Methods for generating polyols

[0001] The present invention relates to methods, catalysts and reactor systems for producing one or more oxidized hydrocarbon products from an aqueous feed stream containing water-soluble oxidized hydrocarbon. Preferably, the reaction products include diols and other polyols, ketones, aldehydes, carboxylic acids and / or alcohols produced by hydrogenating water-soluble polyols (such as glycerol) in the feed material derived from biomass, using hydrogen produced in the reactor system from a portion of the material stream biomass feed.

BACKGROUND [0002] Biomass (material obtained from living or until recently living biological materials) is becoming one of the most important renewable energy sources. The ability to convert biomass into fuels, chemicals, energy and other substances is expected to strengthen rural economies, reduce dependence on oil and gas sources, and reduce air and water pollution. Producing energy and chemicals from renewable sources, such as biomass, also reduces the net volume of carbon dioxide production, an important greenhouse gas that contributes to global warming.

[0003] A key challenge for increasing and maintaining the use of biomass in the industrial sector is the need to develop efficient and environmentally friendly technologies for converting biomass into useful products. Modern biomass conversion technologies unfortunately tend to be associated with additional costs, which makes it difficult to compete with products produced by the use of traditional sources, such as fossil fuels. Such costs often include capital expenditure on equipment and processing systems capable of supporting extreme temperatures and high pressures, and the necessary operating costs of heating fuels and reaction products, such as fermenting organisms, enzyme substances, catalysts and other chemicals involved in the reaction.

[0004] One alternative fuel technology that is gaining considerable interest is biodiesel produced by the esterification of vegetable oils or animal fats. US biodiesel production reaches 113.6-151.4 million liters (30-40 million gallons) per year, but it is projected to increase to the target of 1,514 million liters (400 million gallons) per year by 2012. In Europe, in 2003 over 1.4 metric tons of biodiesel were produced, and larger projects are underway in Brazil and Asia.

[0005] A byproduct of the biodiesel production process is crude glycerol, which has little or no value without further purification. The problem is what to do with the growing supply of crude glycerol. Purification of crude glycerol is one option, however, purification of crude glycerol, which contains catalyst, organic impurities and residual methanol, is difficult and often too expensive for small biodiesel producers. To complicate matters, the demand for pure glycerol also remained constant and prices fell sharply with the delivery of larger supplies on an ongoing basis, especially in Europe.

[0006] The development of effective methods for converting crude glycerol into alternative products such as diols and other polyols, ketones, aldehydes, carboxylic acids and alcohols can provide additional opportunities to increase the cost-effectiveness and environmental benefits of biodiesel production.

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For example, more than one billion pounds of propylene glycol is currently produced in the United States and used in the production of many industrial products and consumer goods, including aircraft and runway deicing fluids, antifreeze, coolants, heat transfer fluids, solvents, flavors and agents aromatic, cosmetic additives, pharmaceuticals, hydraulic fluids, chemical intermediates and in thermosetting plastics. Propylene glycol is currently produced by partially oxidizing propylene from fossil fuel to form propylene oxide, which is then reacted with water to form propylene glycol.

[0007] Researchers have recently developed methods for reacting pure hydrogen with higher biomass-derived polyols (glycerol, xylitol and sorbitol) and sugars (xylose and glucose) against catalytic hydrogenation and hydrogenolysis catalytic materials to produce propylene glycol. Although the biomass is derived from a renewable source, pure hydrogen alone is generally obtained by steam reforming non-renewable natural gas. Due to its origin, pure hydrogen must also be supplied and introduced into the production stream under increased pressure from an external source, thereby reducing the efficiency of the process and increasing the overall cost of the final final product.

[0008] For example, US Pat. Ser. US 6,841,085, US 6,677,385 and US 6,479,713, Werpy et al. Disclose methods for hydrogenolysis of both a carbon-oxygen bond and a carbon-carbon bond using a rhenium-containing (Re) polymetallic catalyst in the presence of external hydrogen to produce products such as propylene glycol (PG). The Re-containing catalyst may also contain Ni, Pd, Ru, Co, Ag, Au, Rh, Pt, Ir, Os and Cu. The transformation takes place at temperatures in the range from 140 ° C to 250 ° C, and more preferably from 170 ° C to 220 ° C and hydrogen pressure from 4137 to 11,032 kPa (600 psi to 1,600 psi) hydrogen.

[0009] Dasari et al. also disclose hydrogenolysis of glycerol to PG in the presence of hydrogen from an external source at temperatures in the range of 150 ° C to 260 ° C and a hydrogen pressure of 1379 kPa (200 psi), against nickel, palladium, platinum, copper and copper chromium catalysts. The authors reported increased yields of propylene glycol with reduced water concentrations and reduced PG selectivity at temperatures above 200 ° C and hydrogen pressures of 1379 kPa (200 psi). The authors then reported that nickel, ruthenium and palladium were not very effective in hydrogenating glycerol. Dasari, MA; Kiatsimkul, P.-P .; Sutterlin, WR; Suppes, GJ Low-pressure hydrogenolysis of glycerol to propylene glycol Applied Catalysis, A: General, 281 (1-2), p. 225 (2005).

[0010] Patent application Ser. US Patent No. 11 / 088,603 (Publication No. US2005 / 0244312 Al), Suppes et al., Discloses a method of converting glycerol with high yield into lower alcohols at a temperature of boiling below 200 ° C. The method involves converting natural glycerin to propylene glycol through the acetol intermediate at temperatures from 150 ° C to 250 ° C, at a pressure in the range of 1 to 25 bar (14.5 to 363 psi), and preferably 5 to 8 bar ( 72.5 to 116 psi) to a palladium, nickel, rhodium, zinc, copper or chromium catalyst. The reaction occurs in the presence or absence of hydrogen, with hydrogen supplied by an external source. The glycerin is reacted in a solution containing 50% by weight or less of water and preferably only from 5% to 15% by weight of water.

[0011] Patent application Ser. US-A-2003/099593 discloses the production of hydrogen at low temperature from oxidized hydrocarbons such as glycerol, glucose and sorbitol, which can

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Occur in the vapor phase or condensed liquid phase in the presence of a group VIII or metal alloy transition catalyst.

[0012] Patent application Ser. US-A-2005/244312 discloses a method for producing lower alcohols from glycerol using a reactive separation process. Copper chromium powder is the preferred catalyst.

SUMMARY [0013] The present invention relates to methods for producing oxidized hydrocarbons, such as polyols, diols, ketones, aldehydes, carboxycyclic acids and alcohols, from an aqueous solution of the feed material using hydrogen produced from a portion of the feed material solution. Thus, the invention provides a method for producing an oxidized compound from an aqueous solution of a feed material comprising water and at least one water-soluble oxidized hydrocarbon having two or more carbon atoms and selected from ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol , glycerol aldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediols, butyric acid, aldotetroses, tartaric acid (ang. tautaric acid), aldopentoses, aldohexose, ketotetroses, ketopentoses, ketohexoses, alditols, sugars, sugar alcohols, cellulose fibers and plastics, lignocellulosic fibers and materials, saccharides, starches and polyols; a method comprising the steps of: (a) producing hydrogen for reforming hydrogen in the aqueous phase ( aqueous phase reforming (APR) by contacting the oxidized hydrocarbon in a first portion of an aqueous solution of the feed material with a first catalyst material containing at least one Group VIII metal; and (b) reacting APR hydrogen with an oxidized hydrocarbon in a second portion of a solution of the feed fed to reduce the oxidized hydrocarbon to a second catalyst material, the second catalyst material being different from the first catalyst material, and wherein the second catalyst material comprises (i) copper , at least one Group VIII metal or alloy thereof or mixture or (ii) a bifunctional catalyst comprising an acidic support; to produce a reaction product containing at least one reduced oxidized hydrocarbon compound selected from the group consisting of diol, polyol, ketone, aldehyde, carboxylic acid and alcohol.

[0014] The aqueous solution of the feed material preferably contains water and an oxidized hydrocarbon with at least two carbon atoms, such as any of many polyols, sugars, sugar alcohols, alcohols, starch, lignins, fibers and cellulosics and water-soluble saccharides. Preferably, the feed solution solution contains glycerol.

[0015] The first catalytic material is preferably a heterogeneous catalyst with one or more substances capable of producing hydrogen under water phase reforming conditions. The material contains at least one metal from Group VIIIB, alone or in combination with metals from Group VIIB, metals from Group VIB, metals from Group VB, metals from Group IVB, metals from Group IIB, metals from Group IB, metals from Group IVA or metals from the VA group. The second catalytic material is preferably a heterogeneous catalyst having one or more substances capable of catalyzing the reaction between the hydrogen produced and a solution of the feed material to produce diols or other polyols, ketones, aldehydes, carboxylic acids and / or alcohols. Preferable examples of the second catalytic material include copper, Group VIII metals, mixtures and alloys thereof, and various bifunctional catalysts. The second catalytic material may include these metals alone or in combination with one or more metals of group VIIIB, metals of group VIIB, metals of group VIB, metals of group VB, metals of group IVB,

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Group IIB metals, Group IB metals, Group IVA metals or Group VA metals. Preferably, the second catalytic material includes iron, ruthenium, copper, rhenium, cobalt or nickel.

[0016] In one embodiment, polyols, diols, ketones, aldehydes, carboxylic acids and / or alcohols are obtained by producing hydrogen from a portion of the aqueous solution of the feed material placed in contact with the first catalytic material at a temperature from about 80 ° C to 400 ° C , mass hourly flow rate ( weight hourly space velocity, WHSV) of at least about 1.0 gram of oxidized hydrocarbon per gram of first catalytic material per hour and pressure at which water and oxidized hydrocarbons are condensed liquids, followed by reacting hydrogen with a second portion of the solution of the material fed to the second catalytic material under temperature conditions, pressure and mass hourly flow rate effective to produce one or more oxidized hydrocarbons, such as diols and other polyols, ketones, aldehydes, carboxylic acids and / or alcohols. The second part of the feed material solution will generally include both primary oxidized hydrocarbons and oxidized hydrocarbons obtained from the hydrogen generation step and may be contacted with the second catalytic material at a temperature from about 100 ° C to 300 ° C, a pressure from 1480 kPa to 8375 kPa (from 200 psig to 1200 psig) and a mass hourly flow rate of at least about 1.0 gram oxidized hydrocarbon per gram of catalytic material per hour. The obtained composition may generally include, without limitation, a multiphase composition having a solid phase, a catalyst composition comprising a first catalytic material and a second catalytic material, preferably platinum and iron, and a liquid phase comprising water, glycerol, carboxylic acid, propylene glycol and carbon dioxide.

BRIEF DESCRIPTION OF THE FIGURES [0017]

Figure 1 is a graph illustrating thermodynamics (AG ° / room temperature as a function of temperature) for the production of CO and H₂ from CH reforming₄, C.₂H₆, C.₃H₈ and C.₆H₁₄, CH₃(OH), C.₂H₄(OH)₂, C.₃H₅(OH)₃ and C.₆H₈(OH)₆; and carbon monoxide steam conversion. Dashed lines represent ln (P) values ​​for vapor pressure as a function of CH temperature₃(OH), C.₂H₄(OH)₂, C.₃H₅(OH)₃ and C.₆H₈(OH)₆(pressure in units of kPa (atm)).

Figure 2 is a reaction diagram illustrating the reaction pathways for producing H₂ and propylene glycol from glycerol.

Figure 3 is a reaction diagram illustrating the reaction pathways for producing H₂ and propyl alcohol from glycerol.

Figure 4 is a reaction diagram illustrating the reaction pathways for producing H₂ and hexanol from sorbitol. Figure 5 is a schematic diagram illustrating a method of converting a polyol into a diol or alcohol using in-situ generated hydrogen (on site).

Figure 6 is a schematic diagram illustrating a method for producing reaction products from a polyol using a reactor having a first reaction chamber for hydrogen production and a second hydrogenation chamber.

Figure 7 is a schematic diagram illustrating a method for producing reaction products from an added polyol using a reactor having a first reaction chamber for hydrogen production and a second hydrogenation chamber.

Figure 8 is a schematic diagram of a reactor system that can be used to evaluate the production of polyols from glycerol by reforming in the aqueous phase; and

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Figure 9 is a graph illustrating the distribution of carbon products during glycerol reforming in the aqueous phase versus the modified platinum catalyst.

DETAILED DESCRIPTION [0018] The present disclosure relates to methods of reforming biomass concentrations using water at low temperatures to produce propylene glycol, ethylene glycol and other polyols, diols, ketones, aldehydes, carboxylic acids and / or alcohols using in-situ generated hydrogen. Hydrogen can be produced by reacting a portion of an aqueous feed material solution containing biomass and water against the catalyst under aqueous phase reforming (APR) conditions. The hydrogen produced by APR can then be used to react with a second portion of the feed material solution including oxidized hydrocarbons derived from the production of APR hydrogen against the second catalyst under conditions suitable to produce the desired products.

Abbreviations and definitions:

[0019] "GC" = gas chromatograph or gas chromatography.

[0020] "GHSV" = hourly gas flow rate.

[0021] "psig" = pounds per square inch relative to atmospheric pressure (ie, hypertension).

[0022] "Volumetric speed" = mass / volume of reactant per catalyst unit per time unit.

[0023] "TOF" = rotation frequency (catalytic cycles).

[0024] "WHSV" = mass hourly flow rate = mass of oxidized compound per mass of catalyst per hour.

[0025] "WGS" = steam conversion of carbon monoxide.

[0026] Water phase reforming (APR) is a catalytic reforming process that produces fuels with a high hydrogen content from oxidized compounds derived from biomass (glycerol, sugars, sugar alcohols, etc.). Various APR methods and techniques are described in US Pat. Ser. U.S. Patent No. 6,699,457; US 6,964,757 and US 6,964,758; and patent application Ser. North America No. US 11,234,727 (all, Cortright et al. and entitled "Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons"); and patent application Ser. US Patent No. 6,953,873 (Cortright et al. And entitled "Low Temperature Hydrocarbon Production from Oxygenated Hydrocarbons"); and, at the same time, the international patent application of the same applicant No. PCT / US2006 / 048030 (Cortright et al. and entitled "Catalyst and Methods for Reforming Oxygenated Compounds"). The terms "aqueous phase reforming" and "APR" will generally mean the general reaction of the oxidized compound and water to form a hydrogen stream, regardless of whether the reactions occur in the gas phase or in the condensed liquid phase. Where distinction is important, it will be advisable. "Hydrogen APR" will generally refer to the hydrogen produced by the APR process.

[0027] The APR process is preferably carried out in the liquid phase, although it can also be carried out in the vapor phase reaction. APR can occur at temperatures where steam conversion of carbon monoxide is preferred (e.g., 80 ° C to 400 ° C), which allows hydrogen to be generated with small amounts of CO in a single chemical reactor. Advantages of the APR process include: (i) conducting reactions at lower pressures (typically 1480-5100 kPa (from 200 to 725 psig)); (ii) the possibility of producing feed material with a high hydrogen content at lower temperatures without the need to conduct water in

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Volatile state, which provides significant energy savings; (iii) the ability to work at temperatures that minimize undesirable decomposition reactions typically occurring when carbohydrates are heated to higher temperatures; and (iv) the use of agricultural input materials. The APR process uses the unique thermodynamic properties of oxidized compounds with favorable stoichiometry of carbon to oxygen, especially hydrocarbons with a C: O ratio of 1: 1 (preferred ratio), to produce hydrogen at relatively low temperatures in a single reaction step. [0028] A stoichiometric reaction for reforming the oxidized hydrocarbon with a C: O ratio of

1: 1 to produce CO and H₂ given in reaction scheme 1.

CnH2yOn θ nCO + yH2 (1) [0029] The reaction conditions for the production of hydrogen from hydrocarbons may be dictated by the thermodynamics of steam reforming alkanes to produce CO and H₂ (reaction 2) and steam conversion of carbon monoxide to produce CO₂ and H₂ with CO (reaction 3).

CnH2n + 2 + nH2O θ nCO + (2n + 1) H2 (2)

CO + H₂O θ CO₂ + H₂ (3) [0030] Figure 1 (constructed from thermodynamic data taken from the Chemical Properties Handbook, CL Yaws, McGraw Hill, 1999) indicates changes in Gibbs Standard Free Energy (AGY room temperature) associated with Equation 2 for a series of alkanes (CH4, C2H6, C3H8, C6H14), normalized per mole of CO produced. It can be seen that the alkane steam reforming is thermodynamically favorable (i.e., negative AG ° / room temperature) only at temperatures exceeding 675 K (402 ° C).

[0031] Illustrated are also suitable oxidized hydrocarbons with a C: O ratio of 1: 1, such as methanol (CH₃OH), ethylene glycol (C₂H₄(OH)₂), glycerol (C₃H₅(OH)₃) and sorbitol (C₆H₈(OH)₆). In Figure 1, the dashed lines show the Inn (P) values ​​for vapor pressures depending on the temperature CH₃(OH), C.₂H₄(OH)₂, C.₃H₅(OH)₃ and C.₆H₈(OH)₆ (pressure in atm units). Figure 1 indicates that the steam reforming of these oxidized hydrocarbons to produce CO and H₂ it is thermodynamically advantageous at much lower temperatures than those required for alkanes with similar numbers of carbon atoms. Figure 1 also indicates that the AG ° value / room temperature for the steam conversion of carbon monoxide from CO to CO₂ and H₂ is more favorable at similarly low temperatures. Consequently, it is possible to reform oxidized hydrocarbons with favorable C: O ratios at low temperatures to produce CO and H₂ and then H.₂ and what₂in a one-step catalytic process.

[0032] Although Figure 1 indicates that the conversion of oxidized compounds in the presence of water to H₂ and what₂ is very beneficial at low temperatures is a subsequent H reaction₂ and oxidized compounds to form alkanes (C_nH_{2n + 2}) and water is also very beneficial at low temperatures.

WHAT₂ + 4H₂ θ CH₄ + 2H₂O (4) [0033] In a first embodiment, methods for producing oxidized compounds are provided. The methods preferably include the steps of (a) contacting the first catalyst material with a first portion of an aqueous feed solution containing water and water-soluble oxidized hydrocarbons to form an APR hydrogen, and (b) contacting the APR hydrogen and a second portion of the feed solution with a second catalyst material to form a second a reaction product that includes, without limitation, polyol, diol, ketone, aldehyde, carboxylic acid and / or alcohol. The second portion of the feed material solution preferably includes oxidized hydrocarbons derived from

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In addition to the oxidized hydrocarbons contained in the feedstock initial solution, the APR hydrogen production may also include aliquots of the feedstock solution without oxidized hydrocarbons produced during APR hydrogen formation. The first catalyst material is preferably an aqueous phase reforming catalyst (APR) and the second catalyst material is preferably a material capable of catalyzing the hydrogenation reaction. Unless otherwise indicated, any discussion of hydrogenation and APR catalysts herein is a non-limiting example of suitable catalytic materials.

[0034] As more fully described below, a more thermodynamically favorable reaction consumes APR hydrogen to give a mixture of polyols, diols, ketones, aldehydes and / or alcohols. Under preferred conditions, the reactor methods and systems described below can give a mixture containing predominantly one or more oxidized compounds, such as diols and other polyols, ketones, aldehydes, carboxylic acids and / or alcohols. For example, the reactor methods and systems described herein can provide a carbon-containing reaction product from more than 50% of one or more polyols, such as propylene glycol. Preferably, substantially all of the APR hydrogen generated in-situ by the APR process is consumed during the reaction with oxidized hydrocarbons against the second catalyst material, without adding pure hydrogen from an external source.

[0035] Figures 2, 3 and 4 are schematic illustrations of possible reaction pathways for producing both H₂ as well as polyols, diols, ketones and alcohols from oxidized hydrocarbons towards the metal catalyst. Generally, hydrogen production includes dehydrogenation and subsequent rearrangement steps that form intermediates containing carbon atoms not bonded to oxygen atoms. The carbohydrate first undergoes dehydrogenation to form adsorbed intermediates, before breaking the CC or CO bond. Subsequent disruption of CC bonds leads to the formation of CO and H₂, with CO then reacting with water to form CO₂ and H₂ by means of the carbon monoxide (WGS) steam conversion reaction. Polyols, diols, ketones, carboxylic acids, aldehydes and / or alcohols are then formed, where the hydroxyl groups of the oxidized hydrocarbon are removed by a dehydration mechanism with subsequent hydrogenation using the hydrogen formed above. It is also possible to form polyols, diols, ketones and / or alcohols on a metal catalyst by first breaking CO bonds in adsorbed carbohydrate intermediates. The intermediates can then be converted to a polyol, diol, ketone, carboxylic acid, aldehyde and / or alcohol depending on the catalyst and reaction conditions.

Feed material solution [0036] Preferred feed material includes water-soluble oxidized hydrocarbons derived from biomass. The term "biomass" as used herein refers to, without limitation, organic materials produced by plants (such as leaves, roots, seeds and stalks) and microbial and animal metabolic waste. Common sources of biomass include: (1) agricultural wastes such as corn stalks, straw, seed husks, sugar cane residues, sugar cane pomace, nut husks and cattle, chicken and pig fertilizer; (2) wood materials such as wood or bark, sawdust, wood chips and sawmill chips; (3) municipal waste, such as waste paper and green waste; and (4) energetic crops such as poplars, willows, shrub millet, alfalfa, prairie grass of the genus Andropogon, maize, soybean, etc. The feed material can be produced from biomass by any means currently known or developed in the future, or it can be simply by-products of other methods, such as crude glycerol from biodiesel production.

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[0037] Oxidized hydrocarbons are hydrocarbons with at least two carbon atoms and at least one oxygen atom. In a preferred embodiment, the oxidized hydrocarbon is water-soluble and has from 2 to 12 carbon atoms, and more preferably from 2 to 6 carbon atoms. The oxidized hydrocarbon also preferably has an oxygen to carbon ratio in the range of 0.5: 1 to 1.5: 1, including a ratio of 0.75: 1.0, 1.0: 1.0, 1.25: 1 , 0, 1.5: 1: 0 and other relationships within them. In the most preferred embodiment, the oxidized hydrocarbons have an oxygen to carbon ratio of 1: 1. The water-soluble oxidized hydrocarbons used in the invention include at least one of ethanediol, ethanedione, acetic acid, propanol, propanediol, propionic acid, glycerol, glyceryl aldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediol, butyric acid, aldotetr tartaric acid tautaric acid), aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, alditols, sugars, sugar alcohols, fibers and cellulosics, fibers and lignocellulosic materials, saccharides, starches and polyols. Most preferably, the oxidized hydrocarbon is sugar, sugar alcohols, cellulose, saccharides and glycerol.

[0038] The oxidized hydrocarbon combines with water to form an aqueous solution of the feed material at a concentration effective to induce the formation of the desired reaction products. Water can be added before contacting the oxidized hydrocarbon with the APR catalyst or simultaneously with contacting the oxidized hydrocarbon with the APR catalyst. In a preferred embodiment, the water is combined with the oxidized hydrocarbon to form an aqueous solution prior to contacting with the APR catalyst for easier processing, but it is also recognized that the oxidized hydrocarbon can also be placed in solution and then added water during contact with the APR catalyst to form an aqueous solution feed material. Preferably, the remainder of the feed material solution is water. In some embodiments, the feed material solution essentially consists of water, one or more oxidized hydrocarbons, and, optionally, one or more feed material modifiers described herein, such as alkali or alkaline earth or alkaline earth metal or acid salts or hydroxides or acids. The feed material solution may also contain negligible amounts of hydrogen, preferably below about 100 kPa (1 bar) (14.5 psi). In preferred embodiments, hydrogen is not added to the feed material.

[0039] The ratio of water to carbon in the solution is preferably from 0.5: 1 to 7: 1, including ratios within them such as 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1 and any relations within them. The solution of the feed material can also be characterized as a solution whose at least 20 percent by weight of the total solution is an oxidized hydrocarbon. For example, the solution may contain one or more oxidized hydrocarbons, with a total concentration of oxidized hydrocarbons in the solution of at least 20%, 30%, 40%, 50%, 60% by weight or more, including any intermediate percentages and depending on the oxidized hydrocarbons used . More preferably, the feed solution solution comprises at least 20%, 30%, 40%, 50% or 60% by weight glycerol, including any intermediate percentages.

Hydrogen production [0040] APR hydrogen is made from material fed under water phase reforming. The reaction temperature and pressure are preferably chosen so as to keep the material fed into the liquid phase. However, it is recognized that temperature and pressure conditions can also be selected to more preferably generate hydrogen in the vapor phase. In general, the APR and subsequent hydrogenation reactions should be carried out at a temperature at which the thermodynamics of the proposed reaction is favorable. The pressure will be

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EP 2 565 176 B1 changes with temperature. For condensed liquid phase reactions, the pressure in the reactor must be sufficient to maintain the reactants in the condensed liquid phase at the reactor inlet. [0041] For the vapor phase reaction, the reaction should be carried out at a temperature at which the vapor pressure of the oxidized hydrocarbon compound is at least 10.13 kPa (0.1 atm) (and preferably is definitely higher) and the thermodynamics of the reaction are favorable. This temperature will vary depending on the particular oxidized hydrocarbon compound used, but is generally in the range of 100 ° C to 450 ° C for vapor phase reactions, and more preferably 100 ° C to 300 ° C for vapor phase reactions.

[0042] In the case of a liquid phase reaction, the reaction temperature may be from 80 ° C to 400 ° C and the reaction pressure from 598 to 9065 kPa (72 psig to 1300 psig). Preferably, the reaction temperature is from 120 ° C to 300 ° C, and more preferably from 150 ° C to 270 ° C. The reaction pressure is preferably from 598 to 8375 kPa (from 72 to 1200 psig) or from 1101 to 8375 kPa (from 145 to 1200 psig) or from 1480 to 5100 kPa (from 200 to 725 psig) or from 2618 to 4238 kPa (from 365 to 600 psig). Because hydrogen is generated in-situ (on site), pressure is provided by a pumping mechanism that also drives the solution of material fed through the reactor system.

[0043] The condensed liquid phase method can also optionally be carried out using a modifier that increases the activity and / or stability of the first (first) and / or second (second) catalytic (catalytic) material (s) (i.e., the catalytic system). It is preferred that the water and the oxidized hydrocarbon are reacted at a suitable pH of 1.0 to 10.0, including pH values ​​in increments between the order of 0.1 and 0.05, and more preferably at a pH of 4.0 to 10.0. Generally, the modifier is added to the solution of material fed in an amount ranging from 0.1% to 10% by weight compared to the total weight of the catalyst system used, although amounts outside this range are included in the present invention.

[0044] To optimize the proportion of hydrogen in the reaction products, alkali salts or alkaline earth salts can also be added to the solution of the feed material. Examples of suitable water-soluble salts include one or more selected from the group consisting of hydroxide, carbonate, nitrate or chloride of alkali or alkaline earth metals. For example, the addition of alkaline (basic) salts to form a pH of pH 4.0 to pH 10.0 may improve the hydrogen selectivity of the reforming reaction.

[0045] The addition of acidic compounds may also provide increased selectivity with respect to the desired reaction products in the hydrogenation reactions described below. It is preferred that the water-soluble acid is selected from the group consisting of salts - nitrate, phosphate, sulfate and chloride and mixtures thereof. If an optional acid modifier is used, it is preferred that it be present in an amount sufficient to lower the pH of the aqueous feed stream to a value from pH 1.0 to pH 4.0. Lowering the pH of the feed stream in this way can increase the proportion of diols, polyols, ketones, carboxylic acids, aldehydes, alcohols or alkanes in the final reaction products.

[0046] In general, the reaction should be carried out under conditions where the residence time of the material solution fed over the APR catalyst was adequate to produce enough APR hydrogen to react with the second portion of the material solution fed over the hydrogenation catalyst to produce the desired products. For example, in one embodiment, the WHSV for the reaction may be at least 1.0 gram of oxidized hydrocarbon per gram of APR catalyst and preferably from

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1.0 to 5.0 grams of oxidized hydrocarbon per gram of APR catalyst, and more preferably from 1.9 to 4.0 grams of oxidized hydrocarbon per gram of APR catalyst.

APR Catalyst [0047] The first catalytic material is preferably an APR catalyst, typically a heterogeneous catalyst capable of catalyzing the reaction of water and oxidized hydrocarbons to produce hydrogen under the conditions described above. The APR catalyst includes at least one transition metal from Group VIIIB, which can be any alloy or a mixture thereof. Preferably, the APR catalyst comprises at least one transition metal from group VIIIB in combination with at least one second metal selected from such as metals from group VIIIB, group VIIB, group VIB, group VB, group IVB, group IIB, group IB, group IVA or VA group. A preferred Group VIIB metal includes rhenium, manganese, or combinations thereof.

Preferred metal from the VIB group includes chromium, molybdenum, tungsten or a combination thereof. Preferred metals of group VIIIB include platinum, rhodium, ruthenium, palladium, nickel or combinations thereof.

[0048] The preferred load of the main Group VIIIB metal is in the range of 0.25% by weight to 25% by weight on carbon, with weight percent increments between them of the order of 0.10% and 0.05%, such as 1.00% , 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio of the second metal is in the range of 0.25 to 1 to 10 to 1, including ratios within them, such as 0.50, 1.00, 2.50, 5.00 and 7, 50 to 1.

[0049] The preferred catalyst composition is then achieved by the addition of Group IIIB oxides and associated rare earth oxides. In this case, lanthanum or cerium oxides would be preferred components. The preferred atomic ratio of compounds of Group IIIB to the main metal of Group VIIIB is in the range of 0.25 to 1 to 10 to 1, including ratios within them, such as 0.50, 1.00, 2, 50, 5.00 and 7.50 to 1.

[0050] Unless otherwise specified, listing the APR bimetallic catalyst composition as "X: Y", where X and Y are metals, refers to catalyst composition groups containing at least X and Y metals in any suitable stoichiometric combination and optionally including other substances. Similarly, listing the catalyst composition as "X_1,0Y_1,0"Refers here to a composition comprising at least the X and Y metals in a stoichiometric 1: 1 molar ratio. Accordingly, particularly preferred catalyst compositions are bimetallic metal compositions described by the formula X: Y in which X is a metal from group VIIIB and Y is a metal from group VIIIB, group VIIB, groups VIB, group VB, group IVB, group IIB, groups IB, group IVA or group VA. For example, the catalysts indicated as "Re: Pt" include bimetallic catalysts Re_1,0pt_1,0 and Re_2,5pt_1,0. In addition, replacement of the bimetallic X: Y catalyst may include additional materials in addition to X and Y, such as La or Ce. For example, the catalysts indicated herein as "Re: Rh" include catalysts such as Re_1,0rh_1,0, Re_1,0rh_3,8, Re_1,0rh_2,0Ce_2,0, ^Re1,0^rh1,0^Ce1,0 ^{and Re}1,0^rh1,0^La3,0^. [0051] In preferred embodiments, the catalyst system may include a substrate suitable for suspending the catalyst in solution of the feed material. The substrate should be one that provides a stable platform for the selected catalyst and reaction conditions. The medium can take any form that is stable under the selected reaction conditions to function at the desired concentrations and particularly stable in aqueous solutions of the feed material. Such carriers include, without limitation, carbon, silica, silica with alumina, alumina, zirconia; titanium dioxide, cerium dioxide, vanadium (V) oxide and mixtures thereof. In addition, nanoporous supports such as zeolites, carbon nanotubes or carbon in the form of fullerene can be used. Particularly useful catalyst systems include, without

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Limitations, platinum on a silica substrate, platinum on a silica and alumina substrate, platinum on an alumina substrate, nickel on a silica and alumina substrate, nickel on an alumina substrate, ruthenium on a silica substrate and alumina, ruthenium on an alumina substrate, palladium on a silica and alumina substrate, and nickel and platinum on a silica and alumina substrate. In one embodiment, the APR catalyst system is platinum on silica and alumina or silica, with platinum then melted or mixed with nickel, ruthenium, copper, iron or rhenium. In another embodiment, the APR catalyst system is nickel on silica and alumina or silica, with nickel subsequently being melted or mixed with copper, rhenium, ruthenium or iron.

[0052] One particularly preferred catalyst support is carbon, especially carbon supports with relatively large surface areas (above 100 square meters per gram). Such coals include activated carbon (granulated, powdered or pelleted), fabric, activated carbon impregnated felts or activated carbon fibers, nanotubes or carbon nanotubes, fullerene carbon, carbon honeycomb structures with a large surface area, carbon (mesh) foams carbon foams) and carbon blocks. Coal can be produced by chemical or steam activation of coal from peat, wood, lignite, fossil coal, coconut shells, olive stones and petroleum. Another preferred substrate is granulated activated carbon made from coconuts.

[0053] The substrate may also be treated or modified to improve its properties. For example, the substrate can be treated, such as by surface modification, to modify surface groups such as hydrogen and hydroxyl. Hydrogen and hydroxyl surface groups can cause local pH changes that affect catalytic efficiency. The substrate can also be modified, e.g. by treatment with sulfates, phosphates, tungstates and silanes. In the case of carbon carriers, carbon can be previously treated with steam, oxygen (from the air), inorganic acids or hydrogen peroxide to create more surface oxygen sites. A preferred pre-treatment would be the use of oxygen or hydrogen peroxide. Pre-treated carbon can also be modified by adding metal oxides of group IVB and metal oxides of group VB. The use of titanium oxides, vanadium oxides, zirconia and mixtures thereof is preferred.

[0054] The APR catalyst system can be prepared by conventional methods known to those skilled in the art. These methods include evaporation impregnation techniques, capillary impregnation techniques, chemical vapor deposition, rinse coating, magnetron sputtering techniques, etc. The method chosen for the preparation of the catalyst is not particularly critical to the function of the invention, with the proviso that different catalysts will give different results depending on such issues as overall surface area, porosity, etc.

Preparation of oxidized compounds [0055] Various oxidized compounds can be prepared by preferred methods and reactor systems. For example, reaction products may include one or more diols or other polyols, ketones, aldehydes, carboxylic acids and alcohols derived from the reaction of hydrogen produced in-situ APR with a portion of the remaining solution of the material fed to a second catalytic material, preferably a hydrogenation catalyst, under reaction temperature conditions , reaction pressure and mass hourly flow rate (WHSV) effective to produce the desired reaction products. The temperature and pressure are preferably selected for carrying out the liquid phase reaction. still

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However, it is recognized that temperature and pressure conditions can also be selected to more preferably produce the desired products in the vapor phase. In general, the reaction should be carried out at a temperature at which the thermodynamics of the proposed reaction is favorable. The pressure will vary with temperature and WHSV. For condensed liquid phase reactions, the reactor pressure must be sufficient to maintain the reactants in the condensed liquid phase at the reactor inlet. [0056] For liquid phase reactions, the reaction temperature may be from 100 ° C to 300 ° C and the reaction pressure from 598 to 9065 kPa (72 psig to 1300 psig). Preferably, the reaction temperature is from 120 ° C to 270 ° C, and more preferably from 200 ° C to 270 ° C. The reaction pressure is preferably from 598 to 8375 kPa (from 72 to 1200 psig) or from 1101 to 8375 kPa (from 145 to 1200 psig) or from 1480 to 5100 kPa (from 200 to 725 psig) or from 2618 to 4238 kPa (from 365 to 600 psig).

[0057] For the vapor phase reaction, the reaction should be carried out at a temperature at which the vapor pressure of the oxidized hydrocarbon compound is at least 10.13 kPa (0.1 atm) (and preferably is much higher) and the thermodynamics of the reaction are favorable. This temperature will vary depending on the particular oxidized hydrocarbon compound used, but generally ranges from 100 ° C to 300 ° C for the vapor phase reaction.

[0058] The method using the condensed liquid phase of the present invention can also be carried out using a modifier that increases the activity and / or stability of the catalyst system. It is preferred that the water and the oxidized hydrocarbon are reacted at a suitable pH of 1.0 to 10.0, including pH values ​​in increments between them of 0.1 and 0.05, and more preferably at a pH of 4.0 to 10.0 . Generally, the modifier is added to the material solution fed in an amount ranging from 0.1% to 10% by weight compared to the total weight of the catalyst system used.

[0059] In general, the reaction should be carried out under conditions where the residence time of the material solution fed over the catalyst is adequate to produce the desired products. For example, the WHSV for the reaction may be at least 1.0 gram of oxidized hydrocarbon per gram of catalyst per hour, and preferably from 1.0 to 5.0 grams of oxidized hydrocarbon per gram of catalyst per hour, and more preferably from 1.9 to 4.0 grams oxidized hydrocarbon per gram of catalyst per hour.

Hydrogenation catalyst [0060] The second catalytic material must contain: (i) copper, at least one Group VIII metal or an alloy thereof, or a mixture thereof; or (ii) a bifunctional catalyst containing an acidic substrate. The second catalytic material is preferably a heterogeneous hydrogenation catalyst capable of catalyzing the reaction of hydrogen and oxidized hydrocarbons to produce the desired reaction products. A preferred hydrogenation catalyst may include copper or at least one transition metal of group VIIIB and any alloys or mixtures thereof. The catalyst may also be designed to include copper or at least one transition metal from Group VIIIB as the first metal and at least one second metal from a group of metals from Group VIIIB, Group VIIB, groups VIB, Group VB, Group IVB, Group IIB, groups IB, group IVA or group VA. A preferred Group VIIB metal includes rhenium, manganese, or combinations thereof. Preferred metal from the VIB group includes chromium, molybdenum, tungsten or a combination thereof. Preferred metals of group VIIIB include platinum, rhodium, ruthenium, palladium, nickel or combinations thereof. In one embodiment, a preferred catalyst includes iron or rhenium and at least one transition metal selected from iridium, nickel, palladium, platinum, rhodium and ruthenium. In another embodiment, the catalyst comprises iron, rhenium and at least copper or one transition metal of group VIIIB.

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[0061] The second catalytic material is preferably a hydrogenation catalyst. It differs from the first catalytic material, which is preferably an APR catalyst. The second catalyst is preferably capable of working in parallel with or independently of the APR catalyst. The hydrogenation catalyst may be a bifunctional catalyst containing an acidic substrate. Acid carriers (e.g. carriers with low isoelectric points) are able to catalyze the dehydration reaction of oxidized compounds, followed by hydrogenation reactions of metallic catalyst sites in the presence of H₂, again leading to carbon atoms unrelated to oxygen atoms. The bifunctional dehydration / hydrogenation pathway consumes H₂ and leads to the subsequent formation of various polyols, diols, ketones, aldehydes and alcohols. Examples of such catalysts include tungsten zirconia, titanium dioxide with zirconia, sulfated zirconia, acid alumina, silica with alumina and heteropolyacid supports. Heteropolyacids are a class of solid phase acids represented, for example, by compounds such as H_{3 + x}PMO_12-xV_xABOUT₄₀, H₄Siw₁₂ABOUT₄₀, H₃PW₁₂ABOUT₄₀, H₆P₂IN₁₈ABOUT₆₂ etc. Heteropolyacids are solid phase acids with a well-defined local structure, the most common of which is Keggin's tungsten-based structure. The Keggin unit contains the central PO tetrahedron₄, surrounded by 12 octahedrons WO₆. The standard unit has a net charge (-3) and therefore requires 3 cations to ensure electro-neutrality. If the cations are protons, then the material functions as Bronsted acid. The acidity of these compounds (as well as other physical properties) can be "tuned" by substituting various metals in the Keggin structure for tungsten. See, e.g., Bardin et al. (1998) "Acidity of

Keggin-Type Heteropolycompounds Evaluated by Catalytic Probe Reactions, Sorption Micro-calorimetry and Density Functional Quantum Chemical Calculations "J. of Physical Chemistry B, 102: 10817-10825. [0062] Similar to the APR catalyst, the hydrogenation catalyst may adhere to the substrate as described above. The support can be the same support that was used for the APR catalyst or the support specific to the hydrogenation catalyst that was selected for the desired reaction result.

[0063] Preferred copper or group VIIIB metal load ranges from 0.25% by weight to 25% by weight on carbon, with weight percentages in increments of the order of 0.10% and 0.05%, such as 1 , 00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio of the second metal is in the range of 0.25 to 1 to 10 to 1; including any relationship between them such as 0.50, 1.00, 2.50, 5.00 and 7.50 to 1. In one embodiment, the hydrogenation catalyst comprises iron (Fe), a Group VIIIB metal, with an atomic ratio of Fe to the main Group VIIIB metal of 0.25 to 1 to 10 to 1. If the catalyst adheres to the substrate, the combination of catalyst and substrate from 0.25% by weight to 10% by weight of copper or primary metal of group VIIIB.

[0064] The heterogeneous catalyst may also be combined with an APR catalyst to form a mixture so as to allow simultaneous or nearly simultaneous occurrence of the APR reaction and the hydrogenation reaction in a single reaction vessel. In this case, listing the bimetallic catalyst composition as "X: Y", where X is the APR catalyst and Y is the hydrogenation catalyst, is intended to refer to a group of catalyst compositions comprising at least the APR X catalyst and the Y hydrogenation catalyst, in any suitable stoichiometric combination and including other materials where indicated. For example, the catalysts indicated as "Pt: Fe" include a Pt mixture_1,0fe_1,0 and Fri._2,5fe_1,0. Particularly preferred catalysts include Pt_1,0Ni_1,0fe_1,0 and Fri._1,0fe_1,0Cu_1,0, where Pt and Pt: Ni are the APR catalyst and Fe and Fe: Cu are the hydrogenation catalyst.

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[0065] The preferred atomic ratio of the APR catalyst (first catalyst material) to the hydrogenation catalyst (second catalyst material) is in the range from 5: 1 to 1: 5, such as, without limitation, 4.5: 1 , 4.0: 1, 3: 5: 1, 3.0: 1, 2.5: 1, 2.0: 1, 1.5: 1, 1: 1, 1: 1.5, 1: 2 , 0, 1: 2.5, 1: 3.0, 1: 3.5, 1: 4.0, 1: 4.5 and any amounts between them. For example, in one embodiment, a mixture of catalysts with an APR catalyst comprising platinum and a hydrogenation catalyst comprising iron (Pt: Fe) in a ratio of 1: 1 is provided. If the catalyst mixture adheres to the substrate, the catalyst and substrate combination may comprise from 0.25% by weight to 10% by weight of the mixture.

[0066] The hydrogenation catalyst system, alone or mixed with an APR catalyst, can be prepared by conventional methods known to those skilled in the art. Such methods include evaporation impregnation, capillary impregnation, chemical vapor deposition, rinse coating, magnetron sputtering techniques, etc. The method chosen for the preparation of the catalyst is not particularly critical to the function of the invention, with the proviso that different catalysts will give different results depending on issues such as overall surface area, porosity, etc.

Reactor [0067] The reaction system can be configured to select the flow direction of the aqueous feed material solution to ensure maximum interaction of the hydrogen generated in-situ (on site) with the feed material solution. For example, the reactor can be designed such that the APR catalyst and hydrogenation catalyst form a stack in a single reaction vessel, or are separated so that the APR catalyst and hydrogenation catalyst are in separate reaction vessels. The reactor can also be designed to contain multiple APR and hydrogenation catalysts to allow for optimal production of more than one reaction product. The reactor system may also include additional inlets to allow additional materials to be fed in or to direct the reaction towards the desired reaction products, and to allow reaction by-products to be recycled for use in the reforming process.

[0068] The reactor can be designed so that the solution of the feed material flows horizontally, vertically or diagonally in relation to the gravitational plane, so as to maximize the efficiency of the system: in systems in which the solution of the feed material flows vertically or diagonally to the gravitational plane, the feed material solution can flow in the opposite direction to gravity (upward flow system) or gravity (downward flow system). In one preferred embodiment, the reactor is designed as an upward flow system such that a solution of the feed material flows up the reactor. In this embodiment, the feed material solution is first contacted with a first reaction bed containing an APR catalyst to produce APR hydrogen. Due to the reactor configuration, the APR hydrogen can then be passed, under certain conditions, through a second reaction bed containing the hydrogenation catalyst at a rate equal to or greater than the feed material solution rate to maximize the interaction of the feed material solution with hydrogen and the hydrogenation catalyst.

[0069] In a single chamber reactor, the APR catalyst and the hydrogenation catalyst may be placed in a stack configuration to allow the feed material solution to first contact the APR catalyst and then the hydrogenation catalyst or a series of hydrogenation catalysts, depending on the desired reaction products. Reaction beds for the catalyst or APR and hydrogenation catalysts can also be placed side by side depending on the particular mechanism used

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Such as a horizontal flow system. In any case, the feed material solution can be introduced into the reaction vessel through one or more inlets and then directed through the processing catalysts. In a preferred embodiment, the feed material solution is directed through the APR catalyst to produce APR hydrogen, and then both the APR hydrogen and the remaining feed material solution are directed, through the hydrogenation catalyst or catalysts, to produce the desired reaction products. In embodiments employing a mixture of an APR catalyst and a hydrogenation catalyst, the production of APR hydrogen and reaction products may occur simultaneously or in parallel.

[0070] In a configuration with separate reactors, the reactor can be designed to allow the production of APR hydrogen to occur in the reaction bed in one reaction vessel with reaction products produced in another reaction vessel. Reaction vessels can be configured to work in parallel or sequentially. In a parallel configuration, the feed material solution can be separated to direct the first part of the feed material solution into the hydrogen reaction bed in which the APR hydrogen is produced and the second part to the hydrogenation reaction bed in which the desired reaction products are produced using the APR hydrogen produced through a hydrogen reaction vessel. Alternatively, the reactor can be configured to be adapted to use two separate feed material solutions, with the first feed material solution directed to the hydrogen reaction vessel and the second feed material solution directed to the hydrogenation reaction vessel. In the sequential operation configuration, the reactor can be designed so that a solution of the material fed flows through the hydrogen reaction vessel and into the hydrogenation reaction vessel. In each of these systems, because APR hydrogen is generated in-situ (on site), pressure is provided by a pumping mechanism that also directs the solution of the material fed through the reactor chambers.

Additional materials [0071] Additional materials and compositions ("additives") can be added to the material solution fed at various stages of the process to enhance the reaction or direct it to produce the desired reaction products. Additives may include, without limitation, acids, salts and additional hydrogen or additional feed material. Such additives can be added directly to the feed stream prior to contacting the hydrogenation catalyst or continuously with it, or directly to the hydrogenation reaction bed.

[0072] In one embodiment, the additive may include an additional solution of the feed material to provide additional oxidized hydrocarbons for the hydrogenation reaction. The feed material may include any one or more oxidized hydrocarbons specified above, including any one or more sugar alcohols, glucose, polyols, glycerol or saccharides. For example, the additional material may include glycerol. In this embodiment, crude glycerol is used to start the reaction and to generate hydrogen so as to avoid contamination of the hydrogenation catalyst with crude glycerol. The purified glycerol is then added to the feed solution before or simultaneously with the primary feed solution being contacted with the hydrogenation catalyst to increase the amount of oxidized hydrocarbons available for processing. The opposite is expected to apply to the crude glycerol serving as the additive, depending on the properties of the APR catalyst and the hydrogenation catalyst.

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[0073] In another embodiment, the additive may include by-products of the present invention recycled for further processing. By-products may include diols, polyols, ketones, aldehydes, carboxylic acids, alcohols and other products produced during the practice of the present invention. For example, the desired reaction product of one embodiment of the present invention is propylene glycol. However, the production of propylene glycol may also result in the production of other polyols, ketones, aldehydes, alcohols and carboxylic acids. The polyols can be recycled and added back to the material solution fed prior to contact with the hydrogenation catalysts to produce additional oxidized hydrocarbons for conversion to propylene glycol. Similarly, ketones and alcohols can be added to the material solution fed prior to contact with the APR catalyst to further supplement hydrogen production.

[0074] In another embodiment, the additional material may include acids and salts. The addition of acidic compounds can provide increased selectivity with respect to the desired reaction products. In preferred embodiments, the water-soluble acid may include, without limitation, nitrate, phosphate, sulfate, chloride salts and mixtures thereof. If an optional acid modifier is used, it is preferred that it be present in an amount sufficient to lower the pH of the aqueous feed stream to a value from pH 1.0 to pH 4.0. Lowering the pH of the feed stream in this way can increase the proportion of diols, polyols, ketones, alcohols or alkanes in the final reaction products.

[0075] In another embodiment, the additive may include additional hydrogen added to the material solution fed to supplement the APR hydrogen and to facilitate the directing of the hydrogenation reaction to the desired reaction product. The term "additional hydrogen" refers to hydrogen that is not produced from oxidized hydrocarbons in the feed material, such as hydrogen added to the feed material from an external source. For example, additional hydrogen may be added to the system to increase the reaction pressure against the hydrogenation catalyst or to increase the molar ratio of hydrogen to carbon and / or oxygen to increase the yield of certain types of reaction products, such as ketones and alcohols. Additional hydrogen may be added in a molar ratio of additional hydrogen to hydrogen APR in amounts not exceeding 1: 1, preferably not exceeding 1: 3, more preferably not exceeding 1:10 and even more preferably not exceeding 1:20. In the most preferred embodiment, no additional hydrogen is added.

[0076] The amount of additional hydrogen to be added can also be calculated taking into account the concentration of oxidized hydrocarbons in the solution of the feed material. Preferably, the amount of additional hydrogen added should provide a molar ratio of hydrogen atoms (i.e., 2 oxygen atoms per molecule of gaseous H₂) to oxygen atoms in oxidized hydrocarbons up to mole less than or equal to 1.0. For example, when the feed material is an aqueous solution consisting of glycerol (3 oxygen atoms), the amount of additional hydrogen added to the feed material is preferably not more than 1.5 moles of hydrogen gas (H₂) per mole of glycerol (C₃H₈ABOUT₃) and preferably not more than 1.25, 1.0, 0.75, 0.50 or 0.25. In general, the amount of additional hydrogen added is preferably below 0.75 times and more preferably not more than 0.67, 0.50, 0.33, 0.30, 0.25, 0.20, 0.15, 0, 10, 0.05, 0.01 times the amount of total hydrogen (APR hydrogen and additional hydrogen) that will provide an atomic oxygen to hydrogen ratio of 1: 1.

[0077] The amount of APR hydrogen in the reactor can be identified or detected by any suitable method. The presence of APR hydrogen is determined on the basis of the product stream composition as a function of the feed stream composition, catalyst composition and reaction conditions, regardless of the actual reaction mechanism present in the feed stream. The amount of hydrogen APR

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EP 2 565 176 B1 can be calculated based on the catalyst, reaction conditions (e.g. flow rate, temperature, pressure) and the content of feed material and reaction products. For example, the feed material can be contacted with an APR catalyst (e.g., platinum) to produce APR hydrogen on site and the first reaction product stream without the hydrogenation catalyst. The feed material can also be contacted with both the APR catalyst and the hydrogenation catalyst to produce a second reaction product stream. By comparing the composition of the first reaction product stream and the second reaction product stream under comparable reaction conditions, the presence of APR hydrogen can be determined and the amount of APR hydrogen produced is calculated. For example, an increase in the amount of oxidized compounds with higher hydrogenation levels in the reaction product compared to the components of the feed material may indicate the production of APR hydrogen.

Reaction Products [0078] The present invention provides new methods for preparing polyols, diols, ketones, aldehydes, carboxylic acids and alcohols in a single catalytic process using in-situ generated hydrogen. Polyols include, without limitation, diols, triols, 1,1,1-tris (hydroxymethyl) ethane (trimethylol ethane), sorbitol and mannitol. Diols include, without limitation, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol and decylene glycol. Triols include, without limitation, glycerol (glycerin), trimethylpropane, hexanetriol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (trimethylpropane). Ketones include, without limitation, acetone, propan-2-one, 2-oxopropanal, butan-2-one, butane-2,3-dione, 2-hydroxypropanal, 3-hydroxybutan-2-one, pentan-2-one, pentane- 2,3-dione, pentane-2,4-dione, hexan-2-one, heptan-2-one, octane-2-one, nonan-2-one, decan-2-one and their isomers. Carboxylic acids include, without limitation, lactic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid and their isomers and derivatives, including hydroxylated derivatives such as 2-hydroxybutanoic acid. Aldehydes may include, without limitation, acetaldehyde, prionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal and their isomers. Alcohols include, without limitation, methanol, ethanol, propyl alcohol, isopropyl alcohol, propanol, butyl alcohol, isobutyl alcohol, butanol, pentanol, hexanol, heptanol.

[0079] The specific reaction products produced as a result of the present invention will depend on various factors, including without limitation, feed material solution, water concentration, reaction temperature, reaction pressure, catalyst reactivity, and feed material solution flow rate as they will be affected by per volumetric velocity (mass / volume of reactant per catalyst unit per unit of time), hourly gas flow rate (GHSV) and mass hourly gas flow rate (W HSV).

[0080] Preferably, the feed material and reaction stream are contacted with the first catalyst material and the second catalyst material, respectively, with a mass hourly flow rate (W HSV) that is large enough to produce a reaction product containing one or more oxidized hydrocarbons. It is assumed that reducing WHSV to less than 0.5 grams of oxidized hydrocarbons in the material fed per hour can increase the amount of hydrocarbons in the reaction products. Thus, WHSV is preferably at least 1.0 gram of oxidized hydrocarbons in the material fed per hour, more preferably WHSV is from 1.0 to 5.0 g / g hour, including WHSV 1.0,

1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2, 3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4, 8, 4.9 and 5.0 g / g per hour. In one

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In an aspect, the feed material comprises glycerol contacted with the first catalyst material at WHSV of 1.9 or 4.0 g glycerol / hour to produce a reaction product containing propylene glycol.

[0081] The skilled person will be aware that alteration of the above factors as well as others will generally lead to a modification of the reaction product yield. For example, increasing the flow rate, and thereby reducing the exposure of the material fed to the catalyst over time, will likely result in a decrease in the amount of hydrogen available for hydrogenation over the hydrogenation catalyst. Increasing the flow rate may also reduce the time to hydrogenation, thereby leading to an increased yield of higher diols and polyols, with a reduction in the yield of ketones and alcohol.

[0082] One skilled in the art can also modify the above conditions to increase the efficiency of the system and reduce the cost of producing the desired reaction products. For example, modifying the ratio of water to oxidized hydrocarbon in the feed material solution can improve the overall thermal efficiency of the process by reducing the need for external temperature control. The process is thermally efficient if it is carried out at a feed concentration of over 20% by weight of the oxidized compound, preferably above 30% by weight, more preferably above 40% by weight and most preferably above 50% by weight.

[0083] In one preferred embodiment, the present invention provides a method of making a polyol from an aqueous solution of the glycerol-containing feed material. Figure 2 shows a reaction scheme for the production of propylene glycol from glycerol with hydrogen production in-situ. In the reaction scheme shown in Figure 2, a portion of glycerol is reacted with water under reforming conditions in the aqueous phase to produce APR hydrogen and a byproduct, carbon dioxide (Route 1 in Figure 2). Stoichiometry for Route 1 is shown in reaction scheme 5 below:

C₃H₃ABOUT₃ [glycerol] + 3H₂About 3 CO₂ + 7H₂ (5)

The APR hydrogen produced is then used for the dehydration / hydrogenation reaction (Route 2 in Figure 2) for the selective production of propylene glycol. Stoichiometry for Route 2 is shown in reaction scheme 6 below:

C3H8O3 [glycerol] + H2 C3H8O2 [propylene glycol] + H2O (6)

At this stage, a portion of the glycerol in the feed material solution is contacted with a portion of the APR hydrogen versus the hydrogenation catalyst under appropriate reforming conditions in the aqueous phase to form polyols such as ethylene glycol and propylene glycol. In a preferred embodiment, the combination of two reaction pathways occurs according to the general reaction shown in reaction scheme 7.

1.14 C.₃H₈ABOUT₃ C₃H₈ABOUT₂ + 0.43 CO₂ + 0.57 H₂AT 7)

From this theoretical stoichiometry, 0.14 glycerol molecules must be reformed to generate enough APR hydrogen to hydrogenate one glycerol molecule to propylene glycol.

[0084] In another embodiment, the present invention provides a method of making alcohol from an aqueous solution of the glycerol-containing feed material. Figure 3 is a schematic illustration showing a method of converting glycerol to alcohol with hydrogen production in-situ. In this process, glycerol is simultaneously (i.e., Steps 1 and 2 are carried out simultaneously over a single reactor bed) converted into APR hydrogen and alcohol (and other APR reaction products such carbon monoxide, dioxide

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Carbon, propylene glycol, methane, ethane, propane). Stoichiometry for Route 1 is shown in reaction scheme 8 below:

C₃H₈ABOUT₃ [glycerol] + 3H₂About 3 CO₂ + 7H₂ (8)

Stoichiometry for Route 2 is shown in reaction scheme 9 below:

C3H8O3 [glycerol] + 2 H2 C3H8O [propyl alcohol] + 2 H2O (9)

The stoichiometry of the general reaction to produce 1 molecule of propyl alcohol is shown in reaction scheme 10 below:

1.28 C3H8O3 [glycerol]> C3H8O [propyl alcohol] + 0.86 CO2 + 1.14 H2O (10)

From this theoretical stoichiometry, 0.28 glycerol molecules must be reformed to generate enough APR hydrogen to hydrogenate one glycerol molecule to propyl alcohol.

[0085] In yet another embodiment, methods are provided for making alcohol from an aqueous solution of the feed material containing sorbitol. Figure 4 is also a schematic illustration showing a method of converting sorbitol to alcohol with hydrogen production in-situ. In this method, sorbitol is converted simultaneously (i.e., Steps 1 and 2 are carried out simultaneously over a single reactor bed) into hydrogen and alcohol (and other APR reaction products such as carbon monoxide, carbon dioxide, methane, ethane, propane, butane, pentane and hexane). The stoichiometry for Route 1 is shown in reaction scheme 11 below:

C₆H₁₄ABOUT₆ [sorbitol] + 6H₂6 o'clock₂ + 13 H₂ (11)

The stoichiometry for Route 2 is shown in reaction scheme 12 below:

C6H14O6 [sorbitol] + 5 H2 C6H14O [hexanol] + 5 H2O (12)

The stoichiometry of the general reaction to produce 1 molecule of hexanol is shown in reaction scheme 13 below:

1.38 C6H14O6 [sorbitol]> C6H14O [hexanol] + 2.30 CO2 + 2.69 H2O (13)

From this theoretical stoichiometry, 0.38 sorbitol molecules are reformed to generate enough APR hydrogen to hydrogenate one sorbitol molecule to hexanol.

[0086] One preferred method for preparing the oxidized compound comprises the steps of: contacting a first catalyst material containing one or more Group VIII metals with a first portion of an aqueous solution of the feed material containing water and at least one water-soluble oxidized hydrocarbon having two or more carbon atoms in: temperature from 80 ° C to 400 ° C;

a mass hourly flow rate of at least 1.0 gram oxidized hydrocarbon per gram of first catalyst material per hour; and pressure at which water and oxidized hydrocarbons are condensed liquids to obtain hydrogen for water phase reforming (APR); and reacting the APR hydrogen with a second portion of the material solution fed to the second catalytic material, wherein the second catalytic material differs from the first catalytic material and is selected from the group consisting of: iron, ruthenium, copper, cobalt, nickel, their alloys and mixtures thereof : temperature from 100 ° C to 300 ° C; and at a pressure of 1480-8375 kPa (from 200 psig to 1200 psig) to produce a reaction product containing one or more oxidized compounds selected from the group consisting of polyol, diol, ketone, aldehyde, carboxylic acid and alcohol. In one aspect, the first portion of the feed material solution and / or the second portion of the feed material solution is contacted with the first catalyst material and the second catalyst material in

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In a reaction vessel at a temperature of 200 ° C to 270 ° C, comprising 210 ° C, 220 ° C, 230 ° C, 240 ° C, 250 ° C, 260 ° C and intervals of 1 ° C between 200 ° C and 270 ° C. In another aspect, the second portion of the feed material solution is contacted with APR hydrogen and the second catalyst material at a pressure above 2618 kPa (365 psig) (e.g., 2618-8375 kPa (365-1200 psig)), preferably above 2859 kPa (400 psig ) (e.g. 3397 kPa or 2859-8325 kPa (478 psig or 400-1200 psig)) or above 3549 kPa (500 psig) (e.g. 4135 kPa or 3549-8375 kPa (585 psig or 500-1200 psig)). The feed material is preferably passed through a mass hourly flow (WHSV) reactor selected to produce a product stream containing one or more oxidized compounds, including at least one of polyol, ketone, aldehyde, carboxylic acid and alcohol. For example, WHSV can be from 1.0 to 5.0 grams (including 1.0-4.0, 1.0-3.0, 1.0-2.0, 2.0-5.0, 3, 0-5.0, 4.0-5.0 and any other interval of the order of 0.1) between them) of oxidized hydrocarbon (oxidized hydrocarbons) in the material given per gram of catalytic mixture per hour.

[0087] Another preferred method for producing propylene glycol includes the step of contacting a heterogeneous catalyst system containing one or more Group VIII metals (e.g., one or more metals including platinum) and a hydrogenation catalyst, with an aqueous solution of the feed material containing water and a water-soluble oxidized hydrocarbon (e.g. glycerol or sorbitol) at a temperature and pressure suitable to maintain the liquid phase feed material (e.g. including temperatures from 100 ° C to 300 ° C) at a mass hourly flow rate of at least 1.0 gram water-soluble oxidized hydrocarbon per gram of heterogeneous catalyst per hour and the pressure at which the feed material remains a condensed liquid to form a reaction product containing one or more oxidized compounds such as polyol (e.g. propylene glycol), aldehyde, ketone, carboxylic acid (e.g. lactic acid) and / or alcohol. The heterogeneous catalyst system may comprise a first group VIII catalyst material or any suitable APR catalyst and a second catalyst comprising a hydrogenation catalyst. The heterogeneous catalyst system may be a catalytic mixture of Group VIII metal and a hydrogenation catalyst. The heterogeneous catalyst system may also be two separate catalyst materials, including an APR catalyst and a hydrogenation catalyst, contacted separately or together with the feed material. Preferably, the heterogeneous catalyst system comprises a first catalyst material (e.g., an APR catalyst comprising at least one Group VIII metal) and a second catalyst material (e.g. hydrogenation catalyst) in a molar ratio of 5: 1 to 1: 5, including 4: 1, 3: 1, 2: 1, 1: 1, 1: 2, 1: 3, 1: 4 ratios and 0: 1 between 5: 1 and 1: 5. [0088] In certain aspects of preferred embodiments, the first catalyst material comprises at least one transition metal selected from the group consisting of platinum, nickel, palladium, ruthenium, rhodium, iridium, their alloys and mixtures thereof. Alternatively, the first catalyst material may also be selected from one of more of the following groups: platinum, nickel, palladium, ruthenium, rhodium, iridium and mixtures thereof; platinum, nickel, palladium, ruthenium, rhodium, iridium and their alloys; platinum, nickel, palladium, ruthenium, rhodium, iridium, their alloys and mixtures thereof; platinum, nickel, palladium, iridium, their alloys and mixtures thereof; and nickel, palladium, ruthenium, rhodium, iridium, their alloys and mixtures thereof.

[0089] In certain aspects of preferred embodiments, the second catalyst material is selected from one or more of the following groups: iron, nickel, ruthenium and cobalt; iron, ruthenium and cobalt; iron, nickel and cobalt; iron, nickel and ruthenium; nickel, ruthenium and cobalt; iron, nickel and ruthenium; and iron and cobalt. The second catalytic material differs from the first catalytic material.

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[0090] Optionally, the first catalyst material and / or the second catalyst material may adhere to one or more suitable support materials, such as a support with acid sites

Br0nsteda. The medium may contain carbon. Also optionally, the heterogeneous catalyst may consist essentially (or consist of) of about 5% by weight of iron and platinum in a molar ratio of about 1: 1 on an activated carbon substrate; the feed material may contain at least 20% by weight (including 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% and amounts in the order of 1% between them) of one or more oxidized hydrocarbons such as glycerol and / or sorbitol; the feed material can be contacted with a heterogeneous catalyst with a mass hourly flow rate of 1.0 to 5.0 grams glycerol per gram of heterogeneous catalyst per hour and at a pressure of 1825-4238 kPa (250600 psig) (including 2170-4238 kPa, 2170- 8375 kPa, 2618-4238 kPa, 2618-8375 kPa, 2859-4238 kPa, 3397 kPa, 3397-8375 kPa, 4135 kPa and 4135-8375 kPa (300-600 psig, 300-1200 psig, 365-600 psig, 365 -1200 psig, 400-600 psig, 478 psig, 478-1200 psig, 585 psig and 585-1200 psig)); or the reaction product has a carbon yield of propylene glycol of 40% or more (including 50%, 60%, 70%, 80%, 90% or more). The amount of propylene glycol in the reaction product is preferably at least 5%, 10%, 20%, 30% or 40% of the amount of the liquid reaction product.

[0091] When this occurs, additional hydrogen is preferably supplied in a small amount. The feed material preferably does not substantially include additional hydrogen in the reaction process. Most preferably, additional external hydrogen is provided in amounts providing less than one hydrogen atom per oxygen atom in all oxidized hydrocarbons in the feed stream prior to contacting the catalyst. For example, the molar ratio between additional hydrogen and all water-soluble oxidized hydrocarbons in the solution of the feed material is preferably selected so as to obtain no more than one hydrogen atom in the additional (external) hydrogen per oxygen atom in the oxidized hydrocarbon. Generally, the molar ratio of oxidized hydrocarbon (oxidized hydrocarbons) in the feed material to the additional (external) hydrogen fed to the feed material preferably does not exceed 1: 1, more preferably up to 2: 1, 3: 1, 5: 1, 10: 1, 20 : 1 or more (including 4: 1, 6: 1, 7: 1, 8: 1, 9: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1 , 17: 1, 18: 1 and 19: 1). The amount (mole) of hydrogen introduced into the material fed from an external source is preferably 0-30%, 0-25%, 0-20%, 0-15%, 0-10%, 0-5%, 0-2%, 0 -1% of the total number of moles of oxidized hydrocarbon (oxidized hydrocarbons) in the feed, including all intervals between them. Also preferably, when the feed material solution or any part of it is reacted with APR hydrogen and hydrogen of external origin such that the molar ratio of APR hydrogen to hydrogen of external origin is at least 3: 1, including ratios 5: 1, 10: 1, 20 : 1 and relations between them (including 4: 1, 6: 1, 7: 1, 8: 1, 9: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16 : 1, 17: 1, 18: 1 and 19: 1).

[0092] The following examples serve to explain the features of the invention.

EXAMPLES

Example 1 Illustrative system of reactor 1 (reference) [0093] Figure 5 is a schematic illustration showing one preferred method of converting feed material solution 1 into the final desired product 12 using a single reactor containing a catalyst consisting of a mixture of an APR catalyst and a hydrogenation catalyst. The feed 1 solution includes water combined with one or more oxidized

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Hydrocarbons such as glycerol or sugar alcohol. Feed material solution 1 is combined with a recycle stream 15 containing unreacted polyols, water and process by-products, such as methanol and ethanol, from the process. The combined stream 2 is fed through an HPLC pump (not shown) into the reactor system 3 containing the APR / hydrogenation catalyst, where part of the stream reacts with water over the catalyst to form the APR hydrogen, which later reacts with another part of the stream over the hydrogenation catalyst to produce the desired products.

[0094] The eluate stream 4 from reactor 3 contains a mixture of water, hydrogen, carbon dioxide, light hydrocarbons, light alcohols (methanol and ethanol), diol product and unreacted glycerol. The mixture is cooled and separated in a two-phase separator 5 in which non-condensed gases (such as hydrogen, carbon dioxide, methane, ethane and propane) are removed via stream 6 from the phase containing water-soluble alcohols and diols. The non-condensing stream 6 can be burned to obtain process heat (e.g. heat to drive the reaction in reactor 3) or sent to a separating system in which hydrogen can be recovered to recycle back to stream 2. The aqueous stream 7 can be sent to the separator 8 in which light alcohols (methanol and ethanol) and water are removed and recycled through stream 10 to the reactor inlet. Purge stream 14 is turned on to prevent water accumulation in the reactor system.

[0095] The crude product stream 9, containing unreacted glycerol and the desired products in the form of polyol, diol, ketone, aldehyde, carboxylic acid and / or alcohol, is recovered from the separator 8 via stream 9 and sent to a finishing separator in which the desired product 12 is separated from unreacted glycerol 13. The unreacted glycerol stream is then added to stream 10 and recycled to the reactor system via stream 15.

Example 2. Illustrative reactor system 2 (reference) [0096] Figure 6 is a diagram showing another preferred method of converting a polyol feed material solution 101 to a final diol product 114 using a reactor system that includes a first reactor bed 103 with an APR catalyst and a second reactor bed 104 with hydrogenation catalyst. The feed material solution 101 includes water combined with one or more oxidized hydrocarbons, such as sugar alcohol or glycerol. The feed material solution 101 is combined with a recycle stream 117 containing unreacted polyols, water, and unwanted by-products (e.g., methanol and ethanol). The combined stream 102 is fed through an HPLC pump (not shown) into the first bed of the reactor 103, in which part of the stream reacts with water against the APR catalyst to form the APR hydrogen. Recycled alcohols (methanol and ethanol) also react with water towards the APR catalyst to form APR hydrogen and light hydrocarbons such as methane and ethane.

[0097] Eluate containing APR hydrogen, water, CO₂, light hydrocarbons and polyols are transferred from the first reactor bed 103 to the second reactor bed 104, in which the APR hydrogen reacts with a portion of the polyols to produce the desired products. In this illustration, the reactor bed 103 and the reactor bed 104 are sent in an upward orientation to allow the APR hydrogen generated to percolate from the reactor bed 103 through the second reactor bed 104 to maximize the interaction of the APR hydrogen and stream 102 with the hydrogenation catalyst. The beds of reactors 103 and 104 can also be designed to assume orientations with downward flow or with horizontal flow.

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[0098] The eluate stream 105 from the reactor system comprises a mixture of water, hydrogen, carbon dioxide, light hydrocarbons, light alcohols (methanol and ethanol), diol and polyol products, and unreacted glycerol. The mixture is cooled and separated in a two-phase separator 106 in which non-condensable gases (such as hydrogen, carbon dioxide, methane, ethane and propane) are removed via stream 107 from the phase containing water-soluble alcohols, diols and polyols. The non-condensing stream 107 can either be burned to obtain process heat or sent to a separating system in which hydrogen is recovered for eventual recycling to stream 102. The aqueous stream 108 is sent to a separator 109 in which light alcohols (methanol and ethanol ) and water is removed and recycled through stream 110 to the reactor inlet. Purge stream 116 is turned on to prevent water accumulation in the reactor system.

[0099] The crude product stream 112, containing unreacted glycerol and the desired polyol, diol and / or alcohol products, is recovered from the separator 109 via stream 112 and sent to a finishing separator 113 in which the desired product 114 is separated from the unreacted glycerol 115 The unreacted glycerol stream is added to stream 110 and recycled back to the reactor system via stream 117.

Example 3. Illustrative system of reactor 3 (reference) [0100] Figure 7 is a diagram showing another preferred method of converting feed material solution 201 into final product 215 with the addition of additive 205. Additive 205 may include various salts, acids, additional feed material solution, hydrogen or process by-products.

[0101] The feed material solution 201 includes water combined with one or more oxidized hydrocarbons, such as glycerol or sugar alcohol. The feed material solution 201 may contain the same combination as the feed material solution 205 or a combination of one or more cheap oxidized compounds, such as waste methanol from the biodiesel production process, ethylene glycol from spent antifreeze or cheap alcohols. Stream 201 can also be combined with recycle stream 218, which contains unreacted polyols, water and unwanted by-products, such as methanol and ethanol, to form the combined stream 202. [0102] The combined stream 202 is fed through an HPLC pump (not shown) to 203 reactor beds with an APR catalyst. Oxidized hydrocarbons in combined stream 202 react with water over the APR catalyst to form the APR hydrogen, while recycled alcohols (e.g., methanol and ethanol) form hydrogen and light hydrocarbons, such as methane and ethane.

[0103] Eluate from the first reactor bed 204, containing APR hydrogen, water, CO₂, light hydrocarbons and unreacted hydrocarbons are combined with Appendix 205. In this illustration, Appendix 205 is a feed material solution containing more oxidized hydrocarbons, such as purified glycerol. The combined eluate 204 and additive 205 are directed to a reactor bed 206 containing a hydrogenation catalyst to react the APR hydrogen with oxidized hydrocarbons to produce the desired product in the form of a polyol, diol and / or alcohol 215. The reactor eluate stream 207 contains a mixture of water, hydrogen, carbon dioxide, light hydrocarbons, light alcohols (methanol and ethanol), polyols, diols, ketones, aldehydes, carboxylic acids and unreacted glycerol.

[0104] The mixture is cooled and separated in a two-phase separator 208 in which non-condensable gases such as hydrogen, carbon dioxide, methane, ethane and propane are removed through stream 209 from the phase 209

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EP 2 565 176 B1 containing water-soluble polyols, alcohols and / or diols. Stream 209 can be burned to obtain process heat or sent to a separating system in which hydrogen can be recovered for possible recycle to stream 201 or used as an additive

205.

[0105] Water stream 210 is sent to separator 211 in which light alcohols (methanol and ethanol) and water are removed and recycled through stream 212 to the reactor inlet. Purge stream 217 is turned on to prevent water accumulation in the reactor system. The crude product stream 213 containing the desired product 215 and unreacted hydrocarbons is recovered from the separator 211 via stream 213 and sent to a finishing separator 214 in which the desired product 215 is separated from the unreacted hydrocarbons 216. The unreacted hydrocarbons stream is added to stream 216 and recycled back to circulation to the reactor system through stream 218 or used as an additive 205.

Example 4. Illustrative system of reactor 4 (reference) [0106] The production of polyols from glycerol is carried out using the test system illustrated in Figure 8. The reactor in the system is configured in a downward orientation that improves contact of aqueous solutions of the feed material with hydrogen APR generated in situ (on site) as it flows through the reactor.

[0107] The catalysts are placed in a stainless steel tubular reactor 1, which is installed in an aluminum block heater 2 to maintain isothermal conditions. The reaction temperature is controlled by the temperature control subsystem. Certain components of the temperature control subsystem (not shown in Figure 8) include a thermocouple introduced into the tubular reactor, resistance heaters mounted on the aluminum block and the PID controller.

[0108] Substrate solutions (i.e., feedstock solutions) can be selected for continuous delivery to the reactor using an HPLC pump 3. The material leaving the reactor is cooled as it passes through the heat exchanger 4 before entering the phase separator 5.

[0109] The gases leave the phase separator through a manifold 6 that the pressure control subsystem maintains at constant pressure. The components of the pressure control subsystem include: pressure sensor 7, pressure control valve 8 and PID controller 9. The amount of gas released by the pressure control valve 8 is measured by mass flow meter 10. The composition of this gas is monitored by gas chromatography.

[0110] The liquid level in the phase separator 5 is kept constant by the level control subsystem. The components of the level control subsystem include a level sensor 11 in a phase separator, a level control valve 12 and a PID controller 13. The aqueous solution drained from the phase separator during the catalyst evaluation experiment is collected and the amount collected is measured gravimetrically. Analysis of this solution may include pH analysis, total organic carbon, GC to determine the concentration of unreacted substrate and specific intermediates and by-products.

Example 5. Method for producing an improved carbon substrate (reference) [0111] Hydrogen peroxide was used to functionalize activated carbon atoms to provide improved catalyst supports. See SR de Miguel, OA Scelza, MC Roman-Martinez, C. Salinas Martinez de Lecea, D. Cazorla-Amoros, A. Linares-Solano, Applied Catalysis A: General 170

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(1998) 93. Activated carbon, 61 g, was slowly added to 1600 ml of a 30% hydrogen peroxide solution. After completion of the carbon addition, the mixture was left overnight. The aqueous phase was decanted and the carbon was washed three times with 1600 ml deionized water, then dried under vacuum at 100 ° C.

Example 6. Method for producing a bimetallic catalyst system (reference) [0112] A bimetallic catalyst system containing a mixture of 5% by weight of platinum (APR catalyst) and iron (hydrogenation catalyst) (1: 1 molar ratio) on an activated carbon substrate was prepared using capillary impregnation techniques . An aqueous solution of equal volume for capillary impregnation for carbon saturation, 10.4 ml and containing 1.72 g of dihydrohexachloroplatinate (IV) hexahydrate (Alfa Aesar, 39.85% Pt) and 1.42 g of iron (III) nitrate nonahydrate ( Alpha

Aesar) was added dropwise, with stirring, to 13.02 g of hydrogen peroxide functionalized carbon (Example 5). The wetted carbon was dried at 100 ° C under reduced pressure.

Example 7. Preparation of propylene glycol [0113] The catalyst system described in Example 6 was tested in the apparatus described in Example 4 using a feed material solution containing 50% by weight glycerol. The catalyst was treated with a stream of hydrogen at 350 ° C before introducing the glycerol feed material solution. The reaction conditions were set at 240 ° C, 3296 kPa (478 psig) and WHSV of 4.0 grams glycerol per gram of catalyst per hour. The conversion of glycerol was 64%. This experiment was repeated using a second feed material solution containing 50% by weight glycerol and 50% water fed over the catalyst of Example 6 under the following reaction conditions: 260 ° C, 4033 kPa (585 psig), WHSV of 1.9 grams glycerol per gram of catalyst for an hour.

[0114] In the low temperature regime, all pressures and amounts of catalyst used were commercially feasible conditions for the APR process. The glycerol transformations for these two cases were 64% and 88% of the theoretical maximum, respectively. Figure 9 summarizes the yield of carbon-containing products and indicates the selectivity of converting glycerol to carbon-containing products for high and low temperature reactions. The graph indicates that propylene glycol was the main product produced, followed by carbon dioxide (a byproduct of APR hydrogen production in-situ), ethanol and ethylene glycol. The gas phase alkanes included methane, ethane and propane, with methane being the most abundant gas phase alkane.

[0115] The results confirm that it is possible to produce propylene glycol in reasonable yields by liquid phase reforming of glycerol aqueous solutions and that it is possible to produce significant or dominant amounts of propylene glycol from glycerol with in-situ generated hydrogen and, preferably, without the simultaneous introduction of hydrogen from an external source. The presence of by-products from the hydrogen production process surprisingly did not significantly affect the ability of glycerol to convert into propylene glycol and other products.

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EP 2 565 176 B1