WO2025224331A1 - Nickel phosphorus catalysts for hydroprocessing - Google Patents

Abstract

The invention introduces a transition metal phosphide catalyst, along with its preparation methodology and application thereof, wherein the method comprises of the following steps: a) providing a first precursor phase, comprising an at least partly reduced nickel precursor, b) providing a second precursor phase, comprising an aqueous solution of a source of phosphorus, c) putting into contact the first precursor phase of step a) with the second precursor phase of step b), to obtain a reaction product, d) drying the reaction product of step c) to obtain a dried reaction product, and e) activating the dried reaction product of step d) by exposure to dihydrogen. The method is simple to operate, safe and low in cost, while the resulting catalyst boasts the capacity for simultaneous hydrodeoxygenation of diverse oxygenated feeds originating from renewable biological sources. The catalyst finds its utility for example in the hydrodeoxygenation of phenolic compounds in pyrolysis oil, lignin oil, or bio-oil obtained from lignocellulosic biomass, fatty acids such as methyl esters (FAME), or triglycerides (in plant or animal fat).

Description

NICKEL PHOSPHORUS CATALYSTS FOR HYDROPROCESSING

BACKGROUND OF THE INVENTION

A. Field of the Invention

The present invention concerns nickel phosphorus assembly and their use as catalyst for hydroprocessing, in particular for hydrodeoxygenation of oxygenated feeds. The present invention more particularly concerns a simple and efficient process to manufacture such nickel phosphorus catalyst.

B. Description of the Related Art

Hydrotreatment is a known strategy to remove heteroatoms such as S, N and O from hydrocarbons under the action of hydrogen gas or another hydrogen donor source in presence of a catalyst. A metal-containing catalyst is capable of activating a hydrogen atom, and upon a surface reaction, the reaction formally eliminates H₂S, NH₃ and H₂O leaving a hydrocarbon, essentially free of such heteroatoms. This catalytic hydrotreatment is known for instance for the cleaning of crude oils and refined fractions therFlaneof, preferably but not excluded to prevent the downstream upgrade processes from catalyst deactivation, but essentially for environmental reasons.

With the shift of carbon feedstock form fossil to renewable or green ones, the chemical industry, other than fossil feedstock are transitioning to the use of biomass, plastic waste streams and carbon dioxide, which contains a high content of oxygen atoms in the molecular structure, to prepare hydrocarbons. The feedstock is often referred to as renewable carbon. Partial and complete removal of the oxygen to form partially oxygenated to essentially oxygen-free hydrocarbons are therefore important strategies to form the desired drop-in or novel hydrocarbon products, going from chemicals to fuels, often referred to as renewable products.

Oxygenated renewable feeds are often limited in their direct applications. For instance, removing oxygen can make biological feedstock suitable for a wider range of uses. Such feedstock includes bio-crude oil generated through pyrolysis or hydrothermal liquefaction of lignocellulosic biomass, as well as triglycerides, fatty acid methyl esters, and fatty acids, and furanics among others. This process assumes importance in the pursuit of substituting petroleum-based hydrocarbon fuels. The oxygen content in such oxygenated feeds leads to high viscosity and acidity, and stability and calorific values are low and hence resulting in lower fuel quality. Therefore, there is a need in the art for deoxygenation of the oxygenated hydrocarbon compound from oxygenated feeds for removing oxygen and saturating unsaturated bonds to improve the fuel's quality thus obtained.

In this context, catalytic hydrodeoxygenation (HDO) becomes a very important strategy to upgrade such renewable feedstock to useful products. The most common way to remove the oxygen functional group in various organic materials for instance bio-feeds or bio-feedstocks is hydrodeoxygenation, which involves contacting the oxygenated stream with catalyst(s) in the presence of hydrogen (or hydrogen donors) at elevated temperatures and pressures.

An efficient and effective catalyst is required for this that is capable of selectively removing the heteroatom such as O, preferably under mild conditions with a control on the cracking of carbon-carbon bonds, in order to limit the formation of gaseous hydrocarbons. While typical catalysts for such HDO, for instance currently used industrially for hydrotreatment of fossil feedstock, e.g. hydrodesulfurization, can be used, it is apparent that catalyst synthesis and optimization towards more efficient HDO (instead of HDS or HDN) is required to get the maximum activity and selectivity from such HDO hydrotreatment reaction or process. This is an essential requirement to be able to ultimately propose an industrially feasible HDO catalyst synthesis method and a process using the oxygen-rich renewable feedstock.

Generally, hydrodeoxygenation catalysts comprise a solid support such as alumina, titania, zirconia, zeolites, and activated carbon, and one more active element in the form of metals, oxides, or phosphides and sulfides of transition and noble metals. Examples of catalysts commonly used for the hydrodeoxygenation of oxygenated feeds include traditional hydrodesulfurization catalysts originally developed for the hydrodesulfurization of removing sulfur included in large quantities in petroleum products from petroleum refineries or petrochemical plants. These catalysts contain molybdenum (Mo) or tungsten (W) as the active species, combined with other transition metal compounds such as nickel (Ni) or cobalt (Co). Usually, these catalysts are dispersed on some support to maximize the metals' effectiveness. However, these catalysts suffer from drawbacks such as the tendency to be attacked by water, deactivation, requiring co-feeding of S-containing compounds to maintain the activity of the sulfide catalysts, and low hydrocarbon yield and sulfur pollution to hydrocarbon products and the like.

For example, U.S. Pat. No. 4,992,605 discloses a method for the hydrodeoxygenation of canola oil, sunflower oil, or rapeseed oil using sulfurized cobalt-molybdenum (Co — Mo) as a catalyst producing C15-C17 paraffin useful as diesel fuel. U.S. Pat. No. 5,705,722 described a method for preparing additives for diesel fuels having high cetane numbers by hydrodeoxygenation of relatively inexpensive oil or fat such as tall oil, used cooking oil, animal oil or fat, etc., using sulfurized nickel-molybdenum (Ni — Mo) supported on alumina as the catalyst. Such vegetable oil hydrotreatment processes using sulfide catalysts have already been described in many patents.

However, the sulfurized Co — Mo or sulfurized Ni — Mo catalysts used in these patents need to be activated before the reaction by introducing sulfides, typically DMDS (DiMethylDi Sulfide) generating in situ noxious hydrogen sulfide (H₂S). When the catalysts are used to remove oxygen from oxygen-containing organic compounds, H₂S is often produced from the reaction between the sulfur contained in the catalyst and the reactant hydrogen, or the sulfur is removed as being replaced by the product. As a result, the catalyst is rapidly deactivated, and the yield is decreased.

Therefore, using the sulfurized Co — Mo or sulfurized Ni — Mo catalyst for the hydrodeoxygenation of biomaterials is not desirable. As such, developing high-efficiency hydrodeoxygenation catalysts with industrial application value and prospect and have important economic and strategic significance for upgrading and modifying various types of oxygenated feeds from the biological feedstock.

Noble metal catalysts have high activity but are expensive, prone to trace sulfur poisoning and have poor stability. Non-noble metal catalysts are not acid resistant and also have the problem of poor stability.

Among the several catalysts, literature is clear that metal-based catalysts that contain phosphorous at low oxidation state, such as Ni phosphide, e.g. Ni₂P and others, are one of the most promising for HDO activity and selectivity. With the latter, it is meant a preferable C-0 cleavage, rather than C-C breakage under action of the catalyst. Despite the generally accepted HDO performance in presence of such catalysts, and their promising HDO performance, their synthesis is challenging from an industrial perspective.

Overall, the catalyst synthesis to reach the highest activity and product selectivity faces several issues. For the high activity and selectivity of the catalyst, pretreatment temperatures too high for a feasible commercial synthesis or pretreatment, e.g., well above 550°C, at various stages in its synthesis, are used, while in other cases the synthesis requires highly inert atmospheres (e.g., water- and oxygen-free) and/or the use of toxic and harmful chemicals such as organic solvents, phosphines, highly self-explosive (hypo)phospite salts and easy flammable phosphorous red, etc. are described. Additionally, phosphinelike products may also be generated in situ during the thermal treatment of the catalyst. These are the main reasons why there is currently no commercial metal phosphide catalyst available, or used in a commercial process, despite its promising catalysis, e.g. for HDO on biomass related feedstock and others.

The general state of the art method of catalyst synthesis follows a certain flow: that is, contacting a metal, e.g., dispersed Ni, or a metal ion, e.g. a salt and a phosphorous source in gas or liquid at a certain temperature and certain synthesis conditions, followed by pretreatments such as a calcination (under air or oxygen) and reduction (under a reducing agent atmosphere such as H₂) step at elevated temperatures. The calcination step is sometimes omitted when low oxidation states of Ni and/or P sources are used in the synthesis procedure.

The following section illustrates the evolution of the research within the metal phosphide, with Ni phosphide as main example, as an attempt to overcome the aforementioned challenges. While some examples are illustrated for HDO, most examples in literature are reported for HDS, for which the mechanism of heteroatom removal is different. The examples also illustrate that the synthesis methods still face conditions, that are not transferrable to a practical commercial method of synthesis or activation.

Classic synthesis methods of metal phosphide catalysts, such as Ni phosphide, follow the reduction of a Ni phosphate salt precursor. Generally, the formation of the phosphate precursor happens through a bulk precipitation synthesis. It relies on the formation of Ni salts, that comes from Ni in the non-metallic state, e.g., an oxide, hydroxide or salt, together with high oxidation state phosphorous source such as phosphoric acid or salt, to form basically the Ni phosphate salt (e.g., Ni₃PO₄), followed by a calcination and reduction step at high temperatures, usually well above 550°C, often much higher than 600°C, in order to form the most catalytically active metal phosphide phase that is capable of removing S or O atoms from the renewable feedstock. The phosphate precursor can be impregnated onto a support for better dispersion, prior to be calcined and reduced, but the treatment temperatures for these supported catalysts remain high. This method using Ni in the high oxidation state +2, has been firstly employed by Robinson (W. R. A. M. Robinson, J. N. M. Van Gestel, T. I. Koranyi, S. Eijsbouts, A. M. Van DerKraan, J. A. R. Van Veen and V. H. J. De Beer, J. Catal., 1996, 161, 539-550 ), and then further improved and applied by Oyama (S. T. Oyama, X. Wang, Y. K. Lee, K. Bando and F. G. Requejo, J. Catal., 2002, 210, 207-217) and his research group. For instance, in this synthesis, Ni(NO₃)₂ was employed as Ni source, while (NH₄)₂HPO₄ was the phosphorous source. There are many examples in literature using the method to synthetize the metal phosphide catalyst. These catalysts, synthesized accordingly, were used for hydrotreatment of S containing impurities, it is HDS, but not for HDO, and certainly not for HDO of real biomass derived products such as lignin and triglycerides etc.

Bui et al. (P. Bui, J. A. Cecilia, S. T. Oyama, A. Takagaki, A. Infantes-Molina, H. Zhao, D. Li, E. Rodriguez-Castellon and A. Jimenez Lopez, J. /to/. , 2012. 294, 184-198)³, developed a Ni phosphide catalyst, following the method reported by Oyama, in order to test its activity in the HDO; they used non-biomass derived synthetically pure 2-Methyl-Tetrahydrofuran. They showed that the reduction temperature should be as high as 590°C in order to be able to achieve HDO activity. Pham et al. (L. K. H. Pham, T. T. V. Tran, S. Kongparakul, P. Reubroycharoen, S. Karnjanakom, G. Guan and C. Samart, Fuel Process. Technol., 2019, 185, 117-125)⁴ followed the same procedure to synthetize similar carbon supported Ni phosphide catalyst, and used them for HDO of waste cooking oil, which is a triglyceride based substrate. In this scenario, the calcination and reduction temperature was further increased to 600°C to be able to get good HDO results. In similar work, Ruangudomsakul et al.(M. Ruangudomsakul, N. Osakoo, J. Wittayakun, C. Keawkumay, T. Butburee, S. Youngjan, K. Faungnawakij, Y. Poo- arporn, P. Kidkhunthod and P. Khemthong, Mol. Catal., 2022, 523, 111422)⁵ employed another NiCO₃.Ni(OH)₂ precursor Ni salt and H₃PO₄ as Ni and P source, respectively. The catalyst was employed for HDO of palm oil, but only after being calcined and reduced at 500°C and very high 650°C, respectively. M. de Oliveira Camargo and his research group (M. de Oliveira Camargo, J. L. Castagnari Willimann Pimenta, M. de Oliveira Camargo and P. A. Arroyo, Fuel, 2020, 281, 118719) carried out the synthesis of Ni phosphide catalyst, according to the procedure of Oyama for HDO of oleic acid. In this work, again high calcination temperature, viz. 500°C, and reduction temperature, viz. at least 650°C, was used in the catalyst synthesis to obtain the best catalytic activity. Schi et.al (H. Shi, J. Chen, Y. Yang and S. Tian, Fuel Process. Technol., 2014, 118, 161-170)⁷, reported in a recent manuscript HDO of methyl laurate with Ni phosphide catalyst prepared according to a similar procedure of Oyama et al.. In this case, the catalyst was firstly calcined and 500°C and then reduced at 650°C.

It is an important to pinpoint that the above classic synthesis using Ni salts and phosphate sources, e.g. the lead work of Oyama’ team and following work, can use lower reduction temperature, when the hydrotreatment such as HDS and HDN is the objective. However, it is also important to realize that, when these catalysts are used for HDO, effective catalysis is only noted when the catalyst undergoes treatment under high calcination and certainly very high reduction temperatures, usually above 600°C and higher.

There is also work done by researchers to reduce the treatment temperatures to be able to propose a commercial synthesis route for such promising catalysts. In order to reduce the temperature of the pretreatments, the formation of phosphide precursor has occurred avoiding the prior synthesis of phosphate salts, but instead they use more reduced forms of phosphorous such as red phosphor, phosphor trihydride, hypophosphite and phosphite precursors. Although necessary to lower the preatment temperatures, these chemicals are less preferable for their toxicity or complexity of handling due to safety, e.g., formation of self-explosive salts with (hypo)phosphite etc, or easy-flammable compounds such as phosphorous red. In this context, methods are illustrated in literature, demonstrating the usage of lower oxidation state phosphorous sources such as phosphite and hypophosphite, in combination with alternative Ni²⁺ (hydroxide)oxide sources (e.g., NiO and Ni(0H)₂). For example, in a recent work of D’Aquino et.al (A. I. D’Aquino, S. I. Danforth, T. R. Clinkingbeard, B. Ilic, L. Pullan, M. A. Reynolds, B. D. Murray and M. E. Bussell, J. Catal., 2016, 335, 204-214)⁸, Ni(0H)₂ in combination with H₃PO₂ was adopted to form the hypophosphite catalytic Ni precursor. In this case, the reduction temperature was lowered to a range of 300-500°C. Although the catalyst showed catalytic performance for HDS and HDN, there was no mentioning and proof of its usefulness (after such low reduction temperature) for HDO. It is in the aforementioned work by Bui et.al (P. Bui, J. A. Cecilia, S. T. Oyama, A. Takagaki, A. Infantes-Molina, H. Zhao, D. Li, E. Rodriguez-Castellon and A. limenez Lopez, J. Catal., 2012, 294, 184-198)³, that the formation of phosphite precursor, achieved by mixing the same Ni salts as mentioned above, with H3PO3 as source of phosphorous, was used for HDO catalysis. In this case, the reduction temperature could be lowered only till 560 °C, compared to the original 590°C in case of using the phosphate precursor, but this is considered still too high. Also, the catalyst was employed for HDO of synthetically pure (and reactive) 2-MTHF, but no activity was reported for other, more challenging feedstock or mixtures thereof, such as containing lignin, and lignin-related fractions, or fatty acids, esters such as triglycerides and the like.

Literature agrees that the formation of metal phosphide, such as Ni phosphide, can be better executed differently, that is by using already reduced, thus metallic Ni, instead of oxidized Ni forms such as those in oxidation state +1 or +2, as a salt or as an oxide or hydroxide, or mixture thereof, in order to lower the temperature in the reduction steps, that are realistic and practical to handle in a commercial process. The following examples illustrate this point.

With regard to low reduction temperature to synthesize the active catalyst, the best available method uses metallic Ni, combined with an organic source of phosphorous such as phosphine, phosphine oxide, and red phosphorous, dissolved in an organic solvent (such as explosive ethers), which are all harmful chemicals, to allow the synthesis of an active metal phosphide phase. Such catalysts are reduced at high 700°C temperature such as in the case of usage of Ni(aca)₂ with [CH₃(CH₂)₇]₃P in di-n-octylether solvent in presence of silica for HDO of palm oil, but there are also examples showing lower reduction temperatures, around 400°C to form the catalytic active phase. While in most cases, the catalyst is used for the easier HDS reaction, and not HDO, there are a few examples as well on HDO. For instance, for Ni on alumina with PPh₃ as P source, the catalyst is activated reductively at 400°C, showing activity for HDO of furfural.

However, besides the potential harmfulness of the method, the synthesis method requires severe inert atmosphere during the phosphidation step, that is the atmosphere should be free of noninert, such as water and molecular oxygen, when contacting the phosphorous source to the reduced Ni, to be able to form the active metal phosphide. The inert conditions are very difficult to achieve on the industrial scale. Thus, despite the lower activation temperatures that can be realized for its synthesis, the inert conditions are hard to realize industrially.

Note that while usage of these metallic Ni and phosphorous sources with easier reduction potential result in lower pretreatment temperatures, they use instead high temperature in the phosphidation step itself, typically above 200°C, liberating in the gas phase volatile phosphide compounds. As for example, Cao et.al (Z. Cao, M. Dierks, M. T. Clough, I. B. Daltro de Castro and R. Rinaldi, Joule, 2018, 2, 1118-1133)⁹ reported aNi phosphide catalyst synthesis, through the phosphidation of supported Ni/SiO₂ by means of trioctylphosphine at 300°C, using explosive di-n-octyl ether as solvent. In this case, the catalyst was employed for the HDO of entire lignin - derived oil. Jia et.al (Z. Jia, N. Ji, X. Diao, X. Li, Y. Zhao, X. Lu, Q. Liu, C. Liu, G. Chen, L. Ma, S. Wang, C. Song and C. Li, ACS Catal., 2022, 12, 1338-1356)¹⁰, also reported the synthesis of Ni phosphide catalyst starting from Ni/Al₂O₃ as precursor. The reduction temperature was lowered to 500°C and the catalyst was employed for HDO of synthetically pure non-biomass derived guaiacol, that may be derived from lignin. The source of phosphorous adopted was here easy-flammable red phosphorous. Hou et al. (Q. Hou, J. Cai, L. Zuo, H. Chen, Y. Fu and J. Shen, Appl. Surf. Set., 2023, 619, 156738)¹¹ reported the synthesis of the phosphide catalyst through the phosphidation of Ni/Al₂O₃ with PPh₃ at 170°C using n-heptane as solvent. In this case, the reduction temperature was 400°C and the catalyst was employed for the HDO of furfural. Yang et.al (S. Yang, C. Liang and R. Prins, J. Catal., 2006, 237, 118-130)¹², reported the synthesis of Ni phosphide supported over SiO₂. In this work, a mixture of PH₃ and H₂ at 250°C, was used to execute the phosphidation step, while the catalyst was reduced at 400°C to be employed for HDS and HDN of dibenzotiophene and o-methylaniline respectively. In the US11725292B2 patented process, for example Ni phosphide catalyst is obtained starting from Ni foam and red phosphorous, using very high temperature such as 450°C in the phosphidation step. In this patent, the aim of the catalyst is not HDO, but water splitting.

Phosphidation of reduced Ni has also been attempted in presence of reduced P species, such as (hypo)phosphite, and PH₃. Generally, these catalysts perform worse with regard to hydrotreatment than the one prepared with phosphine in organic solvent media, as mentioned above. Literature shows low reduction temperature requirement, but only for HDS, HDC (hydrodechlorination) or HDN usage. There is no example in literature, however, with such catalysts for the more difficult HDO reaction with renewable oxygenates, that was activated at a reduction temperature below 650°C. For instance, NH4H₂PO₂ was used with reduced Ni on MOR zeolite support for HDO of 2-methyl furan, showing a 650°C reduction temperature requirement.

In addition to high activation temperatures to achieve HDO activity, another parameter that seems to determine the hydrotreatment such as HDO activity is the composition of the metal phosphide phase. For Ni phosphide, and this is valid for all the above examples, it is generally accepted that synthesis is carried out as to form the most active form, being Ni₂P. or other active Ni phosphide phases such as Ni₃P or Nii₂P₅ that are formed within a typically P to Ni ratio range that is above 0.5, preferably 2 or sometimes higher. Lower values are known to form suboptimal catalysts with worse hydrotreatment (e.g., HDO) performances.

Nowadays, according to literature, the easiest, most safe and efficient methods to prepare Ni phosphided catalyst are based on a simple impregnation of a supported Ni source via the utilization of an aqueous phosphorous source.

As example, Lan et.al shows how to prepare Ni phosphide catalyst starting from NiO/SiO₂ as Ni source (X. Lan, E. J. M. Hensen and T. Weber, Catal. Today, 2017, 292, 121-132).¹³ In this work, the phosphidation happens through a simple wetness impregnation of NiO/SiO₂, where both H3PO3 and H₃PO₂ are proposed as P source. In this case, the catalyst is prepared with a P/Ni molar ration of 2 and the catalyst is reduced at 400°C (using H3PO3) or even 350°C (using H₃PO₂). In this manuscript the employed catalyst is not used to perform HDO of biomass related feedstock, but to perform the easier HDS of thiophene.

Therefore, J. Chen and co - workers, have also synthetized Ni phosphide catalyst through wetness impregnation of supported Ni, but in this scenario, they have employed reduced Ni/SiO₂ and NH4H₂PO₂ (I. Chen, Y. Chen, Q. Yang, K. Li and C. C. Yao, Catal. Commun., 2010, 11, 571-575).¹⁴ In this scenario, the P/Ni ratio for the catalyst has been selected to be 2. The outcome of this work shows the selective removal of chlorine, via hydrodechlorination (HDC) of non-renewable chlorobenzene, being performed after the reduction of the catalysts happened at very high 650°C.

Considering the aforementioned, there is still a need to improve catalysts for real renewable feedstock conversion, in particular to HDO catalysts, that are prepared according to industrially feasible, and safe synthesis methods.

There is in particular a need for novel and efficient method for preparing such catalysts, in particular for preparing Ni phosphorus catalysts, preferably dispersed on a support, using cheap and non-toxic chemicals, safe and stable chemicals, and/or not being subjected of the requirement of too high activation temperatures, and/or nor requiring a high temperature during the phosphidation step, and/or nor the use of an inert atmosphere.

Thus, an aim of the invention is to propose an efficient method for preparing metal phosphorus catalysts, in particular Ni phosphorus catalysts, that solves one, several or all of the above- mentioned issues of existing methods listed above. Another aim of the present invention was a hydroprocessing technology for hydrotreating S, N and/or O-containing hydrocarbons and in particular a hydrodeoxygenation technology for oxygenated feeds derived from biological sources to produce renewable gasoline, kerosene, and diesel components in that the hydrocarbon yield is increased as much as possible, while removing essentially all oxygen in the product composition.

SUMMARY OF THE INVENTION

Thus, the present invention concerns a process to manufacture a nickel phosphorus catalyst, the process comprising the steps of: a) providing a first precursor phase, comprising an at least partly reduced nickel precursor, b) providing a second precursor phase, comprising an aqueous solution of a source of phosphorus oxides, c) putting into contact the first precursor phase of step a) with the second precursor phase of step b), to obtain a reaction product, d) drying the reaction product of step c) to obtain a dried reaction product, and e) activating the dried reaction product of step d) by exposure to dihydrogen.

Indeed, it was surprisingly found that when the catalyst is prepared according to the present invention, a more selective hydrodeoxygenation catalyst can be obtained than an hydrodeoxygenation catalyst obtained by the best state of the art synthesis methods, for instance dispersing fully reduced transition metal catalyst (Ni/SiO₂ catalyst) precursor in di-n-octyl ether, whereby tri-(n-octyl)phosphine is added. Indeed, hydrodeoxygenation of lignin oil performed with the catalyst of the present invention happens with a significantly better hydrocarbon product yield (> 90%) and selectivity, towards C5-C8, C9-C18 and >C18 hydrocarbons, that are essentially free of oxygen, preferably with high jet fuel content in the composition.

The method according to the invention uses cheap and non-toxic chemicals, only safe and stable chemicals, is not subject of the requirement of too high activation temperatures, nor it requires a high temperature during the phosphidation step, nor the use of an inert atmosphere.

The present invention also related to a nickel phosphorus catalyst, comprising an assembly of P and Ni, with a P/Ni atomic ratio inferior or equal to 0.45, preferably inferior or equal to 0.4, preferably comprised between 0.01 and 0.45, preferably comprised between 0.05 and 0.4, preferably comprised between 0.05 and 0.3, preferably comprised between 0.05 and 0.2.

The invention shows for this particular synthesis method a unique P/Ni atomic ratio, that is well below the commonly aimed value of 0.5, preferably it is below 0.2 to generate the most active HDO catalyst for renewable carbon feedstock such as lignin products and others. The catalyst according of the invention shows not only very high HDO activity for various oxygenates (or oxygen containing hydrocarbons), but also the catalyst shows high carbon-oxygen cleavage capabilities, while leaving carbon-carbon bonds (e.g., via hydrocracking) largely and essentially untouched to avoid loss of carbon as light gas fractions.

By using the method according to the invention, it is thus in particular possible to manufacture a nickel phosphorus catalyst for hydrodeoxygenation of lignin oil into hydrocarbon hydrodeoxygenation process with a selectivity /yield of more than 90%, including C5-C8, C CIS, and >C18 hydrocarbons, that has a high jet + diesel fuel yield, with preference for the jet fuels.

The present invention also concerns the use of the nickel phosphorus catalyst according to the invention, as a catalyst of a hydrogenation, hydrodesulphurisation, hydrodenitrification, hydrodeoxygenation, hydrogenolysis, decarbonylation, and/or dehydration reaction of unsaturated hydrocarbons (olefins or aromatics), carbonylic hydrocarbons, carboxylic hydrocarbons, hydroxylic hydrocarbons (alcohols or phenols), sulfur-containing hydrocarbons, nitrogen-containing hydrocarbons and combinations thereof, in particular bio-feeds, preferably as a catalyst of a hydrodeoxygenation reaction of oxygenated feeds, preferably oxygenated biofeed, more preferably as a catalyst of hydrodeoxygenation of lignin oil.

Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION

Process

The process of the invention comprises a step a) of providing a first precursor phase, comprising an at least partly reduced nickel precursor.

Preferably, the at least partly reduced nickel precursor presents a nickel content by mass of at least 10% of the mass of the at least partly reduced nickel precursor, preferably at least 20%, preferably at least 25%, preferably at least 30%, preferably from 40% to 90%, preferably from 50% to 80%, preferably from 55% to 75%, preferably from 60% to 68%.

The mass content of Ni in the at least partly reduced nickel precursor takes into account all Ni atoms, whatever their oxidation state and means the mass of nickel over the mass of the precusor in percent (including the support when present and any other element present in the precursor).

Preferably, the level of reduction of the nickel in the at least partly reduced nickel precursor is between 10 and 99 at%, preferably between 50 and 98 at%, and most preferably between 70 and 96 at%. “at%” means the number of atoms that have valency zero over the total number of present atoms of the same kind. The level of reduction is measured by Temperatureprogrammed reduction (TPR).

TPR is performed in a conventional, U-shaped, quartz microreactor using a 5% H2 in argon mixture flowing at 50 cm3 min-1 (STP). Prior to the TPR measurement, a calibration of the TCD signal is performed allowing later on the quantification of the H2 consumption during the TPR analysis. The correct calibration and operation of the system is checked using a reference sample, silver oxide that will be reduced into metallic silver. A thermal pre-treatment of the sample may be applied to condition the sample before the TPR measurement. For TPR measurements, the temperature range investigated is 100-800°C and the heating rate used, 10°C min-1.

By “at least partly reduced”, it is meant the nickel is present under a mixture of Ni atoms having a oxidation degree of 0 and of Ni atoms having a oxidation degree different from 0, for example + 1 or +2. The level of reduction means the percentage in number of Ni atoms of the at least partly reduced nickel precursor having a oxidation degree of 0 relative to the total number of Ni atoms of the at least partly reduced nickel precursor.

Nickel can be at least partly reduced using a variety of reducing agents, such as dihydrogen, or carbon monoxide. This is done by at least partly reducing nickel oxide to metallic nickel using a reducing agent such as hydrogen gas.

According to an embodiment the at least partly reduced nickel precursor can be in the form of single atom or cluster of atoms without support.

According to a preferred embodiment, the at least partly reduced nickel precursor comprises a support, preferably an inorganic support. Preferably, the at least partly reduced nickel precursor comprises an at least partly reduced nickel phase and a support, preferably an inorganic support. Preferably the at least partly reduced nickel phase is dispersed on the support, preferably on the inorganic support. In particular, the at least partly reduced nickel is dispersed on the support, preferably on the inorganic support, in the form of small nanoparticles or clusters.

Preferably, the catalyst is supported by the support, for example, on a refractory metal oxide, such as silica (SiO2, amorphous and/or mesoporous), alumina (A12O3, crystalline, amorphous and/or mesoporous), cerium oxide (CeO2), titanium oxide (TiO2) and zirconium oxide (ZrO2), a carbon support (such as activated carbon, graphite, graphene, black carbon), silica carbide, amorphous silica-alumina, amorphous silica-alumina-titania, phosphated alumina or phosphated silica-alumina, sulfated zirconia, tungsten zirconia and zeolite, diatomite, hydroxyapatite, or a mixture thereof. Preferably, the support is selected from silica, alumina, titania, zirconia, carbon, ceria, silica carbide, silica-alumina, silica-alumina-titania, phosphated alumina or phosphated silica-alumina, sulfated zirconia, zirconia-tungsten, a zeolite or mixtures thereof.

More preferably, the support is a silica-rich material, preferably silica (SiO2).

Preferably, the at least partly reduced nickel precursor has a high specific surface area. In one embodiment, the specific surface area should be at least 75 m²/g, preferably at least 150 m²/g and more preferably at least 200 m²/g. The surface area is measured by the “Brunauer Emmet and Teller” or BET method. The BET method involves measuring the volume of nitrogen gas adsorbed at various low-pressure levels by the catalyst sample. According to a preferred embodiment, the at least partly reduced nickel precursor which comprises a support, preferably an inorganic support, is extrudate, for example under the form of cylinders, trilobes or quadrulobes with a diameter of at least 0.6 mm and a diameters of at least 1.0 mm. According to an embodiment, the at least partly reduced nickel precursor which comprises a support is under the form of irregular particulate, pellets or pils or balls preferably has an effective size of 1 to 10 millimeter in the different directions.

A specific example of an at least partly reduced nickel precursor is a 65%Ni/SiO2 precursor with a metal content of 65% nickel on a SiO2 support with a surface area of 100-200 m2/g and with nickel particle size: 20-50 nm and pore size: 5-10 nm and bulk density of 0.3-0.5 g/cm3, wherein at least partly reduced nickel phase is stabilized on silica. A surface area of 100-200 m2/g is considered to be a high surface area. Nickel, partially reduced and dispersed on silica means that the nickel is in its partial metallic and oxidized form and is dispersed on silica particles. In industrial practices, nickel-based catalysts are reduced to the metallic state, however they are passivated as metallic nickel, which is pyrophoric when exposed to air, resulting in uncontrolled temperature rise and agglomeration of the nickel particles. The nickel particles are passivated by a gentle treatment to cover the nickel particles with a thin oxidecontaining layer that protects the nickel particle from further oxidation, for instance, using diluted oxygen or CO2, or by contacting with water in a synthesis steps, as known by the catalyst expert. A high surface area provides more sites for the metal to disperse on, which can help to prevent agglomeration.

The process of the invention also comprises a step b) of providing a second precursor phase, comprising an aqueous solution of a source of phosphorus oxides.

A source of phosphorus oxides means a compound comprising at least one phosphorus atom and at least one oxygen atom, preferably comprising at least a P-0 chemical bond, and that is preferably soluble in water. Preferably, the aqueous solution of a source of phosphorus oxides is an aqueous solution of phosphorus oxoacids, preferably is an aqueous solution of phosphoric acid (H3PO4). In the general sense, a phosphorus oxoacid is a compound in which phosphorus (P) atom is in the oxidation state +5, and is bonded to four oxygen (O) atoms, one of them through a double bond, arranged as the corners of a tetrahedron and three acidic OH groups, where the acidic H can be replaced by other cations or alkyl-groups. Two or more orthophosphoric acid molecules can be joined by condensation yielding pyrophosphoric acids, oligophosphoric acids or polyphosphoric acids. When the phosphoric acid units can be bonded together in rings they make cyclic polyphosphates.

These phosphoric acids series are generally water-soluble considering the polarity of the molecules. In particular, hydrogen, ammonium and alkali phosphates or mixtures thereof are soluble in water.

The -OH groups in phosphoric acids can also condense with the hydroxyl groups of alcohols to form phosphate esters a mono-, di-, or triester.

Phosphorous acid (or phosphonic acid or H₃PO₃) is a phosphorus oxyacid in which phosphorus (P) atom is in the oxidation state +3, and is bonded to one hydrogens (H), to three oxygen (O) atoms, one of them through a double bond, and the other through two acidic OH group (H- P(=O)OH₂ in equilibrium with the minor tautomer P(OH)₃), where the acidic H can be replaced by other cations or alkyl-groups.

Phosphinates or hypophosphites is a phosphorus oxoacid (H₃PO₂) in which phosphorus (P) atom is in the oxidation state +1, and is bonded to two hydrogens (H), to two oxygen (O) atoms, one of them through a double bond, and the other through one acidic OH group (H₂-P(=O)(OH) in equilibrium with the minor tautomer HP(OH)2), where the acidic H can be replaced by other cations or alkyl-groups. Hypophosphoric acid is an oxoacid having a P-P bond with formula H4P₂O₆, with phosphorus in a formal oxidation state of +4 and each Phosphorus atom (P) has three oxygen atoms (O), one as a double bond and the other two as acidic OH groups, where the acidic H can be replaced with other cations or alkyl-groups.

All these phosphorus oxoacids or corresponding salts or esters are sufficiently soluble in water for the present invention. Preferably, phosphorus oxoacids are phosphates.

The process of the invention also comprises a step c) of putting into contact the first precursor phase of step a) with the second precursor phase of step b), to obtain a reaction product.

Preferably, step c) comprises a step cl) of mixing the first precursor phase and the second precursor phase, preferably at a temperature between 15°C and 30°C, and preferably under air atmosphere, to obtain a mixture. Step cl) is preferably followed by a step c2) of resting the mixture obtained at step cl) for from 0.1 hours to 24 hours, more preferably from 1 hours to 16 hours, preferably at a temperature between 15°C and 30°C, and preferably under air atmosphere, to obtain the reaction product.

The first precursor phase can be used as such, can be dried or can be priorly wetted with water before use in step c). In step cl), the first precursor phase is preferably brought into contact with the second precursor by a dry or wet impregnation. A dry impregnation means that the whole second precursor phase is absorbed by the first precursor phase and essentially no visible free flowing liquid is present. A wet impregnation means that an excess of second precursor phase is used compared to the absorption capacity of the first precursor phase and hence still free flowing liquid is present. Depending on the phosphorus oxide concentration that can be used, a dry or wet impregnation will be applied (when concentration is high a dry impregnation is possible, whereas when concentration is low a wet impregnation has to be used).

The process of the invention also comprises a step d) of drying the reaction product of step c) to obtain a dried reaction product.

Preferably, step d) is carried out at a temperature between 50°C and 120°C, more preferably between 70°C and 90°C, under air or any inert atmosphere. Preferably, the drying is done under air atmosphere.

Preferably, during step d) the drying of the reaction product of step c) is done at 50°C or higher under an atmosphere containing at least 1 mol% of dioxygen.

Preferably, step d) is carried out for from 0.1 hours to 24 hours, more preferably from 1 hour to 16 hours.

The process of the invention also comprises a step e) of activating the dried reaction product of step d) by exposure to dihydrogen. The dihydrogen can be either pure or diluted in an inert gas (such as Nitrogen).

Preferably, the dried reaction product is exposed to dihydrogen at a temperature between 100°C and 700 °C, preferably between 250°C and 600°C, preferably between 400°C and 550°C. Preferably, step e) is performed for from 1 hour to 8 hours, preferably from 2 hours to 6 hours. Preferably, step e) is carried out under a dihydrogen pressure between 10⁵ and 100.10⁵ Pa. This allows the dihydrogen to chemisorb onto the surface of the Ni particles. Without willing to be bound to any theory, given that the first precursor phase has to be at least partially reduced, it is assumed that the dihydrogen is readily activated on the metallic nickel (dissociative splitting), resulting in very reactive hydrogen atoms that are able to reduce the second precursor phase, containing phosphorus oxoacid compounds, having formal oxidation state higher or equal to + 1.

Preferably, step e) provides a nickel phosphorus assembly, preferably dispersed on the support.

According to an embodiment, the process of the invention further comprises a step f) of passivation of the product obtained at step e) by exposing the product of step e) to a passivation atmosphere, preferably to a mixture of dioxygen and inert gases or to a mixture of carbon dioxide and inert gases or mixtures thereof. The passivation atmosphere is for example a mixture of dioxygen and nitrogen gases, or of carbon dioxide and nitrogen.

This step allows forming a protective layer on the surface of the catalyst (the Ni/P assembly). Preferably, step f) is carried out by flowing the passivating mixture on the product obtained at step e). Such passivation step is recommended when the catalyst has to be exposed to air, for instance during transport or handling.

Preferably, if the passivating mixture is a mixture of dioxygen and nitrogen, it comprises between 0.01% and 5 mol% of dioxygen and between 95 and 99.99 mol% of nitrogen. Preferably, if the passivating mixture is a mixture of carbon dioxide and nitrogen, it comprises between 0.1 and 20 mol% of carbon dioxide and 80 and 99.9 mol% of nitrogen. Preferably, a mixture of dioxygen and carbon dioxide in nitrogen can be used.

Nickel phosphorus catalyst

The present invention also concerns a nickel phosphorus catalyst, comprising an assembly of P and Ni, with a P/Ni atomic ratio inferior or equal to 0.45, preferably inferior or equal to 0.4, preferably comprise between 0.01 and 0.45, preferably comprised between 0.05 and 0.4, preferably comprised between 0.05 and 0.3, preferably comprised between 0.05 and 0.2.

According to some embodiments, the P/Ni atomic ratio is superior or equal to 0.005, preferably superior or equal to 0.01, preferably superior or equal to 0.02, preferably superior or equal to 0.03, preferably superior or equal to 0.04, preferably superior or equal to 0.05, preferably superior or equal to 0.06, preferably superior or equal to 0.07, preferably superior or equal to 0.08, preferably superior or equal to 0.09, preferably superior or equal to 0.10, preferably superior or equal to 0.20, preferably superior or equal to 0.30, preferably superior or equal to 0.40, preferably superior or equal to 0.50, preferably superior or equal to 0.60, preferably superior or equal to 0.70, preferably superior or equal to 0.80.

According to some embodiments, the P/Ni atomic ratio is inferior or equal to 2.0, preferably inferior or equal to 1.8, preferably inferior or equal to 1.6, preferably inferior or equal to 1.4, preferably inferior or equal to 1.2, preferably inferior or equal to 1.0, preferably inferior or equal to 0.90, preferably inferior or equal to 0.80, preferably inferior or equal to 0.70, preferably inferior or equal to 0.60, preferably inferior or equal to 0.50, preferably inferior or equal to 0.40, preferably inferior or equal to 0.30, preferably inferior or equal to 0.20, preferably inferior or equal to 0.10, preferably inferior or equal to 0.05. According to some embodiments, the P/Ni atomic ratio is comprised between 0.01 and 2.0, preferably comprised between 0.02 and 1.6, preferably comprised between 0.03 and 1.2, preferably comprised between 0.04 and 1.0, preferably comprised between 0.05 and 0.90, preferably comprised between 0.06 and 0.80, preferably comprised between 0.07 and 0.70, preferably comprised between 0.08 and 0.60, preferably comprised between 0.09 and 0.50, preferably comprised between 0.10 and 0.40, preferably comprised between 0.10 and 0.30, preferably comprised between 0.10 and 0.20.

The P/Ni atomic ratio is measured using a semi-quantitative elemental analysis performed by X-Ray Fluorescence (XRF). Prior to the analysis, the powder samples are inserted into 25mm- diameter pods sealed with a polypropylene film. Analyses are carried out under helium.

“NiP catalyst” or Nickel Phosphorus catalyst, is a catalyst comprising or consisting of a metallic assembly comprising (or consisting of) Ni and P. The nickel phosphorus catalyst of the invention can be supported.

Preferably, the nickel phosphorus catalyst comprises at least 10 wt% of Ni in relation to the mass of the nickel phosphorus catalyst (thus including the support if present), preferably at least 15wt%, preferably at least 25wt%, preferably at least 40wt%, preferably from 40wt% to 90wt%, preferably from 50wt% to 80wt%, preferably from 50wt% to 75wt%, preferably from 55wt% to 70wt%.

The Ni content in the Nickel Phosphorus catalyst is measured using a semi-quantitative elemental analysis performed by X-Ray Fluorescence (XRF). Prior to the analysis, the powder samples are inserted into 25mm-diameter pods sealed with a polypropylene film. Analyses are carried out under helium.

Preferably, the nickel phosphorus catalyst further comprises a support, preferably an inorganic support, the support preferably being as described above for the at least partly reduced nickel precursor. Preferably, the nickel phosphorus catalyst comprises a nickel phosphorus assembly and a support, preferably an inorganic support. Preferably the nickel phosphorus assembly is dispersed on the support. In particular, the nickel phosphorus assembly is dispersed on the support in the form of small nanoparticles or clusters.

Preferably, the nickel phosphorus catalyst further comprises a carbon-containing support. Preferably, the nickel phosphorus catalyst comprises a nickel phosphorus assembly and a carbon-containing support. Preferably the nickel phosphorus assembly is dispersed on the carbon-containing support. In particular, the nickel phosphorus assembly is dispersed on the carbon-containing support in the form of small nanoparticles or clusters.

In one embodiment, the nickel phosphorus catalyst according to the invention exhibit preferably substantially no x-ray diffractions corresponding to crystalline NiP3, NiP2, NiP, Ni2P, Ni3P, Ni5P4 orNil2P5.

In one embodiment, the nickel phosphorus catalyst according to the invention exhibit preferably substantially no x-ray diffractions corresponding to crystalline Nickel particles.

In one embodiment, the nickel phosphorus catalyst according to the invention exhibit preferably x-ray diffractions corresponding to crystalline Ni2P, Ni3P, and Nil2P5.

In one embodiment, the nickel phosphorus catalyst according to the invention exhibit preferably substantially no x-ray diffractions corresponding to crystalline Nickel phosphorous oxides (like Ni2P2O7, Ni(PO3)2, NiP2O6, NiP4011, Ni3(PO4)2 or Ni2P4O12).Preferably, the nickel phosphorus catalyst according to the invention is obtainable from the process according to the invention.

Uses

The invention also concerns the use of the nickel phosphorus catalyst according to the invention, as a catalyst of a hydrogenation, hydrodesulphurisation, hydrodenitrification, hydrodeoxygenation, hydrogenolysis, decarbonylation, and/or dehydration reaction of unsaturated hydrocarbons, carbonylic hydrocarbons, carboxylic hydrocarbons, hydroxylic hydrocarbons, sulfur-containing hydrocarbons, nitrogen-containing hydrocarbons and combinations thereof, in particular bio-feeds, preferably as a catalyst of a hydrodeoxygenation reaction of oxygenated feeds, preferably oxygenated bio-feed.

The invention thus also concerns the use of the nickel phosphorus catalyst according to the invention, as a catalyst of a hydrogenation, hydrodeoxygenation, hydrogenolysis, decarbonylation, and/or dehydration reaction of oxygen containing bio-feeds, preferably as a catalyst of a hydrodeoxygenation reaction of oxygenated feeds.

Hydrodeoxygenation (HDO) is a hydrogenolysis process for removing oxygen from oxygencontaining compounds. In the present invention, this hydrodeoxygenation involves contacting a catalyst with an oxygenated feed under conditions sufficient to remove essentially all oxygen, e.g. in the form of water and/or alcohols and providing deoxygenized hydrocarbon components. The resulting hydrocarbon components are useful, for instance, as high-quality aviation fuels and as blending stocks or components for high-quality aviation fuels, considered for hydrocarbons between 9 and 17 C atoms. Also, hydrocarbon components useful as diesel fuels (considering between Cl 8 and C25 hydrocarbons) and components suitable as gasoline are obtained.

Bio-feeds are feeds (chemical component s)) that are derived from biological sources, such as plants, animals, and microorganisms. It includes a wide range of biological sources, such as: Plant materials: These include agricultural crops, such as corn, soybeans, and sugarcane; agricultural residues, such as straw and com stover; and forestry residues, such as wood chips and sawdust; Animal materials: These include animal fats, manure, and wastewater; Municipal solid waste: This includes food scraps, yard waste, and paper products; Algae: Algae are a type of microorganism that can be grown in water and used to produce biofuels and other products. Oxygenated feed (or oxygenated feedstock) refers to a feedstock that contains oxygencontaining compounds. Non-limiting examples of oxygenated feeds are feedstock that comprises methanol, ethanol, n-propanol, isopropanol, C4-C20 alcohols, methyl ethyl ether, dimethyl ether, di-ethyl ether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone and/or acetic acid. Some common examples of oxygenated feeds include, alcohols, such as ethanol, methanol, n-propanol, isopropanol, C4-C20 alcohols; ethers, such as methyl ethyl ether, dimethyl ether, diethyl ether, di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone; esters, such as biodiesel and fatty acid methyl esters; fatty acids; organic acids, such as acetic acid and lactic acid and sugars, such as glucose and fructose, furanics etc; pyrolysis oils obtained from the heating of biomass; components obtained from lignocellulose, for example lignins, lignin oils, celluloses, hemicelluloses, proteines, bio-oils (pyrolysis oil or oils obtained by hydrothermal liquifaction), triglycerides, tyre pyrolysis oils, tall oils and plastic pyrolysis oils from plastic-containing materials and mixtures thereof. Preferably, the oxygenated feeds are chosen from components obtained from lignocellulose, for example lignins, lignin oils, celluloses, hemicelluloses, proteines, bio-oils (pyrolysis oil or oils obtained by hydrothermal liquifaction), bio-oils; triglycerides; pyrolysis oils, tyre pyrolysis oils, tall oils and plastic pyrolysis oils from plastic-containing materials and mixtures thereof,

Preferably, the nickel phosphorus catalyst of the invention is used as a catalyst of hydrodeoxygenation of liquid lignin oil. More preferably, the nickel phosphorus catalyst of the invention is used as a catalyst of hydrodeoxygenation of a liquid mixture containing lignin oils and triglycerides, diglycerides, monoglycerides and/or free fatty acids.

General considerations

The terms first, second, third, and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

Moreover, the terms top, bottom, over, under, and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.

It is to be noticed that the term “comprising”, used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression “a device comprising means A and B” should not be limited to the devices consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the device are A and B.

Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearance of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification do not necessarily all refer to the same embodiment but may. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

Similarly, it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.

It is intended that the specification and examples be considered as exemplary only.

Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are part of the description and are a further description and are in addition to the preferred embodiments of the present invention.

Each of the claims set out a particular embodiment of the invention.

The following terms are provided solely to aid in the understanding of the invention.

A comprehensive comprehension of the invention can be attained by referring to the detailed description, combined with the illustrative examples and accompanying diagrams, which are not intended to impose limitations.

EXAMPLES

EXAMPLE 1 - Preparation of Ni phosphorus catalysts according to the invention and comparative

In this example, several Ni phosphorus catalysts were prepared. NiP- l/SiO₂ (according to the invention)

A NiP/SiO₂ catalyst containing 65 wt.% Ni and 5 wt.% Phosphorus on a SiO₂ support (designated as NiP-l/SiO₂) was prepared by the following procedure:

Commercial 65%Ni/SiO₂ was purchased from Strem Chemicals Inc. as a catalyst precursor. The catalyst precursor, as received, is impregnated with phosphorus using phosphoric acid solution (H3PO4, 83 wt.% aqueous solution).

The phosphoric acid solution (0.98g) is dissolved in deionized water (1 mL) to which 65%Ni/SiO₂ (5g) was added and mechanically stirred for Ih to obtain a uniform mixed slurry. The resulting mixed uniform slurry had a phosphorus-to-nickel mole ratio (P/Ni) of 0.16.

The solid solution is then aged at room temperature for 12 h, followed by oven heated at 80 °C under air atmosphere for 12 h, thus preparing dried NiP-l/SiO₂ precursor.

Then, a U-tube reactor was packed with 1 gram of dried NiP-l/SiO₂ precursor, after which the temperature thereof was increased to 550 °C at a rate of 1 °C/min, while allowing the H₂ to flow at a rate of 30 ml/min (normal milliliters) . When the temperature reached 550 °C, activation was performed for 4h. After the activation was completed, the U-tube was cooled down to room temperature, and a mixture of gas about 1% oxygen mixed with nitrogen was flown for 1 h to obtain passivated NiP-l/SiO₂.

NiP-2/SiO₂ (invention) and NiP-3/SiO₂ (comparative)

Two other catalysts with different P/Ni mole ratios, NiP-2/SiO₂ and NiP-3/SiO₂ were prepared in the same manner as explained above for NiP-l/SiO₂.

NiP-l/SiO_2; comprised 65% by weight of Ni and 5% by weight of P supported on silica. The catalyst NiP-l/SiO₂ had a phosphorus-to-nickel mole ratio (P/Ni) of 0.16.

The NiP-2/SiO₂ catalyst comprises 65% by weight of Ni and 15% by weight of P supported on silica. The catalyst NiP-2/SiO₂ had a phosphorus-to-nickel mole ratio (P/Ni) of 0.32.

The catalyst NiP-3/SiO₂ comprises 65% by weight of Ni and 30% by weight of P dispersed on the same type of silica support. The catalyst NiP-3/SiO₂ had a phosphorus-to-nickel mole ratio (P/Ni) equal to 1.26.

NiP-4/SiQ₂ (comparative)

In another comparative example, NiP-4/SiO₂ was synthesized according to nearly the same procedure than NiP-l/SiO₂, excepted that the catalyst precursor comprised of the commercial 65%Ni/SiO₂ was first oxidized under oxygen at elevated temperature (550°C for 5 h) to oxidize essentially all reduced Ni into the corresponding nickel oxide.

NiP-Liq/SiO₂ (comparative)

One of the best available phosphide catalysts of the prior art (Joule “Volume 2, Issue 6, 20 June 2018, Pages 1118-1133”), that are prepared using liquid-phase, is prepared to be compared with the present invention. Liquid-based phosphidation involves the reaction of salts, organometallic reagents, and metal/metal oxide nanoparticles with alkylphosphines. For liquid-phase phosphidation, the reaction was carried out under an inert argon atmosphere. A 65% Ni/SiO₂ (1 g) catalyst precursor was added to di-n-octyl ether (15 mL) from Strem Chemicals Inc., followed by tri-(n-octyl)phosphine (TOP) (30 mL) added to the mixture (equivalent to a TOP:Ni ratio of 6.1). The slurry was stirred for 30 minutes at room temperature, then the temperature was increased to 300 °C and kept at that temperature for 6 hours. After 6 hours, the slurry was cooled down to room temperature and then washed three times with 2-propanol. Finally, the phosphide catalyst NiP-Liq/SiO₂ was obtained by centrifugation. The catalyst was dried at 80 °C before being tested for HDO activity.

EXEMPLE 2 : Deoxygenation of lignin oil

The catalytic hydrodeoxygenation activity of the catalysts of example 1, and also of a commercial catalyst Ni/SiO₂, was measured in the hydrodeoxygenation of an oxygenated feedstock derived from biological origin with the following protocol:

Hydrodeoxygenation catalytic activity measurement is carried out in a 50 mL Parr reactor provided by Parr Instrument Company, Model 4590. The reactor vessel was charged with 0.4 g of catalyst (2% by mass of the total feed), 0.5 g of poplar lignin oil as oxygenated feed (3.2% by mass of the total feed), and 15 g of dodecane as carrier liquid (96.8% by mass of the total feed). The lignin from Poplar wood was prepared according to the methods described in US20190233743. The principal characteristics of the poplar wood lignin oil as oxygenated feed used in the process of the invention are shown in Table 1.

The Parr reactor was flushed three times with nitrogen gas and finally pressurized with 5 MPa of hydrogen at room temperature and sealed before heating to a reaction temperature of 300 °C, which was then allowed to react for 5 h with a constant stirring of 700 rpm. After the hydrodeoxygenation reaction, the reactor was left to cool down to room temperature. After cooling, the gaseous products were measured with a gas chromatograph equipped with TCD to measure the content of C1-C4 hydrocarbons and carbon monoxide, and carbon dioxide. Table 1 Poplar Lignin Oil Properties

The product mixture obtained comprises a liquid product, water, and a solid phase comprising the catalyst. The liquid product was separated from the catalyst and water by centrifugation.

The recovered catalyst was washed with ethanol and oven dried overnight at 80 °C. The coke present on the surface of the catalyst after the hydrodeoxygenation reactions were evaluated using thermogravimetry analysis.

An aliquot of clear liquid product was injected into a gas chromatograph (Agilent) equipped with an HP-5 column and a flame ionization detector to quantify the content of hydrocarbons formed as a result of hydrodeoxygenation reaction, and the values are reported in Table 2.

Gas chromatography /mass spectrometry (GC-MS) was carried out to identify the hydrocarbons present in the liquid phase.

The hydrocarbons in the liquid phase are comprised of alkylated cyclohexane derivates and alkylated bi- and tri-cyclic naphthenic compounds, in the range of C5-C25, including cyclopentane, cyclopentane methyl-, cyclohexane, cyclohexane methyl-, cyclopentane ethyl-, cyclohexane ethyl-, cyclohexane propyl-, cyclohexane propenyl-, l-Ethyl-4- methylcyclohexane, IH-Indene, octahydro-, Cyclohexane, butyl-, (2- Methylbutyl)cyclohexane, Cyclohexane, hexyl, Cyclohexane, (cyclopentylmethyl)-, Heptyl cyclohexane, Cyclohexane, 1,1 methylene bis-, Cyclohexane, octyl-, Cyclohexane, 1,1'-(1,2- ethanediyl)bis, l-Cyclopentyl-4-(l-methylethyl)cyclohexane, Cyclohexane, l,l'-ethylidenebis- , 1 -Cyclohexyl- 1 -(4-methylcy cl ohexyl)ethane, Cyclohexane, 1, l'-(l -methyl- 1,2- ethanediyl)bis-, Cyclohexane, l,l'-(l,3-propanediyl)bis-, Cyclohexane, 1,1'-(1,4- butanediyl)bis-, Cyclohexane, l,l'-(l,4-butanediyl)bis-, Cyclohexane, 1,1'-(1- m ethyl ethylidene)bis-, 1 -Cyclohexyl- 1 -(4-methylcy cl ohexyl)ethane, Cyclohexane, 1,1'- propylidenebis-, l,l'-Bicyclohexyl, 2-propyl-, trans-, Cyclohexane, l,T-propylidenebis, Cyclohexane, l,l'-(l,2-dimethyl-l,2-ethanediyl)bis-, 1 -Cyclohexyl- 1 -(4- ethylcyclohexyl)ethane, Cyclohexane, l,l'-(l-thyl-l,2-ethanediyl)bis-, Cyclohexane, 1,1'- hexylidenebis-, l, r:3',l"-Tercyclohexane, Cyclohexane, l,l',l"-(l-ethanyl-2-ylidene)tris- at an approximate yield of 97 wt.% relative to the theoretical maximum.

The hydrocarbon yield calculations were based on the following equations:

Viscosity measurements were carried out on a stress-controlled rheometer (Anton Paar MCR501). Sample temperature was controlled using a Peltier system (P-PTD200) with a solvent plate bottom and an evaporation blocker to an accuracy of approx. 0.1°C. For viscosities above 0.1 Pa.s, a PP 25 geometry was used, while for viscosities below 0.1 Pa.s, a

PP50 geometry was employed. Viscosity was determined as a function of shear rate, with 5 measurement points per decade. The shear rate range was adapted according to temperature and sample, so that measurements were carried out in the Newtonian regime and above the minimum torque level of the device. In the Newtonian regime, measurements were averaged over 5 points (1 decade). RheoPlus software (Anton Paar GmbH, Austria) was used for data acquisition and analysis.

The mass content of oxygen atoms is defined by elemental analysis in accordance with ASTM 5622, May 2017. Table 2 Hydrodeoxygenation of oxygenated feed.

Comments on the results:

Said hydrocarbons are particularly suitable components for gasoline, kerosene, and diesel. This example demonstrates the ability of NiP-l/SiO₂ to achieve complete deoxygenation of lignin oil as an oxygenated feed to paraffinic hydrocarbons.

The obtained catalyst showed excellent activity in the hydrodeoxygenation of lignin oil, as seen as high total hydrocarbon yield including high jet fuel (C9-C18) yield and essentially no remaining oxygen containing hydrocarbon.

The catalysts NiP-l/SiO₂ and NiP-2/SiO₂, characterized by a lower P/Ni ratio, demonstrated superior hydrocarbon yield in comparison to catalysts with higher P/Ni ratios. The NiP-l/SiO₂ and NiP-2/SiO₂ also exhibited higher selectivity and yield for jet range hydrocarbons (C8-C18) than their counterparts with higher P/Ni ratios. This is surprising given the higher P/Ni ratio values that are typically reported in literature (> 0.5, preferably 2 or higher), as opposed to the low ratio in this invention. The difference in catalytic activity, while varying the P/Ni ratio, might be due to the formation of new active Ni-P species on the catalyst surface and changes in the acidity of the catalysts, advantageously for this HDO.

In the comparison of the invention against the commercial catalyst Ni/SiO₂, Ni that has not been treated with phosphorus according to the invention, the NiP-l/SiO₂ and NiP-2/SiO₂ catalyst of the invention also shows superiority while containing a lower weight percentage of phosphorus components. Under the same reaction conditions, using the NiP-l/SiO₂ resulted in the formation of more than 90% by weight (C5-C25) naphthenic hydrocarbons, with high jet fuel yield, which is better than the results with catalysts having either no P or P/Ni ratio above 0.5.

Thus, the NiP-l/SiO₂ and NiP-2/SiO₂ catalysts of the invention with a P/Ni ratio equal to 0.1 or 0.4 not only allows higher activity with higher total hydrocarbon yield, but also allows the reaction selectivity to be high for the formation of naphthenic hydrocarbons in the range of C8- C18. The results for catalyst NiP-4/SiO₂ show worse HDO activity than the catalyst of the invention, resulting in hydrocarbon yields below 90%, and low jet fuel yield.

Finally, catalyst NiP-Liq/SiO2 according to the best prior art is considerably less efficient in the HDO of oxygenated feed than the catalysts used in Examples 1-2 given the remaining high content of oxygen in the hydrocarbon product, and the lower jet fuel yield.

EXAMPLE 3 - Co-processing of oxygenated feeds

This example demonstrates the capability of nickel phosphorus catalysts of the invention to effectively deoxygenate a wide range of oxygenated feedstocks.

For the co-processing tests, the reactor vessel was charged with 1.3 g of passivated NiP-l/SiO₂ (6.5% by mass of the total feed), a total 6 g of oxygenated feed consisting of 2.7 g of poplar wood lignin oil (13.5 % by mass of the total feed) and 3.3 g of vegetable oil (16.5 % by mass of the total feed), and 14 g of dodecane as a carrier liquid (70% by mass of the total feed) wherein, the mass ratio of poplar wood lignin oil and vegetable oil in the oxygenated feed was 1:1.2.

The composition of lignin oil is similar to Example 2. The composition of vegetable oil is shown in Table 3.

The reactor was purged with nitrogen and than pressurized with hydrogen and heated to the desired temperature of 300°C at which the total pressure was regulated at 10 MPa by addition of hydrogen.

The hydrodeoxygenation reaction, analysis, and separation of reaction products were carried out similarly to Example 2.

The hydrocarbons in the liquid phase are comprised of alkylated cyclohexane derivatives and n-paraffins (Table 4). During the hydrodeoxygenation process, the lignin oil in the oxygenated feed is mainly converted to alkylated bi- and tri-cyclic cyclohexane derivatives in the range of C5-C25 whereas, vegetable oil in the oxygenated feed is converted mainly to C17 and C18 n- paraffins.

The NiP-l/SiO₂ resulted in the formation of 97 wt.% cyclo- and n-paraffin hydrocarbons relative to the oxygenated feed's theoretical maximum. This feed comprised poplar wood lignin oil and vegetable oil, where approximately 33 wt.% was attributed to cycloalkane derivatives and 64 wt.% constituted n-paraffins. The quantities of cycloalkane derivatives and n-paraffins obtained in the product stream are directly linked to the mass ratio of lignin to vegetable oil in the initial oxygenated feed.

Table 3 Vegetable Oil Properties

Table 4 - Coprocessing of lignin oil and vegetable oil as oxygenated feed using NiP-l/SiO₂

EXAMPLE 4 - HDO of other oxygenates.

Hydrodeoxygenation of 4-(furan-2-ylmethyl)-2-methoxyphenol into a solely a 1:3 mixture of pentyl:butylcyclohexane was carried out in a 50 mL stainless steel Parr reactor equipped with digital pressure gauge, temperature controller, and a four bladed impeller. The conversion is 100%. The reactor was loaded with 100 mg substrate sample, 80 mg NiP-l/SiO₂ catalyst, and 20 mL dodecane. Next, the reactor was tightly closed and purged 3 times with N₂ and once with H₂. In the following step, the reactor was pressurized with 50 bar H₂, stirring speed was set to 700 rpm, and afterwards heated to 250 °C. Reaction was allowed to proceed for 22 h.

In summary, compared with the prior art, the invention has beneficial technical effects that:

( i ) Streamlined and industrially feasible approach for creating nickel phosphorus catalysts using commercially pre-synthesized nickel supported as precursors. ( i i ) Versality in deoxygenating various oxygenated feedstocks.

( i i i ) Exceptional hydrodeoxygenation performance.

( iv) High yield and selectivity of desired products.

( v ) Reaction under mild conditions ( vi ) Unlike conventional industrial hydroprocessing catalysts, this catalyst operates and maintains performance without requiring sulfur compounds for activation.

( vii ) Environmentally sustainable, devoid of sulfur compound emissions.

Claims

Claims

1. A process to manufacture a nickel phosphorus catalyst, the process comprising the steps of: a) providing a first precursor phase, comprising an at least partly reduced nickel precursor, b) providing a second precursor phase, comprising an aqueous solution of a source of phosphorus oxides, c) putting into contact the first precursor phase of step a) with the second precursor phase of step b), to obtain a reaction product, d) drying the reaction product of step c) to obtain a dried reaction product, and e) activating the dried reaction product of step d) by exposure to dihydrogen.

2. The process according to claim 1, wherein the at least partly reduced nickel precursor presents a nickel content by mass of at least 10% of the mass of the at least partly reduced nickel precursor, preferably of at least 20%, preferably at least 25%, preferably at least 30%, preferably from 40% to 90%, preferably from 50% to 80%, preferably from 55% to 75%, preferably from 60% to 68%.

3. The process according to claim 1 or 2, wherein the level of reduction of the nickel in the at least partly reduced nickel precursor is between 10 and 99 at%, preferably between 50 and 98 at%, and most preferably between 70 and 96 at%.

4. The process according to any of claims 1 to 3, wherein the at least partly reduced nickel precursor comprises an at least partly reduced nickel phase and a support, preferably an inorganic support, preferably the at least partly reduced nickel phase is dispersed on the support.

5. The process, according to any one of claims 1 to 4, wherein the aqueous solution of a source of phosphorus oxides is an aqueous solution of phosphorus oxoacids, preferably is an aqueous solution of H3PO4.

6. The process according to any one of claims 1 to 5, wherein, during step d) the drying of the reaction product of step c) is done at 50°C or higher under an atmosphere containing at least 1 mol% of dioxygen.

7. The process according to any one of claims 1 to 6, wherein, during step e), the dried reaction product is exposed to dihydrogen at a temperature between 100°C and 700 °C, preferably between 400°C and 550°C and/or under a dihydrogen pressure between 10⁵ and 100.10⁵ Pa.

8. The process, according to any one of claims 1 to 7, further comprising a step f) of exposing the product obtained at step e) to a passivation atmosphere, preferably to a mixture of dioxygen and inert gases or to a mixture of carbon dioxide and inert gases or mixtures thereof.

9. Nickel phosphorus catalyst, comprising an assembly of P and Ni, with a P/Ni atomic ratio inferior or equal to 0.45, preferably inferior or equal to 0.4, preferably comprised between 0.01 and 0.45, preferably comprised between 0.05 and 0.4, preferably comprised between 0.05 and 0.3, preferably comprised between 0.05 and 0.2.

10. The nickel phosphorus catalyst according to claim 9, comprising at least 10% of Ni in relation to the mass of the nickel phosphorus catalyst, preferably at least 15wt%, preferably at least 25wt%, preferably at least 40wt%, preferably from 40wt% to 90wt%, preferably from 50wt% to 80wt%, preferably from 50wt% to 75wt%, preferably from 55wt% to 70wt%.

11. The nickel phosphorus catalyst according to claim 9 or 10, further comprising a support, preferably an inorganic support.

12. The nickel phosphorus catalyst according to claim 9 or 10, further comprising a carbon- containing support.

13. The nickel phosphorus catalyst according to any one of claims 9 to 12, obtainable from the process according to any one of claims 1 to 8.

14. Use of the nickel phosphorus catalyst according to any one of claims 9 to 13, as a catalyst of a hydrogenation, hydrodesulphurisation, hydrodenitrification, hydrodeoxygenation, hydrogenolysis, decarbonylation, and/or dehydration reaction of unsaturated hydrocarbons, carbonylic hydrocarbons, carboxylic hydrocarbons, hydroxylic hydrocarbons, sulfur-containing hydrocarbons, nitrogen-containing hydrocarbons and combinations thereof.

15. Use of the nickel phosphorus catalyst according to any one of claims 9 to 13, as a catalyst of a hydrogenation, hydrodeoxygenation, hydrogenolysis, decarbonylation, and/or dehydration reaction of oxygen containing bio-feeds, preferably as a catalyst of a hydrodeoxygenation reaction of oxygenated feeds.