Patent Description:
The chemical industry has suffered a long felt need to produce branched alcohols in a cost-effective manner. There is a ready and large supply of alpha olefins which are inexpensive. However, there is no known way to efficiently and cost effectively produce branched alcohols on an industrial scale using alpha olefins as a feedstock.

<CIT> describes a process for preparing aldehydes which comprises reacting an olefinic unsaturated compound with hydrogen and carbon monoxide by hydroformylation reaction in the presence of a catalyst and the reaction is carried out in the presence of pressure sectional zones. The first reaction zone has a pressure of <NUM>/cm2 and the second reaction zone has a pressure of <NUM>/cm2.

In an embodiment, a process can have the steps of: providing CO and H2; providing a first catalyst which is an organometallic complex of rhodium and one type of an organophosphorus ligand or an organometallic complex of rhodium and more than one type of an organophosphorus ligand; providing a linear alpha olefin; isomerizing the linear alpha olefin (also herein described as a normal alpha olefin) by the first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin; and hydroformylating the isomerized olefin by the first catalyst in the presence of CO and H2 at a second pressure higher than the first pressure to produce a branched aldehyde.

In an embodiment, that is not in accordance with the claims, hydroformylating the isomerized olefin by the first catalyst in the presence of CO and H2 is performed at a second pressure, different from the first pressure, to produce a branched aldehyde.

In an embodiment, the branched aldehyde is a <NUM>-alkyl branched aldehyde. In an embodiment, the linear alpha olefin is a C4-C36 linear alpha olefin. In an embodiment, the branched aldehyde produced from the C4-C36 linear alpha olefin is a C5-C37 branched aldehyde. In an embodiment, the linear alpha olefin can be <NUM>-Butene and the branched aldehyde can be branched Pentanals. In an embodiment, the linear alpha olefin can be <NUM>-Hexene and the branched aldehyde can be branched Heptanals. In an embodiment, the linear alpha olefin can be <NUM>-Octene and the branched aldehyde can be branched Nonanals. In an embodiment, the linear alpha olefin can be <NUM>-Decene and the branched aldehyde can be branched Undecanals. In an embodiment, the linear alpha olefin can be <NUM>-Dodecene and the branched aldehyde can be branched Tridecanals. In an embodiment, the linear alpha olefin can be <NUM>-Tetradecene and the branched aldehyde can be branched Pentadecanals.

In an embodiment, the linear alpha olefin can be <NUM>-Hexadecene and the branched aldehyde can be branched Heptadecanals. In an embodiment, the linear alpha olefin can be <NUM>-Octadecene and the branched aldehyde can be branched Nonadecanals. In an embodiment, the organophosphorous ligand can be a phosphine. In a nonlimiting example of a phosphine ligand, the phosphine ligand can be triphenylphosphine. In another embodiment, the organophosphorous ligand can be a phosphite. In a nonlimiting example of a phosphite ligand, the phosphite ligand can be tris (<NUM>, <NUM>-di-t-butylphenyl) phosphite. In yet another embodiment, a mixture of organophosphorous ligands of different types can be used, such as a mixture of a phosphine and a phosphite. In a nonlimiting example of a mixture of organophosphorous ligands, the organophosphorous ligands can be a mixture of triphenylphosphine and tris (<NUM>, <NUM>-di-t-butylphenyl) phosphite.

In an embodiment, the first catalyst is formed when the molar ratio of phosphorous to rhodium is in a range of <NUM>:<NUM> to <NUM>: <NUM>. In an embodiment, the first catalyst is formed when the molar ratio of phosphorous to rhodium is in a range of <NUM>:<NUM> to <NUM>: <NUM> in the isomerization step and/or reactor. In an embodiment, the first catalyst is formed when the molar ratio of phosphorous to rhodium is in a range of <NUM>:<NUM> to <NUM>:<NUM> in the hydroformylation step and/or reactor.

The present invention in its several aspects and embodiments solves the problems discussed above and significantly advances the technology of branched compounds and methods for producing and manufacturing branched compounds. The present invention can become more fully understood from the detailed description and the accompanying drawings, wherein:.

Herein, like reference numbers in one figure refer to like reference numbers in another figure.

Described herein is a process for the production of branched C13 and C15 aldehydes and alcohols. According to a nonlimiting embodiment of this process, e.g. as shown in <FIG>, branched C13 aldehydes (branched Tridecanals) can be produced from a C12 linear alpha olefin (i.e. <NUM>-Dodecene). In another embodiment of this process, that is not in accordance with the claims, branched C13 alcohols (branched Tridecanols) can be produced from a C12 linear alpha olefin (i.e. <NUM>-Dodecene). Examples of sales specifications for commercially available C12 linear alpha olefins are shown in <FIG>, <FIG>/<FIG>, and <FIG>. In another embodiment of this process, branched C15 aldehydes (branched Pentadecanals) can be produced from a C14 linear alpha olefin (i.e. <NUM>-Tetradecene). In another embodiment of this process, that is not in accordance with the claims, branched C15 alcohols (branched Pentadecanols) can be produced from a C14 linear alpha olefin (i.e. <NUM>-Tetradecene). Examples of sales specifications for commercially available C14 linear alpha olefins are shown in <FIG>, <FIG>/<FIG>, and <FIG>.

A two-step process is disclosed herein which produces highly branched aldehyde products from linear alpha olefin feedstocks. The two-step process uses a rhodium organophosphorus catalyst for both the first process step and the second step. The first step is an isomerization reaction step and the second process step is a hydroformylation reaction step. The highly branched aldehydes can undergo a further hydrogenation step (that is not in accordance with the claims), to produce highly branched alcohols.

Numeric values and ranges herein, unless otherwise stated, also are intended to have associated with them a tolerance and to account for variances of design and manufacturing. Thus, a number can include values "about" that number. For example, a value X is also intended to be understood as "about X". Likewise, a range of Y-Z, is also intended to be understood as within a range of from "about Y-about Z". Unless otherwise stated, significant digits disclosed for a number are not intended to make the number an exact limiting value. Variance and tolerance are inherent in mechanical design and the numbers disclosed herein are intended to be construed to allow for such factors.

As regarding ranges and endpoints, every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein.

Unless otherwise stated temperatures recited herein are in degrees Celsius ("°C").

Unless otherwise stated pressures recited herein are in bar(g), i.e. bars gauge. Herein, <NUM> bar(g) is atmospheric pressure, e.g. <NUM> psia (aka <NUM> psig).

Unless otherwise stated percentages of composition recited herein are on a weight basis and disclosed as weight percent (wt.

Alternatively, herein, concentration can be expressed in units of parts per million, or ppm.

Herein "branched" is defined as a molecule, compound or chemical structure, having one or more alkyl groups attached along a carbon backbone. "Branched" molecules are isomers of linear (i.e. straight-chain) molecules having the same number of carbon atoms.

Herein, the term "percent branched", in additional to its ordinary and customary meaning, is defined herein to mean the wt. % branched molecules in a composition. The term "percent branching" is use synonymously with "percent branched" and has the same meaning as "percent branched". As an example, for an aldehyde composition, the "percent branching" of the aldehyde means the wt. % of the aldehyde being branched, i.e.:.

Percent branching % = percent branched % = <NUM> * (wt. % branched aldehyde) ÷ (wt. % branched aldehyde + wt. % linear aldehyde).

As an example, a branched C6 aldehyde composition comprising:.

Unless otherwise stated percent branching recited herein are in weight percent (wt. %) is calculated based upon reactant and product weights, excluding nonparticipating compounds.

Herein, the term "percent isomerized", in additional to its ordinary and customary meaning, is defined herein to mean the wt. % of olefin molecules where the olefin has been isomerized from the alpha position to an internal olefin position. Specifically, the "percent isomerized" means the wt. % of the olefin composition being internal olefins, i.e.:
<MAT>.

As an example, a C12 alpha olefin isomerized to produce a composition comprising:.

Unless otherwise stated the term "internal olefin" recited herein means an olefin in which a double bond is present in a position other than the alpha position.

Unless otherwise stated percent isomerized recited herein are in weight percent (wt. %) is calculated based upon reactant and product weights, excluding nonparticipating compounds.

<FIG> shows an embodiment of a chemical manufacturing process having an isomerization reactor, a hydroformylation reactor, catalyst recovery and an aldehyde hydrogenation reactor.

<FIG> shows an embodiment in which Stream <NUM> is fed to an aldehyde hydrogenation reactor <NUM> which produces branched alcohols as Stream <NUM> which is a branched alcohols product stream.

<FIG> shows an embodiment in which Stream <NUM> is the feed stream to the Aldehyde Hydrogenation Reactor (<NUM>) and can have a composition, e.g.:.

In the embodiment of <FIG> (that is not in accordance with the claims), the C5-C37 aldehydes are hydrogenated in the Aldehyde Hydrogenation Reactor (<NUM>) in the presence of hydrogen and a hydrogenation catalyst, e.g. Catalyst A, to produce Stream <NUM>. Stream <NUM> is a branched alcohols product and in an embodiment can have a composition comprising:.

In the embodiment of <FIG> (that is not in accordance with the claims), the C5-C37 alcohols are produced from the hydrogenation of the corresponding aldehydes in aldehyde hydrogenation reactor <NUM> and the C4-C36 paraffins also produced in aldehyde hydrogenation reactor <NUM> resulting from the hydrogenation of the unreacted C4-C36 olefins contained in Stream <NUM>.

Optionally, the C5-C37 alcohols content (purity) can be increased in Stream <NUM>, with a related decrease in the C4-C36 paraffin content by using an optional distillation step after aldehyde hydrogenation reactor <NUM> to remove the low-boiling C4-C36 paraffins and produce a distilled, high purity C5-C37 Branched Alcohols Product which is free of, or nearly free of, C4-C36 paraffins.

In an embodiment (that is not in accordance with the claims), Stream <NUM> can be a branched alcohols product composition having greater than <NUM> % branching.

In the embodiment of <FIG>, the starting Alpha Olefin Feed Composition is shown as Stream <NUM>. In this embodiment, Stream <NUM> can be split into Stream <NUM> (Isomerization Reactor Feed Composition) which is fed to Isomerization Reactor <NUM> and Stream <NUM> (Isomerization Reactor Bypass Composition) which can be bypassed around Isomerization Reactor <NUM> and be provided as a feed to the Hydroformylation reaction. The use of a bypass stream, e.g. Stream <NUM>, is optional. It is not necessary to bypass of a portion of the alpha olefin feed around Isomerization Reactor <NUM>; however, using a bypass such as Stream <NUM> can provide a means to control the percentage of alpha olefin isomerization achieved in Stream <NUM>, the feed stream to Hydroformylation Reactor <NUM>.

In the embodiment of <FIG>, the effluent of Isomerization Reactor <NUM>, i.e. Stream <NUM> - Isomerization Reactor Product Composition, is combined with Stream <NUM> -Isomerization Reactor Bypass Composition to produce Stream <NUM> -Hydroformylation Reactor Feed Composition which is fed to Hydroformylation Reactor <NUM>.

In the embodiment of <FIG>, Hydroformylation Reactor <NUM> produces Stream <NUM> - Hydroformylation Product Composition.

In the embodiment of <FIG>, the Stream <NUM> -Hydroformylation Product Composition is fed to Catalyst Recovery <NUM> which produces Stream <NUM> -Recovered Rhodium Catalyst Stream Composition as recycle feed to Isomerization Reactor <NUM> and Stream <NUM> -Branched Aldehydes/Unreacted Olefins Composition. In <FIG> catalyst recovery is shown as occurring in the unit operation shown as Catalyst Recovery <NUM>.

In the embodiment of <FIG> (that is not in accordance with the claims), Stream <NUM> - Branched Aldehydes/Unreacted Olefins Composition is fed to Aldehyde Hydrogenation Reactor <NUM> which produces Stream <NUM>, Branched Alcohols Product.

The isomerization and hydroformylation reactions disclosed herein can be catalyzed by a rhodium organophosphorus catalyst which can be at least one of: (<NUM>) an organometallic complex of rhodium and one type of an organophosphorus ligand; (<NUM>) or an organometallic complex of rhodium and more than one type of an organophosphorus ligand.

In an embodiment, the organophosphorous ligand can be a phosphine. In a nonlimiting example of a phosphine ligand, the phosphine ligand can be triphenylphosphine. In another embodiment, the organophosphorous ligand can be a phosphite. In a nonlimiting example of a phosphite ligand, the phosphite ligand can be tris (<NUM>, <NUM>-di-t-butylphenyl) phosphite. In yet another embodiment, a mixture of organophosphorous ligands of different types can be used, such as a mixture of a phosphine and a phosphite. In a nonlimiting example of a mixture of organophosphorous ligands, the organophosphorous ligands can be a mixture of triphenylphosphine and tris (<NUM>, <NUM>-di-t-butylphenyl) phosphite. In an embodiment, the reaction system can contain an inert high-boiling solvent, for example a polyalphaolefin. In an embodiment, the first catalyst can be formed when the molar ratio of phosphorous to rhodium is in a range of <NUM>:<NUM> to <NUM>:<NUM>, or <NUM>:<NUM> to <NUM>:<NUM>, or <NUM>:<NUM> to <NUM>:<NUM>. In an embodiment, the rhodium concentration can be in a range of <NUM> ppm to <NUM> ppm, or <NUM> ppm to <NUM> ppm, or <NUM> ppm to <NUM> ppm. In an embodiment, the CO to H2 molar ratio can be in a range of <NUM>:<NUM> to <NUM>:<NUM>, or <NUM>:<NUM> to <NUM>:<NUM>, or <NUM>:<NUM> to <NUM>:<NUM>.

In an embodiment, the first process step can be a reaction isomerizing a linear alpha olefin in the presence of Carbon Monoxide (CO) and Hydrogen (H2) at a first pressure. The isomerizing can be catalyzed by the rhodium organophosphorus catalyst which can be at least one of: (<NUM>) an organometallic complex of rhodium and one type of an organophosphorus ligand; (<NUM>) or an organometallic complex of rhodium and more than one type of an organophosphorus ligand. The isomerization reactions can produce an isomerized olefin comprising linear internal olefins of the same or different types.

In an embodiment, the isomerization step can be performed at a temperature in a range of <NUM> to <NUM>, or <NUM> to <NUM>, or <NUM> to <NUM>. In an embodiment, the isomerization step can be performed at a pressure in a range of <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g).

In an embodiment, the isomerizing step can produce a reaction product comprising a <NUM> wt. % or greater isomerized olefin, or a <NUM> wt. % or greater isomerized olefin, or a <NUM> wt. % or greater isomerized olefin, or a <NUM> wt. % or greater isomerized olefin.

In the embodiment of <FIG>, the isomerizing step is shown as occurring in Isomerization Reactor <NUM>.

The second process step of this embodiment can be a reaction hydroformylating the isomerized olefin in the presence of CO and H2 at a second pressure higher than the first pressure to produce a branched aldehyde. The hydroformylation reaction can be catalyzed by the rhodium organophosphorus catalyst which can be at least one of: (<NUM>) an organometallic complex of rhodium and one type of an organophosphorus ligand; (<NUM>) or an organometallic complex of rhodium and more than one type of an organophosphorus ligand. In an embodiment, the branched aldehyde is a <NUM>-alkyl branched aldehyde. In an embodiment, the linear alpha olefin can be <NUM>-Dodecene and the branched aldehyde can be a branched C13 aldehyde. In an embodiment, the linear alpha olefin can be <NUM>-Tetradecene and the branched aldehyde can be a branched C15 aldehyde.

In an embodiment, the hydroformylating step can be performed at a temperature in a range of <NUM> to <NUM>, or <NUM> to <NUM>, or <NUM> to <NUM>. In an embodiment, the hydroformylating step can be performed at a pressure in a range of <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g).

In an embodiment, the hydroformylating step can produce a reaction product comprising a <NUM> wt. % or greater branched aldehyde, or a <NUM> wt. % or greater branched aldehyde, or a <NUM> wt. % or greater branched aldehyde, or a <NUM> wt. % or greater branched aldehyde.

In the embodiment of <FIG>, the hydroformylating steps is shown as occurring in Hydroformylation Reactor <NUM>.

In an embodiment, the products of the hydroformylation reaction can be distilled. In this embodiment, the process can have the step of separating the branched aldehyde products resulting from hydroformylation as an overhead product from the first catalyst stream via a distillation process. The distillation step can be performed at a temperature in a range of <NUM> to <NUM>, or <NUM> to <NUM>. The distillation step can be performed under vacuum at a pressure of less than <NUM> millibar absolute, or less than <NUM> millibar absolute, or less than <NUM> millibar absolute.

In an embodiment, that is not in accordance with the claims, this process can also have the steps of: hydrogenating the branched aldehyde product in the presence of a hydrogenation catalyst to produce a branched alcohols product composition. In an embodiment, the hydrogenating catalyst can be a base metal catalyst, a supported nickel catalyst, a supported cobalt catalyst, a Raney® (W. Grace & Co. , <NUM> Grace Drive, Columbia, MD <NUM>, US, phone <NUM>-<NUM>-<NUM>-<NUM>) nickel catalyst or a precious metal catalyst. In an embodiment, the hydrogenating step can be performed at a temperature in a range of <NUM> to <NUM>, or <NUM> to <NUM>, or <NUM> to <NUM>. In an embodiment, the hydrogenating step can be performed at a pressure in a range of <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g), or <NUM> bar(g) to <NUM> bar(g).

In the embodiment of <FIG>, which is not in accordance with the claims, the step of hydrogenating the branched aldehyde product in the presence of a hydrogenation catalyst to produce a branched alcohols product composition is shown as occurring in Aldehyde Hydrogenation Reactor <NUM>.

In an embodiment, that is not in accordance with the claims, the hydrogenating step can produce a reaction product comprising <NUM> wt. % or greater branched alcohols, or <NUM> wt. % or greater branched alcohols, or <NUM> wt. % or greater branched alcohols, or <NUM> wt. % or greater branched alcohols.

A C12 linear alpha olefin feedstock (<NUM>-Dodecene) was obtained from the Chevron Phillips Chemical Company LP, as identified by product name AlphaPlus® <NUM>-Dodecene (Chevron Phillips Chemical Company LP, P. Box <NUM>, The Woodlands, TX <NUM>-<NUM>, US, phone (<NUM>) <NUM>-<NUM>). The homogeneous rhodium organophosphorus catalyst used in this example is prepared in a high pressure, stainless steel stirred autoclave. To the autoclave was added <NUM> wt. % Rh(CO)2ACAC ((Acetylacetonato)dicarbonylrhodium(I)), <NUM>. % tris (<NUM>,<NUM>,-di-t-butylphenyl) phosphite ligand and <NUM> wt. % Synfluid® PAO <NUM> cSt (Chevron Phillips Chemical Company LP, P. Box <NUM>, The Woodlands, TX <NUM>-<NUM>, phone (<NUM>) <NUM>-<NUM>) inert solvent. The mixture was heated at <NUM> in the presence of a CO/H2 atmosphere and <NUM> bar(g) pressure for four hours to produce the active rhodium catalyst solution (<NUM> ppm rhodium, P:Rh molar ratio = <NUM>). The <NUM>-Dodecene linear alpha olefin was added to the rhodium catalyst solution in the autoclave producing a starting reaction mixture with a rhodium concentration of <NUM> ppm. The alpha olefin feed was then isomerized at <NUM> in the presence of a CO/H2 atmosphere and <NUM> bar(g) pressure for <NUM> hours. The isomerized olefin was then hydroformylated at <NUM> in the presence of a CO/H2 atmosphere and <NUM> bar(g) pressure for <NUM> hours. The molar ratio of CO to H2 in both the isomerization step and the hydroformylation step was equal to <NUM>:<NUM>. The resulting hydroformylation reaction product was flash distilled at <NUM>-<NUM> and <NUM> millibar to recover the rhodium catalyst solution as a bottoms product and recover a branched C13 Aldehyde overheads product with a composition comprising:.

The weight % branching in the branched C13 aldehyde product was <NUM>%.

In a further embodiment that is not in accordance with the claims, the branched C13 aldehyde product was hydrogenated in a high pressure, Inconel <NUM> stirred autoclave at 150C and <NUM> bar(g) hydrogen pressure. The hydrogenation catalyst used was a Raney® Nickel <NUM> (W. Grace & Co. , <NUM> Grace Drive, Columbia, MD <NUM>, US, phone <NUM>-<NUM>-<NUM>-<NUM>) catalyst used at a <NUM>. The aldehyde was hydrogenated for <NUM> hours and the resultant reaction mixture was filtered to produce a branched C13 alcohol product comprising:.

The weight % branching in the branched C13 alcohol product was <NUM>%.

The recovered rhodium catalyst stream from Example <NUM> was charged to a high pressure, stainless steel stirred autoclave and a C14 linear alpha olefin feedstock (<NUM>-Tetradecene) from the Chevron Phillips Chemical Company LP, (AlphaPlus® <NUM>-Tetradecene by Chevron Phillips Chemical Company LP, P. Box <NUM>, The Woodlands, TX <NUM>-<NUM>, phone (<NUM>) <NUM>-<NUM>) was added. The resulting mixture had a rhodium concentration of approximately <NUM> ppm. The <NUM>-tetradecene linear alpha olefin was then isomerized at <NUM> in the presence of a CO/H2 atmosphere and <NUM> bar(g) pressure for <NUM> hours. The isomerized olefin was then hydroformylated at <NUM> in the presence of a CO/H2 atmosphere and <NUM> bar(g) pressure for <NUM> hours. The resulting reaction product was flash distilled at <NUM>-<NUM> and <NUM> millibar to recover the rhodium catalyst solution as a bottoms product and recover a branched C15 Aldehyde overheads product. The recovered rhodium catalyst solution was then used again to complete a second <NUM>-tetradecene batch isomerization (<NUM> hours) and hydroformylation (<NUM> hours). The resulting C15 aldehyde products from the two batches were combined to give a branched C15 Aldehyde product comprising:.

The weight % branching in the branched C15 aldehyde product was <NUM>%.

In a further embodiment that is not in accordance with the claims, the branched C15 aldehyde product was hydrogenated in a high pressure, Inconel <NUM> stirred autoclave at 150C and <NUM> bar(g) hydrogen pressure. The hydrogenation catalyst used was a Raney® Nickel <NUM> (W. Grace & Co. , <NUM> Grace Drive, Columbia, MD <NUM>, US, phone <NUM>-<NUM>-<NUM>-<NUM>) catalyst used at a <NUM>. The aldehyde was hydrogenated for <NUM> hours and the resultant reaction mixture was filtered to produce a branched C15 alcohol product comprising:.

The weight % branching in the branched C15 alcohols product was <NUM>%.

This disclosure regards branched compounds and methods for producing and manufacturing branched compounds in their many aspects, features and elements. Such compounds and manufacturing processes can be dynamic in use and operation.

Claim 1:
A process, comprising the steps of:
providing CO and H2;
providing a first catalyst which is an organometallic complex of rhodium and one type of an organophosphorus ligand or an organometallic complex of rhodium and more than one type of an organophosphorus ligand;
providing a linear alpha olefin;
isomerizing said linear alpha olefin by said first catalyst in the presence of CO and H2 at a first pressure to produce an isomerized olefin; and
hydroformylating said isomerized olefin by said first catalyst in the presence of CO and H2 at a second pressure higher than said first pressure to produce a branched aldehyde.