Processes for the production of 1,4-butanediol

Abstract

A method for producing 1,4 butanediol is disclosed. The method includes reacting C4 diacids with hydrogen in the presence of a catalyst at a first temperature of from about 70℃ or more to about 150℃ or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate. The method further includes reacting the intermediate with hydrogen at a second temperature of from about 150℃ or more to about 250℃ or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less so as to produce a product comprising 1,4-butanediol, wherein the reacting of the C4 diacids and of the intermediate occurs sequentially in the same reaction vessel.

Description

[0001] PROCESSES FOR THE PRODUCTION OF 1,4-BUTANEDIOL TECHNICAL FIELD

[0002] This disclosure relates to the production of industrial products from bio-based feedstocks and, more specifically, to the production of 1,4-butanediol through single pot hydrogenation of dicarboxylic acids.

[0003] BACKGROUND

[0004] The use of natural products as starting materials for the manufacture of various large-scale chemical and fuel products which are presently made from petroleum- or fossil fuel-based starting materials, or for the manufacture of bio-based equivalents or analogs thereto, has been an area of increasing environmental importance.

[0005] Accordingly, a great deal of research has been conducted into the conversion of natural products into such large-scale chemical and fuel products as a cleaner and more sustainable alternative to the conversion of fossil-fuel based starting materials. For example, succinic acid has historically been commercially produced from crude oil through catalytic hydrogenation of maleic anhydride to succinic anhydride followed by subsequent hydration, or by direct catalytic hydrogenation of maleic acid. These traditional ways of producing succinic acid from petrochemicals is costly and has a negative environmental impact. In recent years however, many have sought to develop a more cost competitive and environmentally-friendly way of producing succinic acid through bio-based fermentative processes. Such biologically-derived succinic acid (BDSA) processes seek to produce succinic acid by fermenting glucose from biomass, separating and purifying the succinic acid, and then catalytically processing it as a platform chemical to produce, for example, 1,4-butanediol (BDO) and related products. Thus, the development of additional pathways and processes for producing valuable and important chemical compounds, such as 1,4-BDO, from natural products is highly desirable.

[0006] SUMMARY

[0007] In an aspect, a method of producing 1 ,4-butanediol is provided. The method includes reacting C4 diacids with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first

[0008] Classification: ConfidentialCP.0209.W001

[0009] hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate. The method further includes reacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less so as to produce a product comprising 1,4-butanediol, wherein the reacting of the C4 diacids and of the intermediate occurs sequentially in the same reaction vessel.

[0010] In another aspect, a method of producing 1,4-butanediol is provided. The method includes reacting C4 diacids comprising malic acid with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate. The method further includes reacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less so as to produce a product comprising 1 ,4-butanediol.

[0011] Further aspects and embodiments are provided in the foregoing drawings, detailed description, and claims.

[0012] BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following drawings are provided to illustrate certain embodiments described herein. The drawings are merely illustrative and are not intended to limit the scope of claimed inventions and are not intended to show every potential feature or embodiment of the claimed inventions. The drawings are not necessarily drawn to scale: in some instances, certain elements of the drawing may be enlarged with respect to other elements of the drawing for purposes of illustration.

[0014] Fig. 1 illustrates an example reaction pathway for converting various C4 diacids to 1,4-butanediol.

[0015] Fig. 2 is a graph illustrating the conversion of example C4 diacids with various different catalysts, including Ni / Re, 5wt%Ru,0.25wt%Pd / C, 5wt% Ru / C, and 5wt%Ru / A12O3.

[0016] Fig. 3 is a graph illustrating the conversion of example C4 diacids with various different catalysts, including Cu-Pd / C, Cu-Pd / TiCh, 3Re-Ru / C, and 3Re-Ru / TiO2.

[0017] 2

[0018] Classification: ConfidentialCP.0209.W001

[0019] Fig. 4 is a graph illustrating the conversion of example C4 diacids with various different catalysts, including Cu-Pd-Zn / C, Raney Ni, 3Re-Ru / C, and 3Re-Ru / TiO2.

[0020] Fig. 5 is a graph illustrating the conversion of example C4 diacids with various different catalysts, including Re-1.5Ru / C, Re-1.5Ru / TiO2, and 3Re-Ru / C.

[0021] DETAILED DESCRIPTION

[0022] The following description recites various aspects and embodiments of the inventions disclosed herein. No particular embodiment is intended to define the scope of the invention. Rather, the embodiments provide non-limiting examples of various compositions, and methods that are included within the scope of the claimed inventions. The description is to be read from the perspective of one of ordinary skill in the art. Therefore, information that is well known to the ordinarily skilled artisan is not necessarily included.

[0023] Definitions

[0024] The following terms and phrases have the meanings indicated below, unless otherwise provided herein. This disclosure may employ other terms and phrases not expressly defined herein. Such other terms and phrases shall have the meanings that they would possess within the context of this disclosure to those of ordinary skill in the art. In some instances, a term or phrase may be defined in the singular or plural. In such instances, it is understood that any term in the singular may include its plural counterpart and vice versa, unless expressly indicated to the contrary.

[0025] As used herein, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. For example, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

[0026] As used herein, “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise expressly indicated, such examples are provided only as an aid for understanding embodiments illustrated in the present disclosure and are not meant to be limiting in any fashion. Nor do these phrases indicate any kind of preference for the disclosed embodiment.

[0027] The present application relates generally to single pot production of 1,4-BDO from C4 diacid starting materials. The C4 diacids may be alkene, C4 dicarboxylic 3

[0028] Classification: ConfidentialCP.0209.W001

[0029] acids such as malic acid, maleic acid, fumaric acid, and succinic acid. Experiments were performed that evaluated the efficacy of producing 1,4-BDO from multiple substrate-catalyst combinations under various reaction conditions. Based on the results, non-traditional pathways and processes for obtaining 1 ,4-BDO were discovered. For example, it was hypothesized and found that malic acid initially undergoes a dehydration and hydrogenation process to produce an intermediate, such as succinic acid. The other substrates disclosed herein, such as maleic acid and fumaric acid, undergo a hydrogenation process to produce succinic acid. The succinic acid may then be hydrogenated further in the presence of the same hydrogenation catalyst used in the first reaction to produce 1,4-BDO. The reactions of the substrates and of the intermediate may occur sequentially in the same reaction vessel, and with the same catalyst. Accordingly, the newly discovered non-traditional pathways and processes for obtaining 1 ,4-BDO disclosed herein provide additional means for converting natural products, such as agricultural bio-based feedstocks, to plastics, organic solvents, and other valuable chemical compounds traditionally derived from petroleum-based feedstocks.

[0030] Referring now to the drawings, Fig. 1 illustrates an example reaction pathway for converting various C4 diacids to 1,4-BDO. In the example reaction pathway, the initial C4 diacids include maleic acid, malic acid, and / or fumaric acid. The initial C4 diacids may be hydrogenated in the presence of a catalyst in a first reaction to saturate the carbon-carbon double bonds of the C4 diacids, thereby producing succinic acid as an intermediate. This first hydrogenation may generally proceed via the following steps: 1) adsorption of the C4 diacid and hydrogen on the catalyst surface, 2) dissociation of hydrogen molecules into atomic hydrogen, 3) addition of hydrogen atoms to the C4 diacid to produce succinic acid, and 4) desorption of the formed succinic acid from the catalyst surface. The intermediate succinic acid may then be hydrogenated in the presence of a catalyst in a second reaction, thereby producing y-butyrolactone (GBE) as another intermediate. In addition to GBE, side products such as propionic acid and butyric acid may also be produced from this second reaction. Propionic acid may be further hydrogenated into propanol, and butyric acid may be further hydrogenated into butanol. Multiple pathways may be available for the conversion of GBE to 1,4-BDO. One pathway may include hydrogenation of the GBE to produce 1,4-BDO directly. Another pathway may include hydrogenation of the

[0031] 4

[0032] Classification: ConfidentialCP.0209.W001

[0033] GBL to produce tetrahydrofuran (THF), and the THF may then be hydrated to produce 1,4-BDO indirectly from GBL.

[0034] In any of the embodiments described herein, the 1,4-BDO is produced by reacting C4 diacids with hydrogen in the presence of a catalyst at a first temperature and at a first hydrogen pressure to produce an intermediate. The intermediate is then reacted with hydrogen in the presence of the same catalyst at a second temperature and at a second hydrogen pressure to produce the 1,4-BDO. The reacting of the C4 diacids and of the intermediate is performed sequentially in the same reaction vessel (i.e., single pot hydrogenation). Thus, it has been discovered that production of 1,4-BDO can be simplified by reacting the intermediate at the second temperature that is higher than the first temperature, thereby enabling 1 ,4-BDO to be produced from C4 diacid starting material in a single vessel using the same catalyst for both reactions.

[0035] In any of the embodiments described herein, the C4 diacids are alkene, C4 dicarboxylic acids. Example C4 diacids include, but are not limited to including, malic acid, maleic acid, fumaric acid, succinic acid, and mixtures thereof. The C4 diacids may be selected from the group consisting of malic acid, maleic acid, fumaric acid, succinic acid, and mixtures thereof.

[0036] In any of the embodiments described herein, the C4 diacids are in an aqueous solution when reacted as described herein, wherein the C4 diacid concentration in the aqueous solution may be from about 0.1 wt% or more to about 25 wt% or less, from about 5 wt% or more to about 20 wt% or less, from about 6 wt% or more to about 16 wt% or less, from about 7 wt% or more to about 14 wt% or less, or from about 8 wt% or more to about 12 wt%, or may be about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4. 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt%.

[0037] In any of the embodiments described herein, the catalyst is a heterogenous catalyst made from a support material and a catalyst material on the support material. Example support materials include, but are not limited to including, carbon, titanium dioxide, and / or aluminum oxide. The support materials may be selected from the group consisting of carbon, titanium dioxide, and aluminum oxide. Example catalyst materials include, but are not limited to including, transition metals such as Group VII, VIII, IX, X, and / or XI transition metals. Specifically, example transition metals include, but are not limited to including, rhenium, ruthenium, nickel, palladium,

[0038] 5

[0039] Classification: ConfidentialCP.0209.W001

[0040] copper, zinc, and / or combinations thereof. The transition metals may be selected from the group consisting of rhenium, ruthenium, nickel, palladium, copper, zinc, and combinations thereof. The catalyst material may be a single metallic material or be more than one metallic material, such as the aforementioned example transition metals.

[0041] In any of the embodiments described herein, the catalyst is a heterogeneous bimetallic catalyst, wherein the catalyst material is a combination of rhenium and ruthenium. The amount of each metal on the support material is typically referred to as catalyst loading. In any of the embodiments described herein, the Re catalyst loading may be from about 1.0 wt% or more to about 5.0 wt% or less, from about 2.0 wt% or more to about 4.0 wt% or less, or from about 2.0 wt% or more to about 3.0 wt% or less, oris about 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 wt%. In any of the embodiments described herein, the Ru catalyst loading may be from about 0.5 wt% or more to about 5.0 wt% or less, from about 1.0 wt% or more to about 4.0 wt% or less, from about 1.0 wt% or more to about 3.0 wt% or less, or from about 1.0 wt% or more to about 2.0 wt% or less, or may be about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 wt%.

[0042] In embodiments where the catalyst material is a combination of rhenium and ruthenium, the molar ratio of Re to Ru in the catalyst material may be from about 1 :5 to about 5:1, from about 1 :4 to about 4:1, from about 1 :3 to about 3:1, from about 1 :2 to about 2:1, from about 2:1 to about 1:2, from about 3:1 to about 1:3, from about 4:1 to about 1:4, or from about 5:1 to about 1:5, or may be 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5. or 1:5.

[0043] In any of the embodiments described herein, the C4 diacids are reacted with hydrogen in the presence of a catalyst at a first temperature. In any of the embodiments described herein, the first temperature may be from about 70°C or more to about 150°C or less, from about 90°C or more to about 130°C or less, or from about 100°C or more to about 120°C or less, or may be about 70°C, 80°C, 90°C, I00°C, I10°C, 120°C, 130°C, 140°C, or l50°C.

[0044] In any of the embodiments described herein, the first hydrogen pressure may be from about 10 psi or more to about 2,000 psi or less, from about 1,100 psi or more to about 1,900 psi or less, from about 1,200 psi or more to about 1,800 psi or less, or from about 1,300 psi or more to about 1,700 psi or less, or may be about 10, 20, 30,

[0045] 6

[0046] Classification: ConfidentialCP.0209.W001

[0047] 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350. 400, 450, 500, 550, 600, 700, 800, 900, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, or 2,000 psi.

[0048] In any of the embodiments described herein, the C4 diacids are reacted with hydrogen in the presence of a catalyst at the first temperature and at the first hydrogen pressure for from about 5 hours or more to about 30 hours or less, from about 6 hours or more to about 25 hours or less, from about 7 hours or more to about 20 hours or less, from about 8 hours or more to about 15 hours or less, from about 10 hours or more to about 30 hours or less, from about 10 hours or more to about 25 hours or less, or from about 10 hours or more to about 20 hours or less, or for about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 hours.

[0049] In any of the embodiments described herein, the intermediate produced from the first reaction is reacted with hydrogen in the presence of a catalyst at a second temperature and at a second hydrogen pressure. In any of the embodiments described herein, the second temperature may be from about 150°C or more to about 250°C or less, from about 160°C or more to about 225°C or less, from about 170°C or more to about 200°C or less, or from about 170°C or more to about 190°C or less, or may be about 150°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, or 250°C.

[0050] In any of the embodiments described herein, the second hydrogen pressure may be from about 10 psi or more to about 2,000 psi or less, from about 1 , 100 psi or more to about 1,900 psi or less, from about 1,200 psi or more to about 1,800 psi or less, or from about 1,300 psi or more to about 1,700 psi or less, or may be about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, or 2,000 psi.

[0051] In any of the embodiments described herein, the intermediate is reacted with hydrogen in the presence of a catalyst at the second temperature and at the second hydrogen pressure for from about 5 hours or more to about 30 hours or less, from about 6 hours or more to about 25 hours or less, from about 7 hours or more to about 20 hours or less, from about 8 hours or more to about 15 hours or less, from about 10 hours or more to about 30 hours or less, from about 10 hours or more to about 25 hours or less, or from about 10 hours or more to about 20 hours or less, or for about 5,

[0052] 7

[0053] Classification: ConfidentialCP.0209.W001

[0054] 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22. 23, 24, 25, 26, 27, 28, 29, or 30 hours.

[0055] In any of the embodiments described herein, the C4 diacids reaction and the intermediate reaction are performed for the same durations or for different durations, wherein the C4 diacids reaction may be performed for a longer duration than the intermediate reaction, or wherein the C4 diacids reaction may be performed for a shorter duration than the intermediate reaction.

[0056] In any of the embodiments described herein, reacting the intermediate as described herein produces a product comprising 1,4-BDO. In any of the embodiments described herein, the concentration of 1,4-BDO in the product may be from about 1 mol% or more to about 75 mol% or less, from about 25 mol% or more to about 70 mol% or less, from about 30 mol% or more to about 65 mol% or less, from about 35 mol% or more to about 60 mol% or less, or from about 40 mol% or more to about 55 mol% or less, or may be about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mol%.

[0057] In any of the embodiments described herein, reacting the intermediate as described herein produces a product comprising GBL. In any of the embodiments described herein, the concentration of GBL in the product may be from about 1 mol% or more to about 75 mol% or less, from about 25 mol% or more to about 70 mol% or less, from about 30 mol% or more to about 65 mol% or less, from about 35 mol% or more to about 60 mol% or less, or from about 40 mol% or more to about 55 mol% or less, or may be about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mol%.

[0058] In any of the embodiments described herein, reacting the intermediate produces a product comprising 1,4-BDO. In any of the embodiments described herein, the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the starting material, may be from about 1 mol% or more to about 60 mol% or less, from about 5 mol% or more to about 55 mol% or less, from about 15 mol% or more to about 50 mol% or less, from about 25 mol% or more to about 45 mol% or less, or may be about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50. 55, 60, 65, or 70 mol%.

[0059] In any of the embodiments described herein, reacting the intermediate produces a product comprising 1,4-BDO. In any of the embodiments described herein,

[0060] 8

[0061] Classification: ConfidentialCP.0209.W001

[0062] the concentration of 1 ,4-BDO in the product, produced from the reaction of maleic acid as the starting material, may be from about 1 mol% or more to about 75 mol% or less, from about 25 mol% or more to about 70 mol% or less, from about 30 mol% or more to about 65 mol% or less, from about 35 mol% or more to about 60 mol% or less, or from about 40 mol% or more to about 55 mol% or less, or may be about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mol%.

[0063] In any of the embodiments described herein, reacting the intermediate produces a product comprising 1,4-BDO. In any of the embodiments described herein, the concentration of 1,4-BDO in the product, produced from the reaction of succinic acid as the starting material, may be from about 1 mol% or more to about 75 mol% or less, from about 25 mol% or more to about 70 mol% or less, from about 30 mol% or more to about 65 mol% or less, from about 35 mol% or more to about 60 mol% or less, or from about 40 mol% or more to about 55 mol% or less, or may be about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mol%.

[0064] In any of the embodiments described herein, reacting the intermediate produces a product comprising 1,4-BDO. In any of the embodiments described herein, the concentration of 1 ,4-BDO in the product, produced from the reaction of fumaric acid as the starting material, may be from about 1 mol% or more to about 5 mol% or less, from about 2 mol% or more to about 4 mol% or less, or may be about 1, 2, 3, 4, or 5 mol%.

[0065] EXAMPLES

[0066] Example 1

[0067] In a specific reaction, 2 mL of 10 wt% malic acid, maleic acid, or succinic acid aqueous solution were added individually into 24 parallel 4 mL glass vials using a Freeslate™ high throughput catalyst screening system. For each substrate, four different catalysts were assessed: Ni / Re, 5% Ru-0.25%Pd / C, 5% Ru / C, and 5% RU / AI2O3. Dry weight 40 mg of catalyst was loaded into each glass vial. The system was heated at 110°C under 1500 psi H2 for 10 hours, then increased the temperature to 180°C under 1500 psi H2 for another 10 hours. After reaction, the product mixture was analyzed by HPLC to identify and quantify the products distribution. The HPLC analysis was performed according to the following parameters: flow rate: 0.7mL / min; column temp: 70°C; RI temp: 50°C; 5mM H2SO4: 1* Sugar column 1011.

[0068] 9

[0069] Classification: ConfidentialCP.0209.W001

[0070] Each substrate-catalyst combination was run in duplicate, and the duplicate results were compared to monitor for notable disparities between the results. No such disparities were detected, and the results from one run of each respective combination are illustrated in Figure 2. In general, the catalysts assessed here had a deficient performance for C4 diacids hydrogenation, in terms of both substrate conversion and target product selectivity. Analytical results indicated that for all the tests in this case, no 1,4-BDO was detected.

[0071] Example 2

[0072] In a specific reaction, 2 mL of 10 wt% malic acid, maleic acid, or succinic acid aqueous solution were individually added into 24 parallel 4 mL glass vials using a Freeslate1Mhigh throughput catalyst screening. For each substrate, four different catalysts were assessed: Cu-Pd / C, Cu-Pd / TiCE, 3Re-Ru / C, 3Re-Ru / TiO2. For the Re-Ru based catalysts, Re loading is 2.5 wt% and Ru loading is E5 wt%, molar ratio of Re:Ru = 3: 1. In the Cu-Pd based catalysts, Cu loading is 8 wt%, and Pd loading is 2 wt%, molar ratio of Cu:Pd = 2.4:1. Dry weight 40mg of catalyst was loaded into each glass vial. The system was heated at 110°C under 1500 psi FE for 10 hours, then increased the temperature to 180°C under 1500 psi EE for another 10 hours. After reaction, the product mixture was analyzed by HPLC to identify and quantify the product distribution. The HPLC analysis was performed according to the following parameters: flow rate: 0.7mL / min; column temp: 70°C; RI temp: 50°C; 5mM H2SO4; 1 * Sugar column 1011.

[0073] Each substrate-catalyst combination was run in duplicate, and the duplicate results were compared to monitor for notable disparities between the results. No such disparities were detected, and the results from one run of each respective combination are illustrated in Figure 3. Analytical results indicated no 1,4-BDO formation using Cu-Pd / C and Cu-Pd / TiO2 catalysts for all three substrates. However, for the 3Re-Ru / C catalyst, a 30 mol% yield of 1,4-BDO was obtained from the reaction of all three different substrates. Using the Re-Ru / TiO2 catalyst, up to a 55 mol% yield of y-butyrolactone (GBL) was obtained from the reactions of maleic acid and succinic acid hydrogenation to form a primary alcohol on one end with a remaining acid on the other. The resulting 4-hydroxy butyric acid, formed presumably from reduction of succinic acid ring closing quickly to form GBL. The Re-Ru / C catalyst is therefore

[0074] 10

[0075] Classification: ConfidentialCP.0209.W001

[0076] able to convert C4 diacids such as malic acid, maleic acid, and succinic acid to 1 ,4-BDO in a single vessel reaction.

[0077] Example 3

[0078] In a specific reaction, 2 mL of 10 wt% malic acid, maleic acid, or fumaric acid aqueous solution were individually added into 24 parallel 4 mL glass vials designed for use in Freeslate™ high throughput catalyst screening equipment. Specifically, for fumaric acid, due to the extremely low solubility in H2O, the fumaric acid solution was prepared using 10 wt% NHvIUO to help dissolve all the solid. For each substrate, four different catalysts were assessed: Cu-Pd-Zn / C, Raney Ni, 3Re-Ru / C, and 3Re-Ru / TiCh. For the Re-Ru based catalysts, Re loading is 2.5wt% and Ru loading is 1.5 wt%, molar ratio of Re:Ru = 3:1. In the Cu / Pd / Zn catalyst, Cu loading is 10wt%, Pd loading is 2wt%, and Zn loading is 2 wt%. Molar ratio of Cu:Pd:Zn = 5:2:1, and molar ratio Re:Ru = 3: 1 in 3Re-Ru / C and 3Re-Ru / TiO2 catalysts. Dry weight 40mg of catalyst was loaded into each glass vial. The system was heated at 110°C under 1500 psi H2 for 20 hours, then increased the temperature to 180°C under 1500 psi H2 for another 20 hours. After reaction, the product mixture was analyzed by HPLC to identify and quantify the products distribution. The HPLC analysis was performed according to the following parameters: flow rate: 0.7mL / min; column temp: 70°C; RI temp: 50°C; 5mM H2SO4; 1* Sugar column 1011.

[0079] Each substrate-catalyst combination was run in duplicate, and the duplicate results were compared to monitor for notable disparities between the results. No such disparities were detected, and the results from one run of each respective combination are illustrated in Figure 4. Analytical results indicated no 1 ,4-BDO formation using Cu-Pd-Zn / C and Raney Ni catalysts for all three substrates. However, using 3Re-Ru / C catalyst, up to 61 mol% yield of 1,4-BDO was obtained from the reaction of maleic acid, and about 25 mol% yield of 1,4-BDO was obtained from the reaction of malic acid. Using 3Re-Ru / TiO2 catalyst, up to 50 mol% yield of 1,4-BDO was obtained from the reactions of maleic acid, and up to 45 mol% yield of 1,4-BDO was obtained from the reaction of malic acid. Compared with Example 2, the results also indicated that extending reaction time will benefit conversion of GBL to 1,4-BDO. Using fumaric acid as substrate, less than 5 mol% of BDO was obtained. The reactions indicate that C4 diacids may be converted to 1,4-BDO in a single vessel. Example 4

[0080] 11

[0081] Classification: ConfidentialCP.0209.W001

[0082] In a specific reaction, 2 mL of 10 wt% malic acid, maleic acid, succinic acid, or fumaric acid aqueous solution were individually added into 24 parallel 4 mL glass vials designed for Freeslate™ high throughput catalyst screening. Specifically, for fumaric acid, due to the extremely low solubility in H2O, the fumaric acid solution was prepared using 10 wt% NHvILO to help dissolve all the solid. For each substrate, three different catalysts were assessed: 3Re-Ru / C, Re-1.5Ru / C, and Re-1.5Ru / TiO2. In the 3Re-Ru based catalyst (3Re-Ru / C), Re loading is 2.5wt% and Ru loading is 1.5 wt%, molar ratio of Re:Ru = 3:1. In the Re-1.5Ru catalysts (Re-1.5Ru / C, and Re-1.5Ru / TiO2), Re loading is 1.8 wt%, and Ru loading is 2.2 wt%, molar ratio of Re:Ru = 1:1.5. Dry weight 40 mg of Re-1.5Ru / C and Re-1.5Ru / TiO2, and 20 mg of 3Re-Ru / C were used for reactions. The system was heated at 120°C under 1500 psi H2 for 15 hours, then increased the temperature to 180°C under 1500 psi H2 for another 20 hours. After reaction, the product mixture was analyzed by HPLC to identify and quantify the products distribution. The HPLC analysis was performed according to the following parameters: flow rate: 0.7mL / min; column temp: 70°C: RI temp: 50°C; 5mM H2SO4; 1* Sugar column 1011.

[0083] Each substrate-catalyst combination was run in duplicate, and the duplicate results were compared to monitor for notable disparities between the results. No such disparities were detected, and the results from one run of each respective combination are illustrated in Figure 5. Analytical results indicated no 1,4-BDO formation using fumaric acid as substrate applying all three different catalysts. For maleic acid and succinic acid, up to 55 mol% of 1,4-BDO was achieved using 3Re-Ru / C catalyst. And for malic acid, up to 32 mol% of 1,4-BDO was achieved using 3Re-Ru / C catalyst. The other two catalysts applied in this example (Re-1.5Ru / C and Re-1.5Ru / TiO2), however, only resulted in relatively small amount of 1,4-BDO formation for all substrates.

[0084] The invention has been described with reference to various specific embodiments and techniques. Nevertheless, it is understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.

[0085] 12

[0086] Classification: ConfidentialCP.0209.W001

[0087] ITEMS:

[0088] 1. A method of producing 1 ,4-butanediol (BDO), the method comprising: reacting C4 diacids with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate; and

[0089] reacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less to produce a product comprising 1,4-BDO, wherein the reacting of the C4 diacids and of the intermediate occurs sequentially in the same reaction vessel.

[0090] 2. A method of producing 1 ,4-butanediol (BDO), the method comprising:

[0091] reacting C4 diacids comprising malic acid with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate; and

[0092] reacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less to produce a product comprising 1,4-BDO.

[0093] 3. The method according to any of the preceding items, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 0.1 wt% or more to about 25 wt% or less.

[0094] 4. The method according to any of the preceding items, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 5 wt% or more to about 20 wt% or less.

[0095] 5. The method according to any of the preceding items, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 6 wt% or more to about 16 wt% or less.

[0096] 13

[0097] Classification: ConfidentialCP.0209.W001

[0098] 6. The method according to any of the preceding items, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 7 wt% or more to about 14 wt% or less.

[0099] 7. The method according to any of the preceding items, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 8 wt% or more to about 12 wt% or less.

[0100] 8. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the rhenium catalyst loading of the rhenium and ruthenium catalyst is from about 1.0 wt% or more to about 5.0 wt% or less.

[0101] 9. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the rhenium catalyst loading of the rhenium and ruthenium catalyst is from about 2.0 wt% or more to about 4.0 wt% or less.

[0102] 10. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the rhenium catalyst loading of the rhenium and ruthenium catalyst is from about 2.0 wt% or more to about 3.0 wt% or less.

[0103] 11. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the ruthenium catalyst loading of the rhenium and ruthenium catalyst is from about 0.5 wt% or more to about 5.0 wt% or less.

[0104] 12. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the ruthenium catalyst loading of the rhenium and ruthenium catalyst is from about 1.0 wt% or more to about 4.0 wt% or less.

[0105] 13. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the ruthenium catalyst loading of the rhenium and ruthenium catalyst is from about 1.0 wt% or more to about 3.0 wt% or less.

[0106] 14. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium,

[0107] 14

[0108] Classification: ConfidentialCP.0209.W001

[0109] wherein the ruthenium catalyst loading of the rhenium and ruthenium catalyst is from about 1.0 wt% or more to about 2.0 wt% or less.

[0110] 15. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 1:5 to about 5:1.

[0111] 16. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 1:4 to about 4:1.

[0112] 17. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 1:3 to about 3:1.

[0113] 18. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 1:2 to about 2:1.

[0114] 19. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 2:1 to about 1:2.

[0115] 20. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 3:1 to about 1:3.

[0116] 21. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 4:1 to about 1:4.

[0117] 22. The method according to any of the preceding items, wherein the catalyst comprises a catalyst material that is combination of rhenium and ruthenium,

[0118] 15

[0119] Classification: ConfidentialCP.0209.W001

[0120] wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 5:1 to about 1:5.

[0121] 23. The method according to any of the preceding items, wherein the first hydrogen pressure is from about 1,100 psi or more to about 1,900 psi or less.

[0122] 24. The method according to any of the preceding items, wherein the first hydrogen pressure is from about 1,200 psi or more to about 1,800 psi or less.

[0123] 25. The method according to any of the preceding items, wherein the first hydrogen pressure is from about 1,300 psi or more to about 1,700 psi or less.

[0124] 26. The method according to any of the preceding items, wherein the second temperature is from about 160°C or more to about 225°C or less.

[0125] 27. The method according to any of the preceding items, wherein the second temperature is from about 170°C or more to about 200°C or less.

[0126] 28. The method according to any of the preceding items, wherein the second temperature is from about 170°C or more to about 190°C or less.

[0127] 29. The method according to any of the preceding items, wherein the second hydrogen pressure is from about 1,100 psi or more to about 1,900 psi or less.

[0128] 30. The method according to any of the preceding items, wherein the second hydrogen pressure is from about 1,200 psi or more to about 1,800 psi or less.

[0129] 31. The method according to any of the preceding items, wherein the second hydrogen pressure is from about 1,300 psi or more to about 1,700 psi or less.

[0130] 32. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 5 hours or more to about 30 hours or less.

[0131] 33. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 6 hours or more to about 25 hours or less.

[0132] 34. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 7 hours or more to about 20 hours or less.

[0133] 35. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 8 hours or more to about 15 hours or less.

[0134] 36. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 10 hours or more to about 30 hours or less.

[0135] 16

[0136] Classification: ConfidentialCP.0209.W001

[0137] 37. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 10 hours or more to about 25 hours or less.

[0138] 38. The method according to any of the preceding items, wherein the C4 diacids are reacted for from about 10 hours or more to about 20 hours or less.

[0139] 39. The method according to any of the preceding items, wherein the intermediate is reacted for from about 5 hours or more to about 30 hours or less.

[0140] 40. The method according to any of the preceding items, wherein the intermediate is reacted for from about 6 hours or more to about 25 hours or less.

[0141] 41. The method according to any of the preceding items, wherein the intermediate is reacted for from about 7 hours or more to about 20 hours or less.

[0142] 42. The method according to any of the preceding items, wherein the intermediate is reacted for from about 8 hours or more to about 15 hours or less.

[0143] 43. The method according to any of the preceding items, wherein the intermediate is reacted for from about 10 hours or more to about 30 hours or less.

[0144] 44. The method according to any of the preceding items, wherein the intermediate is reacted for from about 10 hours or more to about 25 hours or less.

[0145] 45. The method according to any of the preceding items, wherein the intermediate is reacted for from about 10 hours or more to about 20 hours or less.

[0146] 46. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product is from about 1 mol% or more to about 75 mol% or less.

[0147] 47. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product is from about 25 mol% or more to about 70 mol% or less.

[0148] 48. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product is from about 30 mol% or more to about 65 mol% or less.

[0149] 49. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product is from about 35 mol% or more to about 60 mol% or less.

[0150] 17

[0151] Classification: ConfidentialCP.0209.W001

[0152] 50. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product is from about 40 mol% or more to about 55 mol% or less.

[0153] 51. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the C4 diacids, is from about 1 mol% or more to about 60 mol% or less.

[0154] 52. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the C4 diacids, is from about 5 mol% or more to about 55 mol% or less.

[0155] 53. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the C4 diacids, is from about 15 mol% or more to about 50 mol% or less.

[0156] 54. The method according to any of the preceding items, wherein the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the C4 diacids, is from about 25 mol% or more to about 45 mol% or less.

[0157] 18

[0158] Classification: Confidential

Claims

CP.0209.W001WHAT IS CLAIMED IS:

1. A method of producing 1 ,4-butanediol (BDO), the method comprising:reacting C4 diacids with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate; andreacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less to produce a product comprising 1,4-BDO, wherein the reacting of the C4 diacids and of the intermediate occurs sequentially in the same reaction vessel.

2. The method according to claim 1, wherein the C4 diacids are alkenes.

3. The method according to claim 2, wherein the C4 diacids are C4 dicarboxylic acids.

4. The method according to claim 3, wherein the C4 diacids comprise one or more of malic acid, maleic acid, fumaric acid, and succinic acid.

5. The method according to claim 3, wherein the C4 diacids consist of make acid, maleic acid, fumaric acid, or succinic acid.

6. The method according to claim 3, wherein the C4 diacids consist essentially of malic acid, maleic acid, fumaric acid, or succinic acid.

7. A method of producing 1 ,4-butanediol (BDO), the method comprising: reacting C4 diacids comprising malic acid with hydrogen in the presence of a catalyst at a first temperature of from about 70°C or more to about 150°C or less, and at a first hydrogen pressure of from about 10 psi or more to about 2,000 psi or less, so as to form an intermediate; andreacting the intermediate with hydrogen at a second temperature of from about 150°C or more to about 250°C or less at a second hydrogen pressure of from about 10 psi or more to about 2,000 psi or less to produce a product comprising 1,4-BDO.

8. The method according to claim 7, wherein the reacting of the C4 diacids and of the intermediate occurs sequentially in the same reaction vessel.19Classification: ConfidentialCP.0209.W0019. The method according to any of the preceding claims, wherein the C4 diacids are in an aqueous solution when reacted, wherein the C4 diacid concentration in the aqueous solution is from about 0.1 wt% or more to about 25 wt% or less, from about 5 wt% or more to about 20 wt% or less, from about 6 wt% or more to about 16 wt% or less, from about 7 wt% or more to about 14 wt% or less, or from about 8 wt% or more to about 12 wt% or less.

10. The method according to any of the preceding claims, wherein reacting the intermediate occurs in the presence of the same catalyst used in reacting the C4 diacids.

11. The method according to any of the preceding claims, wherein the catalyst is a heterogeneous catalyst.

12. The method according to claim 11, wherein the catalyst comprises a support material that is selected from the group consisting of carbon, titanium dioxide, and aluminum oxide.

13. The method according to any of claims 11 or 12, wherein the catalyst comprises a catalyst material that is one or more transition metals.

14. The method according to claim 13, wherein the catalyst material comprises one or more of rhenium, ruthenium, nickel, palladium, copper, and zinc.

15. The method according to claim 13, wherein the catalyst material consists of rhenium, ruthenium, nickel, palladium, copper, or zinc.

16. The method according to claim 13, wherein the catalyst material consists essentially of rhenium, ruthenium, nickel, palladium, copper, or zinc.

17. The method according to claim 14, wherein the catalyst material is a combination of rhenium and ruthenium.

18. The method according to claim 17, wherein the rhenium catalyst loading of the rhenium and ruthenium catalyst is from about 1.0 wt% or more to about 5.0 wt% or less, from about 2.0 wt% or more to about 4.0 wt% or less, or from about 2.0 wt% or more to about 3.0 wt% or less.

19. The method according to any of claims 16 or 17, wherein the ruthenium catalyst loading of the rhenium and ruthenium catalyst is from about 0.5 wt% or more to about 5.0 wt% or less, from about 1.0 wt% or more to about 4.0 wt%20Classification: ConfidentialCP.0209.W001or less, from about 1.0 wt% or more to about 3.0 wt% or less, or from about 1.0 wt% or more to about 2.0 wt% or less.

20. The method according to any of claims 16-19, wherein the molar ratio of rhenium to ruthenium in the catalyst material is from about 1 :5 to about 5:1, from about 1:4 to about 4:1, from about 1:3 to about 3:1, from about 1:2 to about 2:1, from about 2:1 to about 1:2, from about 3:1 to about 1:3, from about 4:1 to about 1:4, or from about 5:1 to about 1:5.

21. The method according to any of claims 16-20, wherein the rhenium and ruthenium catalyst is a 3Re-Ru / C catalyst or a 3Re-Ru / TiO2 catalyst.

22. The method according to any of the preceding claims, wherein the intermediate comprises one or more of succinic acid, y-butyrolactone (GBL), and tetrahydrofuran.

23. The method according to any of the preceding claims, wherein the intermediate consists of succinic acid, y-butyrolactone (GBL), or tetrahydrofuran.

24. The method according to any of the preceding claims, wherein the intermediate consists essentially of succinic acid, y-butyrolactone (GBL), or tetrahydrofuran.

25. The method according to any of the preceding claims, wherein the first temperature is from about 90°C or more to about 130°C or less, or from about 100°C or more to about 120°C or less.

26. The method according to any of the preceding claims, wherein the first hydrogen pressure is from about 1,100 psi or more to about 1,900 psi or less, from about 1,200 psi or more to about 1,800 psi or less, or from about 1,300 psi or more to about 1,700 psi or less.

27. The method according to any of the preceding claims, wherein the second temperature is from about 160°C or more to about 225°C or less, from about 170°C or more to about 200°C or less, or from about 170°C or more to about 190°C or less.

28. The method according to any of the preceding claims, wherein the second hydrogen pressure is from about 1,100 psi or more to about 1,900 psi or less,21Classification: ConfidentialCP.0209.W001from about 1,200 psi or more to about 1,800 psi or less, or from about 1,300 psi or more to about 1,700 psi or less.

29. The method according to any of the preceding claims, wherein the C4 diacids are reacted for from about 5 hours or more to about 30 hours or less, from about 6 hours or more to about 25 hours or less, from about 7 hours or more to about 20 hours or less, from about 8 hours or more to about 15 hours or less, from about 10 hours or more to about 30 hours or less, from about 10 hours or more to about 25 hours or less, or from about 10 hours or more to about 20 hours or less.

30. The method according to any of the preceding claims, wherein the intermediate is reacted for from about 5 hours or more to about 30 hours or less, from about 6 hours or more to about 25 hours or less, from about 7 hours or more to about 20 hours or less, from about 8 hours or more to about 15 hours or less, from about 10 hours or more to about 30 hours or less, from about 10 hours or more to about 25 hours or less, or from about 10 hours or more to about 20 hours or less.

31. The method according to any of claims 23 or 24, wherein the C4 diacids and the intermediate are reacted for the same duration or for different durations.

32. The method according to any of the preceding claims, wherein the concentration of 1,4-BDO in the product is from about 1 mol% or more to about 75 mol% or less, from about 25 mol% or more to about 70 mol% or less, from about 30 mol% or more to about 65 mol% or less, from about 35 mol% or more to about 60 mol% or less, or from about 40 mol% or more to about 55 mol% or less.

33. The method according to any of the preceding claims, wherein the concentration of 1,4-BDO in the product, produced from the reaction of malic acid as the C4 diacids, is from about 1 mol% or more to about 60 mol% or less, from about 5 mol% or more to about 55 mol% or less, from about 15 mol% or more to about 50 mol% or less, orfrom about 25 mol% or more to about 45 mol% or less.22Classification: Confidential

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