Production of propylene from glycerides

Abstract

The disclosure concerns a process to convert one or more glycerides into propylene and one or more fatty acids, said process is remarkable in that it comprises the steps of (a) providing a first stream comprising one or more glycerides; (b) providing a second stream comprising hydrogen; (c) providing a catalytic system; (d) contacting the first stream and the second stream with the catalytic system provided at step (c) under reaction conditions to form an effluent comprising at least propylene and one or more fatty acids; (e) recovering the propylene from said effluent; wherein the catalytic system provided at step (c) comprises one or more coordination metal complexes, one or more aqueous acidic compounds, one or more ionic liquids, and CO and / or one or more CO-releasing compounds.

Description

[0001] Production of propylene from glycerides

[0002] Technical field

[0003] The present disclosure relates to a process to convert one or more glycerides into propylene, as well as to a method for making polypropylene or sustainable fuel using said process.

[0004] Technical background

[0005] The profusion of glycerides, or more particularly triglycerides, in natural sources, such as vegetable oils, makes them particularly interesting for chemistry. Indeed, the hydrolysis of triglycerides provides, among others, glycerol, which is widely used in different fields, such as in the food industry as notably sweeteners and / or preservatives, in the medical and / or pharmaceutical industry as an antimicrobial and antiviral agent used in treatments of wounds, or the cosmetics industry as soaps. In addition, since glycerol is a compound having three carbon atoms, it can be used to make propylene, which is a valuable starting material to make plastics (such as polypropylene) or sustainable fuels, such as sustainable aviation fuels (SAF).

[0006] While W02020 / 260588 relates to a method of hydrodeoxygenation of oxygenated compounds, such as sugar alcohols or in particular glycerol, into compounds with unsaturated carbon-carbon bonds, such as propylene that could serve the above purposes, this method suffers from practical implementation since glycerol as starting materials is not easily available since its use is widely developed and its access as starting materials available in large quantity is restricted.

[0007] In the way to develop routes towards propylene, starting from triglycerides (as precursors of glycerol) is still not straightforward, since several steps are required. The triglycerides must be firstly hydrolysed into glycerol which must be then converted into propanol before a dehydration step into propylene. This renders cumbersome the formation of propylene from triglycerides.

[0008] The objective of this disclosure is therefore to simplify the conversion of glycerides into propylene, in particular triglycerides.

[0009] Summary

[0010] According to a first aspect, the disclosure relates to a process to convert one or more glycerides into propylene and one or more fatty acids, said process is remarkable in that it comprises the following steps: a) providing a first stream comprising one or more glycerides; b) providing a second stream comprising hydrogen; c) providing a catalytic system; d) contacting the first stream and the second stream with the catalytic system provided at step (c) under reaction conditions to form an effluent comprising at least propylene and one or more fatty acids; e) recovering the propylene from said effluent; wherein the catalytic system provided at step (c) comprises

[0011] - one or more coordination metal complexes,

[0012] - one or more aqueous acidic compounds,

[0013] - one or more ionic liquids, and

[0014] - carbon monoxide and / or one or more CO-releasing compounds.

[0015] Surprisingly, it was found that the process of the present disclosure can directly convert and valorise glycerides into propylene and one or more fatty acids. The glyceride hydrolysis into glycerol and the hydrodeoxygenation of the glycerol into propylene are performed in a one- pot synthesis, avoiding carbon loss ( / .e., propane loss) as it is the case for the direct hydrodeoxygenation (HDO) of glycerides and limiting at the same time the H2 consumption.

[0016] Advantageously, the process further comprises the step of pre-treating the first stream before step (d). For example, the step of pre-treating comprises the step of bleaching the first stream provided at step (a), with an optional step of degumming performed before said step of bleaching.

[0017] Advantageously, the one or more coordination metal complexes are or comprise one or more metallic ions in an amount ranging between 0.1 mol.% and 10.0 mol.% based on the total molar content of the one or more glycerides comprised in the first stream, preferably between 0.5 mol.% and 5.0 mol.%, or between 2.0 mol.% and 4.0 mol.%.

[0018] Advantageously, the one or more coordination metal complexes are or comprise one or more transition metals. For example, the one or more coordination metal complexes are or comprise one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe, Ag, Au, Pt, Cu or a mixture thereof; with preference, one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe or a mixture thereof; more preferably, one or more transition metals selected from Ru and / or Fe, even more preferably, one transition metal is Ru. For example, one transition metal can be Ru(ll) and / or Ru(lll). For example, the one or more coordination metal complexes comprise one or more soluble complexing agents, wherein the one or more soluble complexing agents are injected within the catalytic system provided at step (c) at a concentration ranging between 0.01 mol.% and 10 mol.% based on the total molar content of the one or more coordination metal complexes, preferably between 0.1 mol.% and 5 mol.%.

[0019] For example, the one or more coordination metal complexes comprise one or more gaseous complexing agents, wherein the one or more gaseous complexing agents are injected within the catalytic system provided at step (c) at a partial pressure ranging between 0.01 kPa and 0.6 MPa, preferably ranging between 0.1 kPa and 0.5 MPa. For example, one gaseous complexing agent is carbon monoxide.

[0020] With preference, the catalytic system provided at step (c) is made in situ by contacting one or more metal-containing precursors with one or more complexing agents comprising a carbonyl moiety, one or more aqueous acidic compounds and one or more ionic liquids. For example, the one or more metal-containing precursors are one or more transition metal-containing precursors.

[0021] Advantageously, the one or more CO-releasing compounds are selected from one or more aldehydes, one or more carboxylic acids, one or more metal carbonyls, or a mixture thereof; with preference, the one or more metal carbonyls are one or more CO-releasing compounds and comprise the one or more coordination metal complexes.

[0022] For example, the one or more coordination metal complexes are selected from RuCh(CO3)2, RuBr2(CO3)2, RuCh, RuBrs, or a mixture thereof.

[0023] Advantageously, the one or more ionic liquids are present in an amount ranging between 10 mol.% and 500 mol.% based on the total molar content of the one or more glycerides comprised in the first stream, preferably between 50 mol.% and 450 mol.%, more preferably between 100 mol.% and 400 mol.%, even more preferably between 150 mol.% and 350 mol.%, or between 200 mol.% and 300 mol.%.

[0024] Advantageously, the one or more ionic liquids are selected from one or more phosphonium- based ionic liquids, one or more ammonium-based ionic liquids, one or more sulfonium-based ionic liquids or a mixture thereof; with preference, from one or more phosphonium-based ionic liquids. For example, the one or more ionic liquids comprise tetrabutylphosphonium. For example, the one or more aqueous acidic compounds are one or more acidic compounds dissolved in water.

[0025] With preference, the amount of water is at least 0.01 mol.% of the total molar content of the one or more glycerides comprised in the first stream. More preferably, the amount of water is ranging between 0.01 mol.% and 500 mol.% of the total molar content of the one or more glycerides comprised in the first stream, more preferably between 0.1 mol.% and 300 mol.%, even more preferably between 0.5 mol.% and 100 mol.%, or between 1 mol.% and 100 mol.%.

[0026] - Advantageously, the one or more acidic compounds comprised within the catalytic system acts as one or more co-catalysts.

[0027] - Advantageously, the one or more acidic compounds are present in an amount ranging between 2.5 mol.% and 15 mol.% based on the total molar content of the one or more glycerides comprised in the first stream, preferably between 3 mol.% and 14 mol.%, or between 4 mol.% and 13 mol.%.

[0028] - Advantageously, the one or more acidic compounds are selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, phosphoric acid, pyrophosphoric acid, sulfuric acid, nitric acid, or a mixture thereof; with preference hydrochloric acid.

[0029] Advantageously, the first stream further comprises one or more solvents, or if the one or more ionic liquid functions as one or more solvents, the first stream further comprises one or more co-solvents. With preference, said one or more solvents or said one or more co-solvents are selected from one or more aliphatic compounds and / or one or more aromatic compounds, more preferably from one or more aliphatic compounds. For example, said one or more aliphatic compounds are dodecane, naphtha, jet fuel, diesel or a mixture thereof.

[0030] Advantageously, the process is operated in batch mode, where a stirred reactor vessel is loaded with the first stream, the catalytic system and optionally one or more solvents, brought to a reaction temperature and a hydrogen pressure applied to pursue the reaction during a given time after which the reaction is stopped, the reactor vessel is emptied, and the effluent comprising at least propylene and one or more fatty acids is recovered.

[0031] Advantageously, the process is operated in a continuous stirred-tank reactor, where a mixture of the first stream, the catalytic system and optionally one or more solvents, is continuously preheated to a reaction temperature and fed to the stirred-tank reactor, and a hydrogen pressure is applied to pursue the reaction during a given residence time, wherein the liquid level in the stirred-tank reactor is controlled by withdrawing liquid from the reactor vessel, and wherein the effluent comprising at least propylene and one or more fatty acids is recovered. Dissolved propylene and / or propane and one or more fatty acids are separated from the withdrawn liquid from the reactor and the one or more solvents, including the ionic liquid are recycled back to the reactor

[0032] In a preferred configuration, the one or more ionic liquids, the one or more fatty acids comprised within the effluent formed at step (d) and optionally the one or more solvents form separate liquid phases under the reaction conditions, and the process is operated in a continuous stirred-tank reactor, where a mixture of the first stream, the catalytic system and optionally one or more solvents, is continuously preheated to a reaction temperature and fed to the stirred-tank reactor, and a hydrogen pressure is applied to pursue the reaction during a given residence time, wherein the liquid level in the stirred-tank reactor is controlled by withdrawing liquid from the reactor vessel, and wherein the effluent comprising at least propylene and one or more fatty acids is recovered. The one or more ionic liquids, being a denser immiscible phase and containing substantially most of the one or more coordination metal complexes, can stay in the stirred-tank reactor much longer than the required residence time required to pursue the reaction.

[0033] Advantageously, the process is operated in a loop reactor, where the agitation is provided by pumping around the reactor content or by a gas-lift system.

[0034] Advantageously, the one or more glycerides are selected from one or more monoglycerides, one or more diglycerides, one or more triglycerides or a mixture thereof. More preferably, the one or more glycerides are one or more triglycerides. For example, each triglyceride has three aliphatic chains, and the process is remarkable in that at least two of the three aliphatic chains are identical and have a number of carbons ranging between 2 and 39, preferably between 7 and 24, or between 7 and 23, or between 7 and 20, or between 10 and 20. With preference, each triglyceride has three aliphatic chains, and the process is remarkable in that the three aliphatic chains are identical and have a number of carbons ranging between 2 and 39; or between 7 and 24; more preferably, a number of carbons ranging between 7 and 23, even more preferably, a number of carbons ranging between 7 and 20, or between 10 and 20.

[0035] Advantageously, the effluent formed at step (d) further comprises at least one or more ionic liquids, and the process further comprises the step (f) of separating the one or more fatty acids from the one or more ionic liquids to recover at least a stream of one or more fatty acids and / or at least a stream of one or more ionic liquids.

[0036] For example, the stream of one or more fatty acids is submitted to a hydrodeoxygenation (HDO) reaction, preferably under hydrodeoxygenation conditions, followed by an optional hydroisomerization (HI) reaction, preferably under hydroisomerization conditions, so as to form one or more sustainable hydrocarbon fuels, such as one or more of naphtha, diesel fuel, kerosene or a mixture thereof. For example, the hydrodeoxygenation (HDO) conditions comprise hydrogenolysis conditions and hydrogenation conditions.

[0037] With preference, the stream of one or more ionic liquids is recycled. More preferably, the stream of one or more ionic liquids is recycled within the catalytic system provided in step (d).

[0038] Advantageously, the reaction conditions of step (d) comprise: an H2 partial pressure ranging between 2 MPa and 10 MPa, preferably between 2 MPa and 8 MPa, more preferably between 2 MPa and 6 MPa, and even more preferably between 2.5 MPa and 5.5 MPa; and / or a temperature of at least 150°C, preferably of at least 180°C. For example, the reaction conditions of step (d) comprise a temperature ranging between 150°C and 250°C, or between 180°C and 240°C, or between 200°C and 220°C; and / or a reaction time ranging between 10 minutes and 1 hour, or between 15 minutes and 45 minutes; and / or a residence time ranging from 1 minute to 1 hour, preferably from 10 minutes to 30 minutes, more preferably from 15 minutes to 20 minutes.

[0039] For example, said process is performed in a continuous mode.

[0040] For example, said process is carried out in a one-pot configuration.

[0041] According to a second aspect, the disclosure relates to a method for making polypropylene, said method being remarkable in that it comprises at least one process to convert one or more glycerides into propylene as defined in the first aspect, said process comprising the additional step (g) of using the recovered propylene of step (e) in a polymerization step.

[0042] According to a third aspect, the disclosure relates to a method for making sustainable fuel, said method being remarkable in that it comprises at least one process to convert one or more glycerides into propylene as defined in the first aspect, said process comprising the additional step (g) of using the recovered propylene of step (e) in a catalytic oligomerization step. The propylene is thus converted into mainly olefinic hydrocarbons having 9 to 18 carbons that can be subsequently hydrogenated into the corresponding paraffins. With preference, the method for making sustainable fuel is a method for making sustainable aviation fuel. Description of the figure

[0043] Figure 1 is an overview of the chemistry presented in this disclosure. Optional steps have been drawn in dotted rectangles.

[0044] Detailed description

[0045] For the disclosure, the following definitions are given:

[0046] The terms "comprising", "comprise" and "comprised of" as used herein are synonymous with "including", "include", "containing" and "contain", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. The terms "comprising”, "comprises" and "comprised of" also include the term “consisting of”.

[0047] The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g., 1 to 5 can include 1 , 2, 3, 4, 5 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of endpoints also includes the recited endpoint values themselves (e.g., from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0048] Zeolite codes (e.g., CHA...) are defined according to the “Atlas of Zeolite Framework Types", 6threvised edition, 2007, Elsevier, to which the present application also refers.

[0049] The term “alkali metal” refers to an element classified as an element from the group 1 of the periodic table of elements, excluding hydrogen. According to this definition, the alkali metals are Li, Na, K, Rb, Cs and Fr.

[0050] The term “alkaline earth metal” refers to an element classified as an element from the group 2 of the periodic table of elements. According to this definition, the alkaline earth metals are Be, Mg, Ca, Sr, Ba and Ra.

[0051] The term “transition metal” refers to an element whose atom has a partially filled d sub-shell, or which can give rise to cations with an incomplete d sub-shell (IIIPAC definition). According to this definition, the transition metals are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ac, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, and Cn. The metals Ga, In, Sn, TI, Pb and Bi are considered as “post-transition” metals.

[0052] The name “glyceride” encompasses chemical compounds which are esters derived from glycerol and fatty acids. In particular, “triglyceride” relates to a chemical compound which is an ester of glycerol and three fatty acids. The triglyceride is chemically represented by the below formula, wherein R represent an aliphatic chain. Each aliphatic chain R can have a number of carbons ranging between 2 and 39.

[0053] Rapeseed oil was used as triglyceride in the second example of the present disclosure. According to the document of Warabi Y., et al. (Bioresource Technology, 2004, 91, 283-287), rapeseed oil consists of 98.5% of triglycerides and 1 .5% of free fatty acids.

[0054] The particular features, structures, characteristics or embodiments may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments.

[0055] The disclosure relates to a process to convert one or more glycerides into propylene and one or more fatty acids, said process is remarkable in that it comprises the following steps: a) providing a first stream comprising one or more glycerides; b) providing a second stream comprising hydrogen; c) providing a catalytic system; d) contacting the first stream and the second stream with the catalytic system provided at step (c) under reaction conditions to form an effluent comprising at least propylene and one or more fatty acids; e) recovering the propylene from said effluent; wherein the catalytic system provided at step (c) comprises

[0056] - one or more coordination metal complexes,

[0057] - one or more aqueous acidic compounds,

[0058] - one or more ionic liquids, and

[0059] - carbon monoxide and / or one or more CO-releasing compounds.

[0060] Therefore, as overviewed on figure 1 , from one or more glycerides or more particularly from one or more triglycerides, without any need to isolate the intermediate glycerol ( / .e., said process is advantageously carried out in a one-pot configuration), it is possible to produce propylene and one or more fatty acids. The propylene recovered at step (e) can thus be used in a method for making polypropylene when conveyed into a polymerization unit and / or used in a polymerization step; or in a method for making sustainable fuel ( / .e., biofuel), or preferably sustainable aviation fuel (SAF), when used into a catalytic oligomerization step, followed by an hydrogenation step and fractionation. In addition, the one or more fatty acids that can also be recovered from the effluent formed at step (d) can be transformed into sustainable fuel when subjected to an hydrodeoxygenation (HDO) reaction followed by an optional hydroisomerization (HI) reaction.

[0061] An aqueous acidic reaction mixture also comprising one or more ionic liquids is required for triggering the hydrolysis of the one or more glycerides into one or more fatty acids and glycerol.

[0062] The one or more aqueous acidic compounds can be advantageously one or more acidic compounds, which acts as one or more co-catalysts, and are dissolved in water. In combination with the one or more ionic liquids which act as dehydrating agents, the hydrolysis of one or more glycerides into one or more fatty acids and glycerol is facilitated since the activation energy is decreased, increasing subsequently the kinetics energy (and thus the rate) of the reaction.

[0063] For example, the amount of water is at least 0.01 mol.% of the total molar content of the one or more glycerides comprised in the first stream. Once the deoxygenation reactions starts to produce propylene from the glycerol moiety, also water is produced that can hence be further used in the hydrolysis of the one or more glycerides. More preferably, the amount of water is ranging between 0.01 mol.% and 500 mol.% of the total molar content of the one or more glycerides comprised in the first stream, more preferably between 0.1 mol.% and 300 mol.%, even more preferably between 0.5 mol.% and 100 mol.%, or between 1 mol.% and 100 mol.%. For example, the one or more acid compounds which acts as one or more co-catalysts are selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, phosphoric acid, pyrophosphoric acid, sulfuric acid, nitric acid, or a mixture thereof; with preference, the one or more acid compounds are or comprise hydrochloric acid. Since pyrophosphoric acid is a solid, an amount of water of at least 0.01 mol.% of the total molar content of the one or more glycerides comprised in the first stream can be sufficient to trigger the hydrolysis of the one or more glycerides into one or more fatty acids and glycerol.

[0064] Nevertheless, in practice, the use of water as such can be avoided, since the following aqueous solutions are readily commercially available: hydrochloric acid as an aqueous solution with 37 wt.% of hydrochloric acid based on the total weight of said aqueous solution, hydrobromic acid as an aqueous solution with 48 wt.% of hydrobromic acid based on the total weight of said aqueous solution, hydroiodic acid as an aqueous solution with 57 wt.% of hydroiodic acid based on the total weight of said aqueous solution, acetic acid as an aqueous solution with 1 mol of acetic acid per litre of said aqueous solution, phosphoric acid as an aqueous solution with 85 wt.% of phosphoric acid based on the total weight of said aqueous solution, sulfuric acid as an aqueous solution with 5 mol of sulfuric acid per litre of said aqueous solution, nitric acid as an aqueous solution with 0.5 mol of nitric acid per litre of said aqueous solution.

[0065] For example, the one or more ionic liquids are selected from one or more phosphonium-based ionic liquids, one or more ammonium-based ionic liquids, one or more sulfonium-based ionic liquids or a mixture thereof; with preference, from one or more phosphonium-based ionic liquids. For example, the one or more ionic liquids comprise tetrabutylphosphonium, methyltributylphosphonium, tributylphosphonium, tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium or any mixture thereof, more preferably tetrabutylphosphonium. The one or more ionic liquids also comprise one or more anions, which can be either one or more organic anions or one or more inorganic anions, preferably one or more inorganic anions. For example, one or more organic anions can be selected from one or more carboxylate anions (such as acetate, lactate, decanoate, benzoate, amino acids), one or more alkylsuflate anions, one or more alkylphoshpate anions, alkylphosphinate anions, one or more tosylate anions, one or more methanesulfonate anions, or any mixture thereof. For example, one or more inorganic anions can be selected from Cl Br, I OH NO3; BF4; PF6; CF3SO3; (CF3SO3)2N; preferably Ch.

[0066] Ionic liquids that are readily commercially available are for example Bu4PBr and BU4PCI.

[0067] As the one or more ionic liquids can also serve as a solvent to dissolve the required one or more acidic compounds, they are present at least in a stoichiometric amount compared to the one or more glycerides comprised in the first stream. For example, the one or more ionic liquids are present in an amount ranging between 10 mol.% and 500 mol.% based on the total molar content of the one or more glycerides comprised in the first stream, preferably between 50 mol.% and 450 mol.%, more preferably between 100 mol.% and 400 mol.%, even more preferably between 150 mol.% and 350 mol.%, or between 200 mol.% and 300 mol.%. The formation of a small quantity of glycerol is sufficient to displace the equilibrium towards the one or more products of the reaction since at the end gaseous propylene will be formed and will be removed from the reaction mixture. Glycerol is transformed into 1- hydroxypropanone, while generating water that will serve to further hydrolyse the one or more glycerides.

[0068] Reduction of 1-1 into propane-1 , 2-diol

[0069] 1 -hydroxypropanone is then reduced into propane-1 , 2-diol ( / .e., propylene glycol) thanks to the presence of the one or more coordination metal complexes, the CO atmosphere and the second stream comprising hydrogen. For example, the partial hydrogen pressure is ranging between 2 MPa and 10 MPa, or between 2 MPa and 8 MPa, or between 2 MPa and 6 MPa, or between 2.5 MPa and 5.5 MPa.

[0070] Those one or more coordination metal complexes are or comprise one or more transition metals, preferably selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au or any combination thereof; with preference, one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe, Ag, Au, Pt, Cu or a mixture thereof; more preferably, one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe or a mixture thereof; even more preferably, one or more transition metals selected from Ru and / or Fe, most preferably, one transition metal is Ru. For example, one transition metal can be Ru(ll) and / or Ru(lll), preferably Ru(lll). The one or more transition metals can be for example present in an amount ranging between 0.1 mol.% and 10.0 mol.% based on the total molar content of the one or more glycerides comprised in the first stream, preferably between 0.5 mol.% and 5.0 mol.%, or between 2.0 mol.% and 4.0 mol.%.

[0071] With preference, the catalytic system provided at step (c) is made in situ by contacting one or more metal-containing precursors with one or more complexing agents comprising a carbonyl moiety, one or more aqueous acidic compounds and one or more ionic liquids. For example, the one or more metal-containing precursors are one or more transition metal-containing precursors. Indeed, the one or more coordination metal complexes can be one or more metallic compounds formed in the reaction conditions from one or more metal-containing precursors.

[0072] The one or more metal-containing precursors can be any transition metal compound that, at least partially, forms a dissolved transition metal species in the reaction conditions. Examples of suitable transition metals from the one or more transition metal compounds are Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, or any mixtures thereof, with preference, Ru, Rh, Ir, Co, Ni, Fe, Ag, Au, Pt, Cu or a mixture thereof; more preferably, one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe or a mixture thereof; even more preferably, one or more transition metals selected from Ru and / or Fe, most preferably, one transition metal is Ru.

[0073] In some embodiments of the present disclosure, the external addition of carbon monoxide to the reaction system has an advantageous effect on catalysis. Apart from the addition of CO itself, also carbon monoxide-releasing molecules (CO-RMs) such as aldehydes, carboxylic acids or metal carbonyls can be used. Non-limiting examples of aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 3- oxobutanal, benzaldehyde, furfural, hydroxymethylfurfural, cinnamaldehyde and vanillin. Non-limiting examples of carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, lactic acid, citric acid and benzoic acid. Non-limiting examples of metal carbonyls are triruthenium dodecacarbonyl (RU3(CO)I2), tricarbonyldichlororuthenium(ll) dimer ([RuCh(CO)3]2), ruthenium pentacarbonyl (Ru(CO)s), carbonylchlorohydridotris(triphenylphosphine)ruthenium(ll), vanadium hexacarbonyl (V(CO)e), molybdenum hexacarbonyl (Mo(CO)e), chromium hexacarbonyl (Cr(CO)e), tungsten hexacarbonyl (W(CO)e), dimanganese decacarbonyl (Mn2(CO) ), dirhenium decacarbonyl (Re2(CO) ), iron pentacarbonyl (Fe(CO)s), triiron dodecacarbonyl, diiron nonacarbonyl, dicobalt octacarbonyl (Co2(CO)s) and nickel tetracarbonyl (Ni(CO)4). Alternatively, CO can be incorporated in the metal catalyst in a pre-treatment step, in which the metal precursor is contacted with a CO-releasing molecule, of which multiple examples have been mentioned above, at high temperature before reaction, in the ionic liquid, in another solvent or in the absence of a solvent. This pre-treatment step can be performed under an inert or an H2 atmosphere and with or without acid. One non-limiting example of a pre-treatment method is heating RuBra to 210°C for 1 h in the presence of formaldehyde, Bu4PBr and 40 bar H2. Alternatively, CO can also be released in the reaction conditions from the oxygenated compound substrate or from reaction intermediates formed from the oxygenated compound.

[0074] Preferred Ru-containing precursors are compounds in which Ru is in the Ru(ll) or Ru(lll) oxidation state; non-limiting examples are RuBra, RuCh, tricarbonyl-dichlororuthenium(ll) dimer ([RuCh(CO)3]2), tricarbonyldibromoruthenium(ll) dimer ([RuBr2(CO)3]2, carbonylchlorohydridotris(triphenylphosphine)ruthenium(ll) and Ru(ll) and Ru(lll) complexes containing ligands such as carbonyl (CO), bromide, chloride, iodide, fluoride, water, carboxylates (e.g., formate, acetates), p-diketonates (e.g., acetylacetonate), phosphines (e.g., triphenylphosphine, tricyclohexylphosphine, BINAP), carbenes (e.g., / V-heterocyclic), aromatics (e.g., benzene, toluene, mesitylene, para-cymene), cyclopentadienyls, cyclooctadiene, alkoxides, alkenes, alkynes, amines, polyamines, heteroaromatics, bipyridines, terpyridines, hybrid phosphine amines, pincer ligands (e.g., PCP-type, PNP-type), porphyrins, or sulfonamides. These compounds can be used in anhydric form or as hydrates containing one or more equivalents of water per Ru atom. Other examples of Ru precursors are compounds synthesized from the aforementioned compounds. The catalyst can also be a mixture of different Ru compounds.

[0075] Examples of suitable Ru-containing precursors corresponding to suitable one or more coordination metal complexes can be RuBra, RuCb, [RuBr2(CO)a]2, [RuCh(CO)3]2. i-1 ,2-diol into acetone

[0076] The presence in the catalytic system provided at step (c) of one or more ionic liquids and one or more aqueous acidic compounds is of paramount importance in the process since the one or more ionic liquids are among others dehydrating agents. Subsequently, the generated propane-1 , 2-diol is then dehydrated into acetone thanks to the one or more ionic liquids and the one or more acidic co-catalyst.

[0077] End of the : reduction of acetone into 2- and formation of

[0078] Under the reductive reaction conditions due to the presence of the second stream comprising hydrogen and the one or more coordination metal complexes, acetone is reduced into 2- propanol which is further dehydrated thanks to the one or more ionic liquids and to the one or more aqueous acidic compounds into propylene, which is easily removed from the reaction mixture, thus displacing the equilibrium of the reaction towards its formation. A minimum amount of propylene can be further reduced into propane due to the reductive reaction conditions. However, the overreduction of propylene to propane is a side-reaction, that is successfully limited thanks to the presence of a small amount of CO, either through in situ decarbonylation of the substrate, or by a formaldehyde additive, or else via the addition of small partial pressures of CO gas.

[0079] Further features of the process of the disclosure

[0080] The process of the present disclosure is advantageous because it allows the use of one or more glycerides as starting materials for producing propylene and one or more free fatty acids. For example, the one or more glycerides are selected from one or more monoglycerides, one or more diglycerides, one or more triglycerides or a mixture thereof. More preferably, the one or more glycerides are one or more triglycerides.

[0081] The one or more glycerides can be pre-treated to make the process functioning. This step of pre-treating the first stream is dependent of the capacity of the process of the present disclosure to manage the presence of any potential impurities in the first stream comprising one or more glycerides. Advantageously, the step of pre-treating can comprise the step of bleaching the first stream provided at step (a), with an optionally step of degumming performed before said step of bleaching.

[0082] For example, the step of bleaching is a well-known technique usually performed to decolour and purify chemically or physically refined oil, such as rapeseed oil. It usually ensures the removal of soaps, residual phosphatides, trace metals, and some oxidation products, and it catalyses the removal of carotene and the adsorbent also catalyses the decomposition of peroxides. Another function is the removal of the peroxides and secondary oxidation products. The step of bleaching consists in contacting the refined oil with an absorbent, such as adsorptive clays, synthetic amorphous silica and activated carbons. The key parameters for the bleaching process are procedure, adsorbent type and dosage, temperature, time, moisture and filtration, as shown in the Lipid Handbook (The lipid handbook, edited by Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra. 3rd ed., chapter 3.7).

[0083] For example, the optional step of degumming is carried out for removing the phosphatides present in refined oil, such as rapeseed oil. Four major well-known degumming processes are most commonly used, such as the water degumming process (which consists in mixing oil with water), acid degumming process (which consists in mixing oil with acidic water), dry degumming process (which consists in treating the oil with a strong acid), or enzymatic degumming process (which consists in the enzymatic hydrolysis of phosphatide into lysophospholipids and fatty acid). The lipid handbook (The lipid handbook, edited by Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra. 3rd ed.) describes many variants and details of the degumming processes.

[0084] In addition, the process of the present disclosure works with any kind of glycerides, more particularly with any kind of triglycerides. For example, each aliphatic chain of the one or more triglycerides can be identical. In other examples, the aliphatic chains can be different or two aliphatic chains can be identical and the third one is different. The aliphatic chain can have a number of carbons ranging between 2 and 39. With preference, the number of carbons is comprised between 7 and 24, or between 7 and 23 or between 7 and 20, or between 10 and 20, or between 10 and 17. When 7 carbons are present in the aliphatic chains, and when the three aliphatic chains are identical, the triglyceride is tricaprylin. When 17 carbons are present in the aliphatic chains and when the three aliphatic chains are identical, the triglyceride is originating from rapeseed oil. Such rapeseed oil and / or tricaprylin can be for example pretreated, with preferably a step of degumming carried out before a step of bleaching.

[0085] The first stream comprising the one or more glycerides provided at step (a) can further comprise one or more solvents, or if the one or more ionic liquid necessary to the several dehydration steps functions as one or more solvents, the first stream can further comprise one or more co-solvents. The one or more co-solvents can be miscible or immiscible with the one or more ionic liquids. Advantageously, the one or more solvents and / or the one or more cosolvents are immiscible with the one or more ionic liquids. With preference, said one or more solvents or said one or more co-solvents are selected from one or more aliphatic compounds and / or one or more aromatic compounds, more preferably from one or more aliphatic compounds. For example, said one or more aliphatic compounds are selected from dodecane, naphtha, jet fuel, diesel, or a mixture thereof.

[0086] The fact that the one or more triglycerides have a density which is lower than the density of the glycerol, for example at 20°C, the density of glycerol is about 1.26 g / ml while the density of the one or more triglycerides is ranging between about 0.90 g / ml and about 1.16 g / ml, and / or the fact that the one or more triglycerides have a viscosity which is lower than the viscosity of the glycerol, for example at 70°C, the viscosity of glycerol is about 50 mPa.s while the viscosity of the one or more triglycerides is ranging between about 5 mPa.s and 20 mPa.s, facilitate the implementation of the process of the present disclosure in a large reactor.

[0087] The effluent which is formed at step (d) comprises in addition to the propylene and the one or more fatty acids, at least one or more ionic liquids. The process can advantageously further comprise the step (f) of separating the one or more fatty acids from the one or more ionic liquids so as to recover at least a stream of one or more fatty acids and at least a stream of one or more ionic liquids.

[0088] With preference, the stream of one or more fatty acids is submitted to a hydrodeoxygenation (HDO) reaction followed by an optional hydroisomerization (HI) reaction, to form one or more sustainable hydrocarbons fuels ( / .e., one or more biofuels), more preferably to both a hydrodeoxygenation (HDO) reaction and a hydroisomerization (HI) reaction.

[0089] Examples of one or more sustainable hydrocarbons fuels are naphtha, diesel fuel and kerosene. For example, the hydrodeoxygenation (HDO) reaction is carried out under hydrodeoxygenation conditions, which comprises hydrogenolysis conditions and hydrogenation conditions.

[0090] Hydrodeoxygenation of fats & oils has been reported in 1989 (W.H. Craig and D.W. Soveran, “Production of hydrocarbons with relatively high cetane rating”, US 4992605 and Gusmao J, Brodzki D, Djega-Mariadassou G, Frety R., “Utilization of vegetable oils as an alternative source for diesel-type fuel: Hydrocracking on reduced Ni / SiO2 and sulphided Ni-Mo / y-AhOa”, Cat. Today 1989 (5) 533) in which conventional CoMo or NiMo sulphided catalysts are used. These catalysts are well-known in hydrodesulphurization and are known to catalyze also hydrodeoxygenation (E. Furimsky, Applied Catalysis A, General, 199, pages 147-190, 2000).

[0091] Hydrodeoxygenation of fats & oils is preferentially done in continuous fixed bed reactors, continuous stirred tank reactors or slurry type reactors containing a solid catalyst that can be selected among Ni, Mo, W, Co or mixtures like NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphides as catalytic phase, preferably supported on carbon, alumina, silica, titania, zirconia or mixture thereof.

[0092] It is preferred that the support for the catalytic active phase exhibit a high surface area. In one embodiment, the surface area should be at least 5 m2per gram, preferentially at least 50 m2per gram and most preferably at least 75 m2per gram, such specific surface area can be measured with methods known by the art like the BET method where the adsorption of nitrogen allows to estimate the specific surface area of the solid material.

[0093] It is preferred that the support for the catalytic active phase exhibits low acidity, preferably neutral or basic to avoid hydro-isomerisation reactions that would result in branched paraffin’s and cracking at elevated temperature and pressure in the presence of dihydrogen.

[0094] The hydrodeoxygenation of the free fatty acids can be carried out at a temperature from 200°C to 500°C, preferably from 250 to 400°C, under a pressure from 1 MPa to 10 MPa, preferably from 3 MPa to 9 MPa, more preferably between 5 MPa to 9 MPa, for example of 6 MPa, and with a dihydrogen to refined oils ratio from 100 to 2000 Nl / I, preferably from 250 to 1200 Nl / I for example of 600 NI H2 / I oil.

[0095] For optimum performance and stable continuous operation, it is preferred that the active metal component of the catalyst in the case of Ni, Mo, W, Co or mixtures, is in the form of sulphides. Thereto, it is preferred that trace amounts of decomposable (thermal or catalytically) sulphur compounds are present or added on purpose to the feedstock to keep the metal sulphide in its sulphide state. By way of example, these sulphur compounds can be H2S, COS, CS2, mercaptans (e.g., methylsulfide), thio-ethers (e.g. dimethylsulfide), disulfides (e.g. dimethyldisulfide), thiophenic and tetrahydrothiophenic compounds.

[0096] Under hydrodeoxygenation conditions, several reactions occur. The easiest is the hydrogenation of the double bonds in the alkyl-chain. The more difficult reaction is the removal of oxygen atoms from the C-0 bonds. Both the carboxyl-group of the fatty acid and the hydroxyl-group of the glycerol-moiety are hydrodeoxygenated. This results in the production of linear paraffin, resulting from the acyl-moiety. Depending on the conditions (catalyst, temperature, dihydrogen etc), the carboxyl-group can also be decomposed into CO / CO2 (decarboxylation or decarbonylation) and which in their turn can be even further hydrogenated into methane. These hydrodeoxygenation reactions consume a lot of dihydrogen.

[0097] As a way of example is given the equation for triolein hydrodeoxygenation:

[0098] [Ci8H33O]3C3H5O3 + 15 H23 CI8H38+ C3H8+ 6 H2O

[0099] Hydrodeoxygenation of fatty acids:

[0100] R-CH2-CH2-COOH + 3 H2R-CH2-CH2-CH3+ 2 H2O

[0101] The n-paraffins formed during hydrodeoxygenation reaction of fatty acids can thus be contacted with an isomerization catalyst in the presence of dihydrogen at isomerization conditions to isomerize the normal paraffins to branched paraffins. The isomerization of n- paraffins into / so-paraffins allows for a decrease in the cloud point of the paraffins. The cloud point refers to the temperature below which paraffin wax in diesels or biowax in biodiesel forms a cloudy appearance. The presence of solidified waxes thickens the oil and clogs fuels filters and are to be avoided when possible. The / so-paraffins have indeed improved cold flow properties when compared to n-paraffins. An isomerization catalyst can be advantageously used, for example, amorphous carriers that are moderately acidic. For example, suitable support materials include amorphous alumina, amorphous silica-alumina, amorphous silicaborate, amorphous silica-alumina-titania, one or more zeolites.

[0102] With preference, said one or more zeolites are selected from the group of ATO, AEL, FAU, AFO, BEA, FER, TON, MFI, MTW, MTT, MRE, MWW, EUO, MFS, MOR families, or any mixture thereof.

[0103] For example, the one or more zeolites are or comprise ALPO-31 and / or SAPO-31 from the ATO family. For example, the one or more zeolites are or comprise SAPO-11 from the AEL family.

[0104] For example, the one or more zeolites are or comprise SAPO-37 and / or ZSM-3 from the FAU family. For example, the one or more zeolites are or comprise SAPO-41 from the AFO family. For example, the one or more zeolites are or comprise one or more of Fll-9, Nll-23, ZSM-35 or any mixtures thereof from the FER family.

[0105] For example, the one or more zeolites are or comprise one or more of Nll-10, ZSM- 22, theta-1 , I SI-1 , KZ-2 or any mixtures thereof from the TON family.

[0106] For example, the one or more zeolites are or comprise ZSM-12 from the MTW family. For example, the one or more zeolites are or comprise one or more of ZSM-23, EU- 13, ISI-4, KZ-1 or any mixture thereof from the MTT family.

[0107] For example, the one or more zeolites are or comprise ZSM-48 from the MRE family. For example, the one or more zeolites are or comprise ZSM-50 and / or Ell-1 from the EUO family.

[0108] For example, the one or more zeolites are or comprise ZSM-57 from the MFS family.

[0109] For example, the one or more zeolites are or comprise MgAPSO-31 , MeAPO-11 , MeAPO-31 , MeAPO-41 , MeAPSO-11 , MeAPSO-31 , MeAPSO-41 , MeAPSO-46, ELAPO-11 , ELAPO-31 , ELAPO-41 , ELAPSO-11 , ELAPSO-31 , ELAPSO-41 , or any mixture thereof.

[0110] Isomerization catalyst can in addition contain an active metal component such as Ni, Mo, W, Co or mixture thereof, in the form of sulphides; in that case, trace amounts of decomposable sulfur compounds are either present or added on purpose to the feedstock to keep the metal sulfide in its sulfided state. Other type of active metal component can also be noble metals such as Pt and / or Pd.

[0111] The isomerization conditions include for example a temperature ranging between 150°C and 500°C, more preferably ranging between 220°C and 450°C, even more preferably between 250°C and 420°C and / or a pressure ranging between 1 MPa and 15 MPa, preferably ranging between 1.5 MPa and 9 MPa, more preferably ranging between 2 MPa and 6 MPa. The hourly space velocity can range between 0.1 h-1and 20 h’1, preferably between 0.2 h-1and 10 h’1, more preferably between 0.3 h-1and 4 h’1, even more preferably between 0.4 h-1and 1 h’1. Dihydrogen-containing gases are for example introduced simultaneously with the feedstock at a ratio of 75 to 2500 NI (H2) / l (liquid feedstock), more preferably of 150 to 1500, most preferably of 250 to 1000, or even most preferably of 280 to 500.

[0112] As hydroisomerization (HI) reaction is in competition with hydrocracking reaction, means to control the degree of hydroisomerisation versus hydrocracking are (i) the proper selection of the catalyst ( / .e., amorphous carriers that are moderately acidic, having the right metal to acidic balance) (ii) controlling the temperature of the catalyst ( / .e., not too high), (iii) controlling the hourly space velocity, for example between 0.4 h-1and 1 h’1, and (iv) controlling the dihydrogen to liquid feedstock ratio, for example between 280 NI (H2) / l and 500 NI (H2) / l (liquid feedstock). Other indirect means to control the relative ratio of hydrocracking and hydroisomerisation by influencing the above-mentioned parameters is by optimizing the quenching of the reactor content. Often quenching is applied to control the temperature rise during exothermic hydrocracking. By quenching more with either additional cold dihydrogen and by cold fresh feedstock or cold recycle stream a lower average catalyst bed temperature can be controlled, thus favouring hydroisomerisation.

[0113] Upon fractionation, it is possible to recover one or more sustainable hydrocarbon fuels, such as one or more of naphtha, diesel fuel, and kerosene. The fractionation can also be useful for recovering hydrogen and any unreacted n-paraffins formed during hydrodeoxygenation reaction, so that these compounds can be reused. For example, the fractionation can be carried out using a distillation column or a side-stream distillation column.

[0114] The naphtha fraction has for example an initial boiling point of 30°C and a final boiling point ranging between 80°C and 180°C, the initial and final boiling point being determined in accordance with ASTM D86-12. The naphtha can be used as fuel for light motorized equipment, such as lighters, camping stoves, oil lanterns.

[0115] The diesel fuel fraction has for example an initial boiling point ranging between 80°C and 180°C and a final boiling point being below or equal to 360°C, the initial and final boiling point being determined in accordance with ASTM D86-12. The diesel fuel can be used as a motor fuel for diesel engine.

[0116] The kerosene fraction has for example an initial boiling point ranging between 120°C and 185°C and a final boiling point below 300°C, the initial and final boiling point being determined in accordance with ASTM D86-12. The kerosene can be used as an aviation fuel.

[0117] With preference, the stream of one or more ionic liquids is recycled. More preferably, the stream of one or more ionic liquids is recycled within the catalytic system provided in step (d).

[0118] Advantageously, the reaction conditions of step (d) comprise a temperature of at least 150°C, preferably of at least 180°C. For example, the reaction conditions of step (d) comprise a temperature ranging between 150°C and 250°C, or between 180°C and 240°C, or between 200°C and 220°C.

[0119] Advantageously, the reaction conditions of step (d) comprise a reaction time ranging between 10 minutes and 1 hour, or between 15 minutes and 45 minutes. Advantageously, the reaction conditions of step (d) comprise a residence time ranging from 1 minute to 1 hour, preferably from 10 minutes to 30 minutes, more preferably from 15 minutes to 20 minutes.

[0120] In a batch-wise operation the residence time is the time that the reaction can occur before the reaction is stopped.

[0121] In case of continuous operation, the residence time is the average time that the mixture of the first stream and the catalyst remains in the stirred-tank reactor (calculated by dividing the effective reactor volume (Vr in litres) by the volumetric flow rate (Fm in litres per minutes) of the mixture, Vr / Fm in minutes). Persons skilled in the art are able to estimate the appropriate amount of catalyst needed in the reactor to accomplish the desired residence time

[0122] For example, said process is performed in a continuous mode.

[0123] Overall, the conversion of the one or more glycerides has been determined by gas chromatography analysis as being of at least 80%, preferably at least 85%, more preferably at least 90%.

[0124] The efficiency of the glyceride hydrolysis step has been determined by gas chromatography analysis as being of at least 40 mol.% based on the total molar content of the one or more converted glycerides, preferably at least 45 mol.%, more preferably at least 50 mol.%, even more preferably at least 55 mol.%, most preferably at least 60 mol.%, even most preferably at least 65 mol.% or at least 70 mol.%. For example, the efficiency of the glyceride hydrolysis step is comprised between 40 mol.% and 80 mol.% based on the total molar content of the one or more converted glycerides, preferably between 45 mol.% and 75 mol.%, or between 50 mol.% and 75 mol.%.

[0125] The formation of the gaseous compounds, which are propylene and propane, is high, since from the one or more converted glycerides, between 90 mol.% and 100 mol.% of gaseous compounds are formed, preferably between 92 mol.% and 99 mol.%, or between 93 mol.% and 99 mol.%.

[0126] Among the gaseous compounds which are propylene and propane, the selectivity into propylene is high since it is comprised between 75% and 99%, preferably between 80 and 95%, or between 80% and 90%. Test and determination methods

[0127] Gas chromatography (GC)

[0128] After the reaction, a spontaneous phase separation occurs between the ionic liquid and the dodecane layer. A liquid aliquot of the dodecane layer was taken for GC analysis, performed on a Shimadzu GC-2013 instrument equipped with a DB-FFAP column as this allows for the separation of propene and propane and quantification of even highly volatile compounds. GC analysis of the silylated polar intermediates was performed on a Shimadzu GC-2010 instrument equipped with a CP SIL-5 CB column.

[0129] The conversion of triglycerides was determined by Proton Nuclear Magnetic resonance (1H NMR). Initially, mesitylene was added as an external standard, by comparison of its characteristic singlet CH3 peak at 6.7ppm to the CH3 of the free fatty acid (FFA, triplet at 0.82 ppm). Later, an optimized NMR analysis was used resulting in a more accurate representation of the yield of free fatty acid (FFA) by relative comparison of the CH3 peak of the FFA chains (triplet, 0.82 ppm) with the CH3 peak of the tetrabutylphosphonium ionic liquid (IL) (triplet, 0.92 ppm) which is present in the catalytic system as an internal standard. Here, since each phosphonium molecule has four side chains, the relative integration is four to one free fatty acid. Simultaneously, it is possible to do a similar comparison between the four CH2 peak of the IL, closest to the phosphonium cation around 2.40 ppm, and the CH2 of the FFA closest to the carboxylic acid (2.28 ppm) giving an accurate representation of the overall triglyceride conversion.

[0130] At high conversions and propene selectivities, the amount of propane is very low compared to propene. Therefore, to maintain high accuracy on the exact propene / propane selectivity, in addition to quantitative GC analysis, we performed an independent analysis to determine the propene vs propane selectivity. Fourier Transformed Infrared (FT-IR) spectroscopy was performed on the gas in the headspace of the reactor, injecting a gas sample into a N2 flow on a Gasmet DX 4000 FT-IR gas analyzer. Spectra were processed using Calcmet standard software (v. 12.161), and corresponded well with the liquid phase composition. The use of FT- IR relies on a difference in vibrations of the =C-H alkene stretch (above 3000 cm-1) compared to the -C-H alkane stretch (2800-3000 cm-1). The Calcmet software allows for the accurate calculation of the propene vs propene+propane ratio, thus indicating the selectivity of the system even at very low concentrations (below 1% of the formed C3-compounds is present in the gaseous phase). Examples

[0131] The embodiments of the present disclosure will be better understood by looking at the different examples below.

[0132] First, the active catalyst is formed in situ during a pretreatment step using a CO source. Standard experiments start from RuCh.x W (10 pmol, 4.0 mg), HCI (x mol%), BU4PCI (1.7 mmol, 577 mg) and CO gas (4barg). All components are loaded in a glass liner inside a stainless-steel pressure reactor and stirred for 30 minutes under 4 MPa F^ at 180°C. After pretreatment, the reactor is cooled on ice and the remaining H2 / CO is released into the waste exhaust. Secondly, the actual catalytic hydrodeoxygenation of triglycerides is performed. Triglyceride (0.5 mmol), dodecane (1 mL, as an extracting apolar layer) and tetradecane (0.5 mmol, 0.13 mL, internal standard in dodecane layer) were additionally loaded into the reactor containing the pretreated catalyst. The reaction is performed typically for 15-30 min under 4 MPa H2 at 210-220°C, after which the reactor is again cooled, and a gaseous sample (for FT- IR gas phase analysis) is taken via a syringe. The yield of the apolar compounds is determined via GC analysis of the dodecane layer. Finally, an additional derivatization step is performed using / V,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) (1 mL), silylating the remaining unconverted polar intermediates in the polar IL layer for GC analysis.

[0133] In the following examples, water, indispensable to initialize the hydrolysis of the one or more triglycerides, is not added as such, but it is added along with the acid compound, which is HCI. The commercially available HCI is an aqueous solution of 37 wt.% of HCI based on the total weight of the aqueous solution and comprises thus 63 wt.% of H2O.

[0134] Example 1 : tricaprylin as triglyceride

[0135] The catalytic system comprises 10 pmol of RuCh and gaseous CO is provided at a pressure of 0.4 MPa. The first stream comprises 0.5 mmol of tricaprylin (CAS number 538-23-8). BU4PCI (1 .5 mmol) is used as an ionic liquid. 1 ml of dodecane is added as a co-solvent. The pressure of H2 has been set to 4 MPa. The amount of HCI will be varied as indicated in table 1 and is based on the total molecular weight of the tricaprylin used as starting material.

[0136] Table 1: Conversion of tricaprylin into propylene aConversion of triglyceride as determined by1H NMR using mesitylene as external standardbFraction of tri-substituted glycerol recoveredcFraction of di-substituted glycerol recovereddFraction of mono-substituted glycerol recovered

[0137] Table 1 - sequel: Conversion of tricaprylin into propylene eFraction of deacylated compounds formed, such as glycerol, propane-1 , 2-diol, propane-1 , 3- diol, propylene and propanefPart of the fully deacylated backbones that is recovered as glycerol and intermediate products ( / .e., propane-1 , 2-diol and propane-1 , 3-diol)gSelectivity into propene over propane in the gas phase

[0138] The sum of Tri-R, Di-R, Mono-R and fully deacylated should theoretically be amount to 100%.

[0139] The result of table 1 indicates that tricaprylin is converted at a minimum conversion of 84% (entry 4). The analysis of the gas phase which is a mixture of propylene and propane has allowed observing a selectivity of 83% to propylene.

[0140] Entry 1 is the experiment where the best conversion of tricaprylin has been observed, namely 95%, which means that only 5% of the tricaprylin remains unhydrolyzed, as indicated by the fraction (5 mol.%) of tri-substitued glycerol recovered. Partial hydrolysis has been also demonstrated, as 11 mol.% of di-subsituted glycerol and 16 mol.% of mono-subsituted glycerol have been observed, based on the total molar content of the converted tricaprylin.

[0141] Only 4 mol.% of the fully deacylated backbones is recovered as glycerol and intermediate products ( / .e., propane-1 , 2-diol and propane-1 , 3-diol). This means that 96 mol.% of the fully deacylated backbones is converted into gaseous C3 compounds, such as propylene (84%) and propane (16%). Example 2: Conversion of rapeseed oil as triglyceride

[0142] The raw rapeseed oil has been subjected to a first acid degumming step consisting in heating the raw rapeseed oil in presence of citric acid in a centrifugal mixer. The oil was then separated by centrifugation from the gums, impurities and aqueous phase. It was then subjected to a water-degumming step followed by a bleaching step using clay adsorbent, leading to a refined rapeseed oil. Thanks to this pre-treatment, the refined rapeseed oil contains very low amount of impurities as described in the table 2 below:

[0143] Table 2: Content of impurities in refined rapeseed oil

[0144] * as determined by procedure A of normalized UOP-398 method The catalytic system comprises 10 pmol of RuCh and gaseous CO is provided at a pressure of 0.4 MPa. The first stream comprises 0.25 mmol of rapeseed oil. BU4PCI (0.75 mmol) is used as an ionic liquid. 1ml of dodecane is added as a co-solvent. The pressure of H2 has been set to 4 MPa. 0.025 mmol of HCI has been added.

[0145] Table 3: Conversion of refined rapeseed oil into propylene aConversion of triglyceride as determined by1H NMR using mesitylene as external standardbConversion of triglyceride as determined by1H NMR using tetrabutylphosphonium chloride as internal standardcFraction of deacylated compounds formed, such as glycerol, propane-1 , 2-diol, propane-1 , 3- diol, propylene and propanedPart of the fully deacylated backbones that is recovered as glycerol and intermediate products ( / .e., propane-1 , 2-diol and propane-1 , 3-diol)eSelectivity into propene over propane in the gas phase as determined by FT-IR

[0146] Entry 1 indicates that the complete hydrolysis of converted rapeseed oil into glycerol has occurred at 72 mol.% based on the total molar content of the starting material rapeseed oil. Only 2 mol.% of the fully deacylated backbone is recovered as glycerol and intermediate products ( / .e., propane-1 , 2-diol and propane-1 , 3-diol). This means that 98 mol.% of the fully deacylated backbone is in fact converted into gaseous C3 compounds, such as propylene (83%) and propane (17%) as given by the last column of table 3.

[0147] Example 3: Conversion of unrefined or partially refined oils

[0148] The unrefined rapeseed oil and the used cooking oil have not been subjected to any pretreatments.

[0149] The unrefined rapeseed oil contains the following impurities (table 4):

[0150] Table 4: Content of impurities in unrefined rapeseed oil as determined by XRF elemental analysis

[0151] The used cooking oil contains the following impurities (table 5):

[0152] Table 5: Content of impurities in used cooking oil as determined by XRF elemental analysis

[0153] The experiments are performed in a 50mL batch reactor.

[0154] The catalytic system comprises 10.2g of Bu4PBr (6 eq to oil) as ionic liquid, 0.054mL H2SO4 (50%vol) and 54mg of RuCh. A gaseous CO stream at a pressure of 1 MPa is used to pre- treat the catalyst.

[0155] 5.0 mL of not refined or semi-refined oil is then introduced into the batch reactor.

[0156] The operating conditions used are : 4 MPa H2, 220°C. The duration of the reaction is 1hour.

[0157] Table 6: Conversion of different non purified oils aConversion of triglyceride as determined by1H-NMR using tetrabutylphosphonium chloride as internal standardbFraction of Free Fatty Acids recovered after BSTFA derivatization (GC analysis)cPart of the fully deacylated backbones that is recovered as glycerol and intermediate products ( / .e., propane-1 ,2-diol and propane-1 ,3-diol) after BSTFA derivatization (GC analysis)eSelectivity into propene over propane in the gas phase as determined by FT-IR

[0158] The results demonstrate the robustness of the catalytic system towards impurities present in the feed (such as P, Si, alkalines) : indeed even if the oil has not been subjected to any pre- 1 treatments (degumming and / or bleaching for example), a high triglyceride conversion of the triglycerides is achieved.

[0159] Example 4: Conversion of unrefined rapeseed oil at higher temperature

[0160] The experiments are performed in a 50mL batch reactor.

[0161] The catalytic system comprises 5.1g of Bu4PBr (6 eq to oil) as ionic liquid, 0.027mL H2SO4 (50%vol).

[0162] For the example 4.1 , the catalytic system further comprises 27mg of RuCh. A gaseous CO stream at a pressure of 10bar is then used to pre-treat the catalyst.

[0163] For the example 4.2, commercial [RuCh(CO)3]2 (25.6 mg) was used instead of RuCh.

[0164] For the example 4.3, the catalytic system also comprises 27mg of RuCh. Aqueous formaldehyde (38 wt.% H2CO in water, 25eq. to Ru) is used to pretreat the catalyst instead of a gaseous CO stream.

[0165] 2.5mL of unrefined rapeseed oil is then introduced into the batch reactor.

[0166] The operating conditions used are: 1 MPa H2, 250°C. The duration of the reaction is 1hour.

[0167] Table 7 Conversion of different non purified oils aConversion of triglyceride as determined by1H-NMR using tetrabutylphosphonium chloride as internal standardbFraction of Free Fatty Acids recovered after BSTFA derivatization (GC analysis)cPart of the fully deacylated backbones that is recovered as glycerol and intermediate products ( / .e., propane-1 ,2-diol and propane-1 ,3-diol)eSelectivity into propene over propane in the gas phase as determined by FT-IR

[0168] These results show that optimizing the operating conditions high propene selectivity and near complete triglyceride conversion is obtained after 1h and 250°C, even if the raw rapeseed oil has not been pre-treated. It also confirms once more the robustness of the catalytic system towards impurities present in the unrefined rapeseed oil.

Claims

CLAIMS1 . Process to convert one or more glycerides into propylene and one or more fatty acids, said process is characterized in that it comprises the following steps: a) providing a first stream comprising one or more glycerides; b) providing a second stream comprising hydrogen; c) providing a catalytic system; d) contacting the first stream and the second stream with the catalytic system provided at step (c) under reaction conditions to form an effluent comprising at least propylene and one or more fatty acids; e) recovering the propylene from said effluent; wherein the catalytic system provided at step (c) comprises- one or more coordination metal complexes,- one or more aqueous acidic compounds,- one or more ionic liquids, and- carbon monoxide and / or one or more CO-releasing compounds.

2. The process according to claim 1 is characterized in that the one or more coordination metal complexes comprise one or more metallic ions in an amount ranging between 0.1 mol.% and 10.0 mol.% based on the total molar content of the one or more glycerides comprised in the first stream.

3. The process according to claim 1 or 2, characterized in that the one or more coordination metal complexes comprise one or more transition metals selected from Ru, Rh, Ir, Co, Ni, Fe, Ag, Au, Pt, Cu or a mixture thereof.

4. The process according to claim 3, characterized in that one or more transition metals selected from Ru and / or Fe.

5. The process according to any one of claims 1 to 4 is characterized in that the catalytic system provided at step (c) is made in situ by contacting one or more metal-containing precursors with one or more complexing agents comprising a carbonyl moiety, one or more aqueous acidic compounds and one or more ionic liquids.

6. The process according to any one of claims 1 to 5 is characterized in that the one or more CO-releasing compounds are selected from one or more aldehydes, one or more carboxylic acids, one or more metal carbonyls, or a mixture thereof.

7. The process according to claim 6, characterized in that the one or more metal carbonyls are one or more CO-releasing compounds and comprise the one or more coordination metal complexes.

8. The process according to any one of claims 1 to 7 is characterized in that the one or more coordination metal complexes are selected from RuCh(CO3)2, RuBr2(CO3)2, RuCh, RuBrs, or a mixture thereof.

9. The process according to any one of claims 1 to 8 is characterized in that the one or more ionic liquids are present in an amount ranging between 10 mol.% and 500 mol.% based on the total molar content of the one or more glycerides comprised in the first stream10. The process according to any one of claims 1 to 9, characterized in that the one or more ionic liquids are selected from one or more phosphonium-based ionic liquids, one or more ammonium-based ionic liquids, one or more sulfonium-based ionic liquids or a mixture thereof.11 . The process according to claim 10, characterized in that the one or more ionic liquids are selected from one or more phosphonium-based ionic liquids.

12. The process according to any one of claims 1 to 11 is characterized in that the one or more aqueous acidic compounds are one or more acidic compounds dissolved in water; wherein the one or more acidic compounds are present in an amount ranging between 2.5 mol.% and 15 mol.% based on the total molar content of the one or more glycerides comprised in the first stream.

13. The process according to any one of claims 1 to 12, characterized in that the one or more acid compounds are selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, phosphoric acid, pyrophosphoric acid, sulfuric acid, nitric acid, or a mixture thereof.

14. The process according to claim 13, characterized in that one acid compound is hydrochloric acid.

15. The process according to any one of claims 1 to 14 is characterized in that said first stream further comprises one or more solvents.

16. The process according to claim 15, characterized in that said one or more solvents are selected from one or more aliphatic compounds.

17. The process according to any one of claims 1 to 16 is characterized in that said one or more glycerides are selected from one or more monoglycerides, one or more diglycerides, one or more triglycerides, or a mixture thereof.

18. The process according to claim 17, characterized in that said one or more glycerides are one or more triglycerides.

19. The process according to any one of claims 1 to 18 is characterized in that the process further comprises the step of pre-treating the first stream before step (d).

20. The process according to claim 19, characterized in that the step of pre-treating comprises the step of bleaching the first stream provided at step (a), with an optional step of degumming performed before said step of bleaching.21 . The process according to any one of claims 1 to 20 is characterized in that the reaction conditions of step (d) comprise an H2 partial pressure ranging between 2 MPa and 10 MPa.

22. The process according to any one of claims 1 to 21 is characterized in that the reaction conditions of step (d) comprise a temperature of at least 180°C.

23. The process according to any one of claims 1 to 22 is characterized in that the reaction conditions of step (d) comprise a temperature ranging between 200°C and 250°C.

24. The process according to any one of claims 1 to 23 is characterized in that the reaction conditions of step (d) comprise a residence time ranging from 1 minute to 1 hour.

25. The process according to any one of claims 1 to 24 is characterized in that said process is performed in a continuous mode.

26. The process according to any one of claims 1 to 25 is characterized in that said process is carried out in a one-pot configuration.

27. The process according to any one of claims 1 to 26 is characterized in that the effluent formed at step (d) further comprises at least one or more ionic liquids, and in that theprocess further comprises the step (f) of separating the one or more fatty acids from the one or more ionic liquids to recover at least a stream of one or more fatty acids.

28. The process according to claim 27, characterized in that, the stream of one or more fatty acids is submitted to an hydrodeoxygenation reaction followed by an optional hydroisomerization reaction, so as to form one or more sustainable hydrocarbon fuels.

29. Method for making polypropylene, said method being characterized in that it comprises at least one process to convert one or more glycerides into propylene as defined in any one of claims 1 to 28, said process comprising the additional step (g) of using the recovered propylene of step (e) in a polymerization step.

30. Method for making sustainable fuel, said method being characterized in that it comprises at least one process to convert one or more glycerides into propylene as defined in any one of claims 1 to 28, said process comprising the additional step (g) of using the recovered propylene of step (e) in a catalytic oligomerization step.

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