recovered as the bottom product, and a mixture of branched C13 aldehydes and branched C15 aldehydes was recovered as the overhead product. The composition of this C13 / C15 aldehyde mixture was 49.3 wt% C13 aldehyde and 45.0 wt% C15 aldehyde. The isomer distribution of the produced C13 aldehyde and C15 aldehyde was as follows: weight% C13 aldehyde 1-Tridecanal 8.0% 2-Methyldodecanal 17.5% 2-Ethylundecanal 11.0% 2-Propyldecanal 5.9% 2-Butylnonanal 3.8% 2-Pentyloctanal 3.1% Total C13 aldehydes: 49.3% C15 aldehyde 1-Pentadecanal 6.8% 2-Methyltetradecanal 15.8% 2-Ethyltridecanal 10.1% 2-Propyl-dodecanal 5.4% 2-Butylundecanal 3.6% 2-Pentyldecanal + 2-Hexylnonanal 3.3% Total of C15 aldehydes: 45.0%

[0369] The total weight percent of C13 aldehydes and C15 aldehydes in the aldehyde mixture was 94.3%. The total weight percent of branched C13 aldehydes and branched C15 aldehydes in the aldehyde mixture was 79.5%. The branching ratio of the branched C13 / C15 aldehyde mixture was 84.3% (i.e., =79.5% ÷ 94.3%). The total weight percent of linear C13 aldehydes and linear C15 aldehydes in the aldehyde mixture was 14.8% (i.e., =8.0% + 6.8%). The proportion of linear aldehydes was 15.7% (i.e., =14.8% ÷ 94.3%). The total weight percent of 2-methyl branched C13 aldehydes and 2-methyl branched C15 aldehydes in the aldehyde mixture was 33.3% (i.e., =17.5% + 15.8%). The percentage of 2-methyl branched aldehyde was 35.3% (i.e., = 33.3% ÷ 94.3%). The total weight percent of 2-ethyl branched C13 aldehyde and 2-ethyl branched C15 aldehyde in the aldehyde mixture was 21.1% (i.e., = 11.0% + 10.1%). The percentage of 2-ethyl branched aldehyde was 22.4% (i.e., = 21.1% ÷ 94.3%).

[0370] This branched C13 / C15 aldehyde mixture was hydrogenated in a high-pressure stainless steel stirred autoclave at 150 °C and 25 bar(g) hydrogen pressure. The hydrogenation catalyst used was Raney® Nickel 3111 (WR Grace & Company, 7500 Grace Drive, Columbia, MD 21044, USA, tel. 1-410-531-4000) catalyst with a loading of 0.50 wt%. The branched C13 / C15 aldehyde mixture was hydrogenated for 4 hours, and the resulting reaction mixture was filtered to produce a branched C13 / C15 alcohol mixture containing 49.4 wt% branched C13 alcohol and 44.1 wt% branched C15 alcohol. The isomer distribution of the resulting C13 alcohol and C15 alcohol was as follows: weight% C13 alcohol 1-Tridecanol 7.9% 2-Methyldodecanol 17.7% 2-Ethylundecanol 11.0% 2-Propyldecanol 6.0% 2-Butylnonanol 3.8% 2-Pentyloctanol 3.0% Total C13 alcohols: 49.4% C15 Alcohol 1-Pentadecanol 6.5% 2-Methyltetradecanol 16.0% 2-Ethyltridecanol 9.5% 2-Propyl-dodecanol 5.3% 2-Butylundecanol 3.3% 2-Pentyldecanol + 2-Hexylnonanol 3.5% Total C15 alcohols: 44.1%

[0371] The total weight percent of C13 alcohols and C15 alcohols in the alcohol mixture was 93.5%. The total weight percent of branched C13 alcohols and branched C15 alcohols in the alcohol mixture was 79.1%. The branching ratio of the branched C13 / C15 alcohol mixture was 84.6% (i.e., = 79.1% ÷ 93.5%). The total weight percent of linear C13 alcohols and linear C15 alcohols in the alcohol mixture was 14.4% (i.e., = 7.9% + 6.5%). The percentage of linear alcohols was 15.4% (i.e., = 14.4% ÷ 93.5%). The total weight percent of 2-methyl branched C13 alcohols and 2-methyl branched C15 alcohols in the alcohol mixture was 33.7% (i.e., = 17.7% + 16.0%). The percentage of 2-methyl branched alcohols was 36.0% (i.e., = 33.7% ÷ 93.5%). The total weight percent of 2-ethyl branched C13 alcohols and 2-ethyl branched C15 alcohols in the alcohol mixture was 20.5% (i.e., = 11.0% + 9.5%). The percentage of 2-ethyl branched alcohols was 21.9% (i.e., = 20.5% ÷ 93.5%).

[0372] The hydrogenation product also contains 2.4 wt% C12 alkanes (paraffins) and 2.7 wt% C14 alkanes (paraffins), which are the hydrogenation products of unreacted C12 and C14 olefins. These C12 and C14 alkane by-products are easily removed as the "lights" stream in the distillation process used to refine the hydrogenation product into high-purity C13 and C15 branched alcohol products.

[0373] Example 8: Preparation of branched C15 aldehyde / C15 alcohol product using a cobalt catalyst

[0374] The C14 linear alpha olefin feedstock (1-tetradecene) was obtained from Chevron Phillips Chemical Company under the product name AlphaPlus® 1-tetradecene (Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260). The homogeneous cobalt organophosphorus catalyst solution used in this example was a mixture containing 1.36 wt% cobalt(II) 2-ethylhexanoate (65% solution), 16.44 wt% tris(2,4-di-t-butylphenyl)phosphite ligand, and 82.2 wt% Synfluid® PAO 4cSt (Chevron Phillips Chemical Company) inert solvent. This mixture was heated at 150°C for 2 hours with stirring under a nitrogen atmosphere to produce an active cobalt catalyst solution (1500 ppm cobalt, P:Co molar ratio = 10). The starting reaction mixture consisted of 53.3 wt% C14 linear alpha olefin feedstock and 46.7 wt% active cobalt catalyst solution.

[0375] The reaction was carried out in a batch process using a starting reaction mixture containing 700 ppm cobalt. The mixture was placed in a high-pressure stainless steel autoclave. The C14 alpha-olefin feed mixture was isomerized at 180°C for 3 hours under a CO / H2 atmosphere at 20 bar(g). The isomerized olefin mixture was then hydroformylated at 180°C for 3 hours under a CO / H2 atmosphere at 60 bar(g). The molar ratio of CO to H2 in both the isomerization and hydroformylation steps was 1:1.1. The conversion of the starting olefins to aldehyde and alcohol products was 69.6%. The resulting hydroformylation reaction product contained a mixture of C15 aldehydes and C15 alcohols. The isomer distribution of the C15 aldehyde and C15 alcohol mixture was as follows: C15 aldehyde 1-Pentadecanal 30.2% 2-Methyltetradecanal 13.2% 2-Ethyltridecanal 6.2% 2-Propyl-dodecanal 4.8% 2-butyl / 2-pentyl / 2-hexyl isomers 13.8% Total C15 aldehydes: 68.2% C15 Alcohol 1-Pentadecanol 18.9% 2-Methyltetradecanol 8.7% 2-Ethyltridecanol 1.8% 2-Propyl / 2-butyl / 2-pentyl / 2-hexyl isomers 2.4% Total C15 alcohols: 31.8%

[0376] The weight percent linearity of the C15 aldehyde / alcohol mixture was 49.1%. The weight percent branchedness of the C15 aldehyde / alcohol mixture was 50.9%. The weight percent 2-methyl isomer of the C15 aldehyde / alcohol mixture was 21.9%. The weight percent 2-ethyl isomer of the C15 aldehyde / alcohol mixture was 8.0%. The combined weight percent of 2-propyl / 2-butyl / 2-pentyl / 2-hexyl isomers of the C15 aldehyde / alcohol mixture was 21.0%.

[0377] Example 9: Preparation of branched C15 aldehyde / C15 alcohol product using cobalt-rhodium mixed catalyst

[0378] The C14 linear alpha olefin feedstock (1-tetradecene) was obtained from Chevron Phillips Chemical Company under the product name AlphaPlus® 1-tetradecene (Chevron Phillips Chemical Company, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260). The homogeneous cobalt-rhodium organophosphorus catalyst solution used in this example was a mixture containing 1.36 wt% cobalt(II) 2-ethylhexanoate (65% solution), 0.005 wt% Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)), 16.44 wt% tris(2,4-di-t-butylphenyl)phosphite ligand, and 82.2 wt% Synfluid® PAO4cSt (Chevron Phillips Chemical Co., P.O. Box 4910, The Woodlands, TX 77387-4910, USA, phone number (800) 231-3260) inert solvent. This mixture was heated at 150 °C for 2 hours with stirring under a nitrogen atmosphere to produce an active cobalt-rhodium catalyst solution (1500 ppm cobalt, P:Co molar ratio = 10, 21 ppm rhodium). The starting reaction mixture contained 53.3 wt% C14 linear alpha olefin feedstock and 46.7 wt% active cobalt-rhodium catalyst solution.

[0379] The reaction was carried out in a batch process using a starting reaction mixture containing 700 ppm cobalt and 10 ppm rhodium in a high-pressure stainless steel autoclave. The C14 α-olefin feed mixture was isomerized at 80°C for 1.5 hours under a CO / H2 atmosphere at 2 bar (g). The isomerized olefin mixture was then hydroformylated at 180°C for 2.5 hours under a CO / H2 atmosphere at 30 bar (g). The molar ratio of CO to H2 in both the isomerization and hydroformylation steps was 1:1.1. The conversion of the starting olefins to aldehyde and alcohol products was 83.0%. The resulting hydroformylation reaction product contained a mixture of C15 aldehydes and C15 alcohols. The isomer distribution of the C15 aldehyde and C15 alcohol mixture was as follows: C15 aldehyde 1-Pentadecanal 29.2% 2-Methyltetradecanal 35.3% 2-Ethyltridecanal 8.9% 2-Propyl-dodecanal 5.3% 2-butyl / 2-pentyl / 2-hexyl isomers 12.3% Total of C15 aldehydes: 91.0% C15 Alcohol 1-Pentadecanol 4.1% 2-Methyltetradecanol 3.8% 2-Ethyltridecanol 0.8% 2-Propyl / 2-butyl / 2-pentyl / 2-hexyl isomers 0.3% Total C15 alcohols: 9.0%

[0380] The weight percent linearity of the C15 aldehyde / alcohol mixture was 33.3%. The weight percent branchedness of the C15 aldehyde / alcohol mixture was 66.7%. The weight percent 2-methyl isomer of the C15 aldehyde / alcohol mixture was 39.1%. The weight percent 2-ethyl isomer of the C15 aldehyde / alcohol mixture was 9.7%. The combined weight percent of 2-propyl / 2-butyl / 2-pentyl / 2-hexyl isomers of the C15 aldehyde / alcohol mixture was 18.0%.

[0381] (Conclusion)

[0382] The present disclosure, in its many aspects, features, and elements, relates to branched products and methods for producing and manufacturing branched products. Such compounds and manufacturing processes can be dynamic in their use and operation. The present disclosure is intended to encompass equivalents, means, systems, methods of using branched products, methods for producing and manufacturing branched products, and many aspects thereof, consistent with the description and spirit of the apparatus, means, methods, functions, and operations disclosed herein. Other embodiments and modifications will be recognized by those skilled in the art as being enabled by and within the scope of the present disclosure.

[0383] The scope of the present disclosure is intended to be broadly construed. The embodiments herein may be used together, separately, mixed, or in combination. The present disclosure is intended to disclose equivalents, means, systems, and methods for achieving the apparatus, designs, operations, control systems, controls, activities, mechanical actions, dynamics, and results disclosed herein. For each disclosed compound, process, method, manufacturing method, mechanical element, or mechanism, the present disclosure is also intended to encompass and teach, within its scope, equivalents, means, systems, and methods for implementing the various aspects, compounds, processes, mechanisms, and apparatuses disclosed herein. The scope of the claims of this application is likewise intended to be broadly construed.

[0384] The description of the technology herein is merely illustrative in its many diverse embodiments, and variations that do not depart from the gist of the disclosure are intended to be included within the scope of the claims and disclosure. Such variations should not be considered as departing from the spirit and scope of the disclosed technology.

[0385] It will be understood that various modifications and variations can be made to the above-described embodiments of the methods and resulting branched products disclosed herein without departing from the spirit and scope of the claims.

Claims

1. providing a first catalyst comprising an organometallic complex comprising at least one of rhodium and cobalt and at least one organophosphorus ligand; providing a mixture of one or more C4 to C36 linear alpha olefins; providing a gas phase comprising carbon monoxide; isomerizing the linear alpha olefins over the first catalyst in the presence of carbon monoxide at a first pressure to produce isomerized olefins; hydroformylating the isomerized olefins over the first catalyst in the presence of carbon monoxide and hydrogen at a second pressure different from the first pressure to produce branched aldehydes; A method for producing a branched product comprising:

2. The method for producing a branched product according to claim 1, wherein the branched aldehyde is a 2-alkyl branched aldehyde.

3. 2. The method for producing a branched product according to claim 1, wherein the organophosphorus ligand is a phosphite ligand.

4. 2. The method for producing a branched product according to claim 1, wherein the organophosphorus ligand is a phosphite ligand which is tris(2,4-di-t-butylphenyl)phosphite.

5. a first organophosphorus ligand that is triphenylphosphine; and and a second organophosphorus ligand which is tris(2,4-di-t-butylphenyl)phosphite.

6. providing a hydrogenation catalyst; providing hydrogen; 2. The method of claim 1, further comprising hydrogenating the branched aldehyde in the presence of the hydrogenation catalyst and hydrogen to produce a branched alcohol.

Images