NL2005292C2

NL2005292C2 - Process for the hydrotreatment of vegetal materials.

Info

Publication number: NL2005292C2
Application number: NL2005292A
Authority: NL
Inventors: Hero Jan Heeres; Robertus Hendrikus Venderbosch; Agnes Retno Ardiyanti; Vadim Yakovlev; Dmitry Ermakov; Sofia Khromova; Valentin Parmon
Original assignee: Btg Biomass Technology Group B V
Priority date: 2010-08-30
Filing date: 2010-08-30
Publication date: 2012-03-01

Description

PROCESS FOR THE HYDROTREATMENT OF VEGETAL MATERIALS

The present invention relates to a process for the hydrotreatment of a vegetable biomass, to a catalyst and 5 the use of the catalyst.

Being the only sustainable product containing carbon, biomass is the only alternative for fossil derived crude oil derivatives. Research on the use of biomass, particularly from vegetable sources, for first generation 10 biofuels is rapidly expanding (e.g. bio-ethanol from sugar sources and starches and bio-diesel from pure plant oils). Biomass, in particular the one consisting of ligno-cellulosic materials, is difficult to convert that easily into transportation fuels. Conventional refinery scales (up 15 to 100 t/hr crude oil equivalence) are preferable for economic reason, but problematic for biomass resources, as they are scattered and collection is difficult. In addition, various types of biomass are very different in structure and composition (accordingly the handling procedures have 20 continuously to be adapted), have a low energy density compared to many fossil resources, and often contain significant amounts of water and ash.

Such disadvantages can be overcome if the biomass is first de-centrally restructured, densified at a smaller 25 scale (say 2 to 10 t/hr) while the intermediate product can be transported to a large central processing unit where it is transformed to a more stable product (at a scale of say 50 to 200 t/hr). A potentially attractive technology for this purpose is fast pyrolysis. Fast pyrolysis is a process 30 in which organic materials are heated to 450 - 600 °C with a short temperature/time ramp, in absence of air. The meaning of a short temperature/time ramp depends on the type of material to be fast pyrolysed. Under these conditions, 2 organic vapours, permanent gases and charcoal are produced. The vapours are condensed to pyrolysis oil. Typically, 50 -75 wt. % of the feedstock is converted into pyrolysis oil. Fast pyrolysis transforms difficult-to-handle biomass of 5 different nature into a clean and uniform liquid, called pyrolysis oil. Pyrolysis oil (obtained by fast pyrolysis) can be used for the production of renewable/sustainable energy and chemicals. Its energy density is four to five times higher than wood, and more than tenfold for fluffy 10 agricultural residues. This offers important logistic advantages. Pyrolysis liquids contain negligible amounts of ash, and have a volumetric energetic density 5 to 20 times higher than the original biomass.

An indicator to assess the degree of mild 15 hydrogenation for the bio-oil (and possibly its use as a cofeed) is its tendency to produce coke, via the residue retained upon distillation, for example the 'Conradson Carbon Residue', or the 'Micron Carbon Residue Testing' (abbreviated CCR and MCRT, respectively). The CCR and the 20 MCRT both can measured via a Standard Test Method for

Conradson Carbon Residue (for example from the American National Standard Institute). Both of this carbon residues are given via a standard industrial coking test for characterizing the coke forming tendency. A similar analysis 25 can be carried out using thermogravimetric analysis (or thermal gravimetric analysis, 'TGA'), in which a sample of material is heated up to a temperature of 900°C under nitrogen in the absence of air while the weight of the remaining sample is continuously measured. The weight of the 30 residue remaining is referred to as the 'TGA residue'. In general, pyrolysis-oils show CCR values around 10 to 50 %, while CCR-values for Fluid Catalytic Cracking (FCC) feed generally < 5 wt. %. Pure pyrolysis oils are immiscible with 3 conventional crude oil derivatives, and cannot be processed in FCC units due to the large CCR value. Products from mild hydrotreatment (treatment with hydrogen) are reportedly to be distillable, with no significant coke formation, and co-5 processing in a laboratory FCC facility (designated as'Micro Activity Testing' or MAT) with aromatic hydrocarbonaceous feedstocks is successfully demonstrated.

Several processes for upgrading the pyrolysis oil have been proposed in the literature. Examples of these 10 processes include hydrogenation under hydrogen pressures, Catalytic Cracking and a High Pressure Thermal Treatment (HPTT). These upgrading processes for the pyrolysis oil may involve, for instance, removal of the oxygen (usually >95%), decarboxylation, viscosity reduction, sulphur removal, 15 nitrogen removal, and the like. Existing processes include the hydrodeoxygenation of bio-oil, (HDO), in which a simultaneous hydrogenation, deoxygenation and cracking takes place. These processes apparently reguire high pressures of hydrogen, for instance, in the range of 50 bar to 350 bar 20 and temperatures ranging from 50 up to 450°C, for the removal of oxygen from the pyrolysis oil in the form of water, CO or CO2 (COx) , with a long multi-step hydrodeoxygenation to achieve significant (-95%) oxygen removal, whereas significant methanation due to the presence of COx also leads 25 to high hydrogen consumption. These processes entail very high hydrogen consumption, which makes them uneconomical and difficult to carry out.

Pure pyrolysis oils are immiscible with conventional crude oil derivatives, and cannot be processed 30 in FCC units due to the large CCR value. After hydrotreatment, however (up to 25 wt. % oxygen), coprocessing in a small FCC (MAT) facility with aromatic hydrocarbonaceous feedstocks is successfully demonstrated, 4 producing bio-gasoline with high RON value, meeting EU specifications. Fluid Catalytic Cracking of hydrogenated oils affects the way the oxygen is removed, viz. by decarboxylation rather than dehydration, while coke is 5 formed together with additional water.

US2009253948 discloses a method of conversion of pyrolysis oils to hydrocarbon products, first by partial hydrotreatment over a hydrotreatment catalyst such as Nickel or Nickel/Molybdenum on a high surface area support or Pt 10 and/or Pd dispersed on gamma-alumina or activated carbon, followed by separation of the partially deoxygenated oil stream to separate a hydrocarbon stream, and finally by full hydrotreating of the hydrocarbon stream in the presence of a hydrocracking catalyst. Another example includes Re-15 containing catalysts used for the hydrogenolysis of 6 carbon sugar, 6 carbon sugar alcohols and glycerol disclosed in US6841085. US7425657 further provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Using Re, Ru or Pd or any other noble metal as active 20 material, though, renders the catalyst very expensive.

A problem with the catalysts known from the conventional refinery processes, such as Nickel/Molybdenum or Cobalt/Molybdenum on alumina supports, is that they are not meant to handle high water contents, however high water 25 content are common in pyrolysis oils. Usually catalysts applied are designated as supported catalysts, viz. limited amounts of active components are impregnated on porous support materials such as A1203, Si02, and alike. The method of impregnation usually is of a wet-type, in which water-30 soluble active components are deposit on the envisaged catalyst support. Consequently, those catalysts will decay under reaction conditions, wherein a large amount of water is present and rather high temperatures are applied. In 5 addition, experiments also showed that due to the tendency of pyrolysis oils to form coke, porous catalysts, prepared by impregnation of active metals on a porous support material, causes part of the (initially) high internal 5 surface area to be come inaccessible for the reactant. All this may lead to quick catalyst inactivation, as the catalyst support disintegrates, leaching of active components into the water takes place, rendering the catalyst inactive and clogging catalyst pores, and / or 10 clogging of the reactor, and / or severe char formation that will lead to pressure build-up in the reactor. A lower temperature for the hydrogenation reaction is profitable, as deactivation of the catalyst is less pronounced at lower temperatures. Hence, while some processes for upgrading the 15 pyrolysis oil to produce hydrocarbon products have been disclosed, there is a need for catalyst as well as for process improvements for conversion of pyrolysis oils into useful (and more stable) products.

Accordingly, there is a continuous need in the 20 prior art to provide better treatments for biomasses coming from vegetable sources which are easier to carry out and/or can be carried out in a shorter amount of time, and / or at less severe conditions (namely high temperatures).

It is a goal of the present invention, amongst 25 others, to provide an improved process and an improved catalyst for treating vegetable biomasses, which does not present these drawbacks, but renders a product that is better suited for further processing. The present invention relates to a process for the hydrotreatment of a vegetable 30 biomass comprising contacting said vegetable biomass with a mixed metal oxide or metal-metalloid oxide catalyst comprising nickel and at least one other element chosen from a group 6 and/or 8 and/or 9 and/or 10 and/or 11 metal and/or β at least one group 13 element, in an aqueous medium at a pressure in the range of 10 to 400 bar and at a temperature in the range of 50 °C to 450 °C until a predetermined level of hydrotreatment of said biomass is obtained. The treated 5 biomass has better characteristics than the original biomass, such as, but not limited to, lower TGA-residue for the product, inhibited deactivation of the catalyst, promotion of hydrogenation reaction while suppressing repolymerisation reactions.

10 A biomass is to be understood as being a carbohydrate such as a lipid material (such as oil or fat) or such as a material containing lignitic hemicellulose and/or lignitic cellulose ('lignocellulosic materials') and can contain sugars or starch. The biomass has a vegetal, or 15 vegetable, origin (any type of plant) and can accordingly be a triglyceride, a vegetable fats, a vegetable oil. They can also contain free fatty acids, mono- and di- glycerides, and unsaponifiable lipids.

The aqueous medium is to be understood as any 20 suitable aqueous medium (such as, but not limited by, distilled water, de-ionised water, de-gazed water). The aqueous medium can be any water content and may be at least partly provided by the vegetable biomass.

According to the present invention, a mixed metal 25 oxide catalyst is a catalyst comprising at least two different metals, one of them being nickel. The mixed metal oxide can be designated by the oxide of the formula: NiM1, wherein M1 is one or more subsequent different metals (the catalyst can also comprise three, four, five or six 30 different metals in total) . The above-mentioned formula can also be applied where one of M corresponds to a metalloid, namely boron. In this case, the catalyst is a metal-metalloid oxide (comprising nickel and boron, or 7 additionally contain one, two, three, four or five other metals) .

Groups 6, 8, 9, 10, 11 and 13 refer to the IUPAC periodic table nomenclature to designate the elements in the 5 respective column. When referring to an element, it is understood an element of the periodic table. According to the invention, group 6 designates the elements Cr and/or Mo and/or W, group 8 designates the elements Fe and/or Ru and/ or Os. Group 9 designates the elements Co and/or Rh, and/or 10 Ir. Group 10 designates the element Pd. Group 11 designates the element Cu. Group 13 designates the elements B and/or A1 and/or Ga and/or In and/or Tl.

As an active metal Ni is known to have a high hydrogenation activity, and is a potential active metal for 15 hydrotreatment. However, Ni alone (on silicium oxide, γ- or δ-alumina, or any other type of stabilizer or support at the high temperature and pressures applied here) is not suitable to be used as a hydrogenation catalyst. There are basically two reasons: 1) the high reduction temperature required to 20 achieve the reduced state (700 °C is required to achieve complete reduction), and 2) deactivation via char deposition ("coking"). Coking is a general problem found in transition catalyst, such as Fe, Co, Ni. The carbon deposition can block the nickel surface, or the pore mouths, and this 25 second case can also produce physical breakdown of the catalyst support. The morphology of the carbon has been identified as well-ordered graphitic deposits, carbon whiskers, non-oriented deposits, or various carbides. Also for this reason, Ni is often used as catalyst for formation 30 of carbon nanofibers and nanotubes.

These two drawbacks regarding the use of Ni can be solved by the present invention by using another element, metal or non-metal, also designated as a promoter, by the 8 preparation of such a catalyst with a higher amount of active metals to promote the hydrogenation of the oil, and by selecting the best suitable catalyst binder. An additional advantage using such catalysts is that, as the 5 extent of the, likely thermally induced, repolymerisation reactions are reduced and the hydrogenation reactions are promoted. Promoting of hydrogenation reaction instead of repolymerisation also lead to limited formation of carbon-oxides (CO and C02) , consequently limiting the amount of 10 methane formed and thus the hydrogen consumption. Finally, promoting hydrogenation over repolymerisation yields product streams, which are much less viscous than products derived from conventional catalysts such as conventional Nickel/Molybdenum catalyst on a Al203-support.

15 According to the processes of the present invention, the hydrotreatment is a treatment with hydrogen (H2) . It can be a hydrogenation or a hydrodeoxygenation (also designated by the abbreviation HDO). In the processes according to the present invention, the contacting between 20 the catalyst and the biomass and/or the gaseous hydrogen can be done, for example by stirring in well-known stirred tank reactors. In the process of the present invention, the stirring can be carried out by mechanical stirring or magnetical stirring, or by passing the oil over the catalyst 25 bed in a packed bed mode. The reactors used in the process according to the present invention can be any suitable reactor, such as an autoclave.

The gaseous hydrogen can be designated by H2. It can be pure or mixed with another gas such as CO or C02 or 30 CH4, or recycle gas from the process, in which gaseous products derived from the process (CO, C02 and CH4) can be concentrated. The feed of gaseous hydrogen can be for example continuous until completion of the treatment.

9

Maintaining the gaseous hydrogen feed continuous is to be understood as keeping the feed of gaseous hydrogen in order to continuously feed the reactor with hydrogen and accordingly keep the pressure of hydrogen constant in the 5 reactor, until the end of the treatment.

The temperature is in the range of 50 C to 450°C, such as any temperature above 50°C, such as any temperature below 450 C, such as equal to or below 400°C. The pressure is in the range of 10 bar to 400 bar, such as any pressure 10 above 10 bar, such as any pressure below 350 bar or below 300 bar. The predetermined level of hydrotreatment defines the completion of the hydrotreatment reaction. It is to be understood as the moment in time, wherein the desired yield of hydrogenation is achieved determined by favorable product 15 characteristics here defined by the value for the CCR (and/or MCRT, and/or residue) below < 10%.

The treated biomass can be obtained at the end of the treatment by a subsequent isolation step and/or a purification step, for example by distillation, and /or by 20 phase separation, and/or sedimentation and/or filtration and/or chromatography.

According to the process of the present invention, the mixed metal oxide or metal-metalloid oxide catalyst comprises nickel and at least one element chosen 25 from the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In, Tl. The catalyst can be represented by the oxide of the elements with the general formula:

NinMi^n wherein M at least one of the element chosen from 30 the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In, Tl and 0.01<n<0.99. M can be more than one element, such as two elements, three elements, four elements, five elements of the periodic table.

10

According to process of the present invention, the original biomass is pretreated, before carrying out the process of the present invention, at a temperature ranging 200 °C to 800 °C, preferably 300°C to 700°C, more preferably 5 450°C to 650°C, such as below 650°C, such as above 450°C, in absence of air. This is also designated as pretreatment.

This pretreatment is also designated as pyrolysis. It can be a fast pyrolysis. The resulting product (pretreated vegetable biomass) is also designated as pyrolysis oil.

10 According to the process of the present invention, the catalyst comprises a stabilizing agent.

According to the present invention, the catalyst comprise a stabilizing agent in amount of not more than 30 % by mass, such as 1%, 2%, 3%, 4%, 5%, 6%, 8%, 9%, 10%, 12%, 15 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30% by mass of the catalyst and/or is chosen from the group AI2O3, or SiC>2, or Zr02, or CeÜ2, or T1O2, or Cr2C>3, or M0O2, or WO2, or V2O5, or MnC>2.

According to a preferred embodiment of the 20 present invention, the vegetable biomass is derived from a material containing lignitic and/or hemi-cellulosic and/or cellulosic materials.

According to another preferred embodiment, the temperature is a temperature in the range of 50°C to 400°C, 25 such as 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95 °C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135 °C, 140 °C, 1450 C, 150°C, 155°C, 160°C, 165°C, 160°C, 165 °C, 17 0 0 C, 1750 C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210 °C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 30 245°C, 250 °C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290 °C, 295°C, 300°C, 305°C, 310°C, 315°C, 320°C, 325 °C, 330 °C, 335 °C, 340°C, 345°C, 350°C, 355°C, 360°C, 365 °C, 3 70 °C, 3 75 °C, 380°C, 385°C, 390°C, 395°C, 400°C.

11

According to still another preferred embodiment of the present invention, the pressure of the process is a pressure in the range of 10 bar to 350 bar, such as 10 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar, 40 bar, 45 bar, 50 5 bar, 55 bar, 60 bar, 65 bar, 70 bar, 75 bar, 80 bar, 85 bar, 90 bar, 95 bar, 100 bar, 105 bar, 110 bar, 120 bar, 125 bar, 130 bar, 140 bar, 150 bar, 160 bar, 170 bar, 180 bar, 190 bar, 200 bar, 210 bar, 220 bar, 230 bar, 240 bar, 250 bar, 260 bar, 270 bar, 280 bar, 290 bar, 300 bar, 310 bar, 320 10 bar, 330 bar, 340bar, 350 bar.

According to another aspect, the present invention relates to a catalyst. The catalyst of the present invention comprises the oxide of nickel and at least one other element chosen from a group 6 and/or 8 and/or 9 and/or 15 10 and/or 11 metal and/or at least one group 13 element with the general formula: mJmo /=1 wherein Mi is the element different from Ni, n is n 1 < n < 5, and wherein the atomic ratio Ni / is in the /=1 20 range 0.01 to 99, preferably from 5 to 99, more preferably 9 to 99 .

n

The general formula Ni^M'O can also be /=1 designated by NinMi_n wherein M is at least one of the element chosen from the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In, 25 T1 and 0.01<n<0.99. M can be more than one element, such as two elements, three elements, four elements, five elements of the periodic table. With two elements or more, the formula can be Nin (M4M2) i_n, or Nin (M1M2M3) i_n, or Nin (M1M2M3M4) i_ n, or Nin(M1M2M3M4M5) i-n.

12

According to the present invention, the catalyst comprises nickel and at least two other elements chosen from a group 6 and/or 8 and/or 9 and/or 10 and/or 11 metal and/or at least one group 13 element, with the general formula: n

5 NiJ^M'O

(=1 wherein M1 is the element different from Ni, n is 1 ^ n ^ 5, n and wherein the atomic ratio Ni / is in the range 0.01 i=1 to 99, preferably from 5 to 99, more preferably 9 to 99.

According to the present invention, the catalyst 10 comprises at least one or two other element(s) is/are chosen from the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In, Tl.

According to the present invention, the catalyst comprises an oxide of NiCu, or an oxide of PdNi, or an oxide of NiB, an oxide of NiMo, an oxide of NiW, an oxide of 15 NiCuFe, an oxide of NiCuGa, an oxide of NiCuTl, an oxide of

NiCuB, and oxide of NiCuCo, an oxide of NiCoFe, an oxide of

PdNiCu, an oxide of NiMoW, an oxide of NiCuCoFe, an oxide of NiFelnGa,.

According to the present invention, the catalyst 20 comprises a stabilizing agent in amount of not more than 30 % by mass and/or is chosen from the group AI2O3, or S1O2, or

ZrC>2, or CeC>2, or T1O2, or Cr2C>3, or M0O2, or WO2, or V2O5, or

MnC>2.

When the catalyst according to the present 25 invention, used for treatment of vegetable biomasses in the presence hydrogen provide a better treatment of the vegetable biomass because it prevents the polymerization of said biomass and causes less methanation (also designated as production of methane) during the treatment, resulting in 30 obtaining a treated vegetable biomass product of higher quality .

13

According to yet another aspect of the present invention, the catalyst is used for hydrogenation or hydrodeoxygenation. A hydrogenation is a treatment with hydrogen. A hydrodeoxygenation (HDO) is a treatment with 5 hydrogen comprising the removal of oxygenated compounds from the treated products.

According to the present invention, catalyst is used for the hydrogenation or hydrodeoxygenation of organic materials. Organic materials are materials of any origin and 10 can be hydrocarbons, hydrocarbons with heteroatoms such as, but not limited to, N, O, S, F, Cl, Br.

According to the present invention, catalyst is used for the hydrogenation or hydrodeoxygenation of pyrolyzed organic materials.

15 According to the present invention, catalyst is used for the preparation of biofuels. Biofuels are a wide range of energy source derived from biomass. The term designates solid or liquid fuels (e.g. bioethanol, biodiesel) and various biogases. Bioethanol is an alcohol 20 made by fermenting the sugar components of plant materials and it is made mostly from sugar and starch crops. With advanced technology being developed, cellulosic biomass, such as trees and grasses, are also used as feedstocks for ethanol production. Biodiesel is made from vegetable oils, 25 animal fats or recycled greases. Biodiesel can be used as a fuel for vehicles in its pure form, but it is usually used as a diesel additive to reduce levels of particulates, carbon monoxide, and hydrocarbons from diesel-powered vehicles .

30 The present invention is further described, without being limited, by the following figures and

Examples .

14

Figures

Figure 1. vegetable biomass after the treatment according to the invention using supported and unsupported catalysts 5 Figure 2. Van Krevelen plot for various catalysts Figure 3. Conradson Carbon Residu (wt%) versus H2 consumption

Figure 4. (A) residue (wt%) for catalyst Ru/C and the catalyst NiCu; (B) average molecular weight of 10 final product (treated biomass)

Examples

Example 1 15 1 kg of commercial NiC03-mNi (OH) 2-nH20, 0.13 kg of

CuC03-mCu (OH) 2 and 0,313 1 of a 25% NH3 solution were added to 1.25 1 of water and stirred for 4 hr. Subsequently a 1.5 kg of solution, containing 0.66 kg of ethyl silicate in ethyl alcohol was added to the suspension and the obtained 20 solution was stirred for 4 hr. Then, during stirring, the solution was heated to 80°C until a viscous mixture was formed. This mixture was dried at 120 °C for 4 hr during which a light-green solid was obtained. Next, the resulting catalyst is calcined, while increasing the temperature from 25 room temperature to 400°C with the heating rate of 5°C/min, and keeping it at 400°C for a further 2 hr. After that the material is cooled down to the room temperature, leaving approx. 0.9 kg. Finally the catalyst is pressed into tablets, with size 10 x 4 mm. The pressure applied was 30 approx 3000 kg for each tablet, yielding the 'unsupported catalyst' being referred to in the latter examples.

15

The packed bed was filled with approx. 150 gram of this crushed unsupported catalyst, after being conditioned for another 4 hours at 650°C under air. The bed of catalyst was firstly activated by passing hydrogen over the bed for 2 h, 5 at pressures up to 5 bar, and temperatures of 350°C. Hydrogen (5.0 quality) was obtained from Indugas.

Example 2 A vegetable biomass, also designated as fast pyrolysis oil 10 (e.g. a wood oil, such as pine oil or palm oil), was hydrotreated in a 100-mL batch autoclave setup (Buchi AG), with a maximum pressure and temperature of 350 bar and 450 °C, respectively. The temperature of the system was controlled using an electric heating mantle combined with a 15 cooling spiral using water. The reactor content was stirred at 1300 rpm with a magnetically driven gas-inducing impeller. The impeller was of the Rushton type with four blades (diameter=24 mm, height=12 mm, and thickness=5.5 mm). Temperature and pressure in the reactor vessel were measured 20 and monitored by a PC. The reactor was filled with fast pyrolysis oil (25 g) and the unsupported catalyst (1.25 g, 5 wt % on the basis of wet pyrolysis oil). Subsequently, the reactor was flushed with nitrogen gas and pressurized with 20 bar of hydrogen at room temperature. The reactor was 25 heated to the intended reaction temperature (250 or 350 °C) at a heating rate of 16 °C/min and kept at that temperature for the intended reaction time. The hydrogen pressure in the reactor was set to the predetermined value. The pressure during a run was kept constant by continuous feeding of 30 hydrogen. After completion of the reaction, typically 4 h, the reactor was cooled to ambient temperature. The pressure was recorded for mass balance calculations, and the gas phase was sampled intermittently. The liquid product, 16 consisting of a water phase and, depending on the catalyst and reaction temperature, one or two organic phases, was recovered the reactor using a syringe, and the liquid product was weighed. Subsequently, the reactor was rinsed 5 with acetone. The combined acetone fractions with suspended solids were filtered. After filtration, the filter was dried and weighed. The amount of solids minus the original catalyst intake was taken as the amount of solids formed during the hydrodeoxygenation (HDO) process.

10

Example 3

Experiments using supported and unsupported catalyst (PdNi and NiCu) are reported in the figures. Figure 1 shows the vegetable biomass after hydrogenation, showing that the 15 biomass at the bottom of the sample volume, with water floating on the top. Surprisingly, the biomass treated with unsupported catalyst (reference cat A and cat B which correspond to PdNi and NiCu respectively) is already much more clearer than those derived from supported catalysts, 20 indicating that much more hydrogenation occurred than repolymerisation. In addition, TGA values of the samples derived from PdNi or NiCu at these severe conditions are < 1 wt. % in comparison with values of > 5 wt. % for the Ru/C catalyst. Both of the biomasses treated with supported and 25 of unsupported catalysts are higher in density than water. The hydrogenation of the oil is thus much better, which is also elucidated in Figure 2, where in a well-known Van Krevelen plot (O/C versus H/C), it is shown that, at a similar oxygen content, the ratio of H/C is higher for the 30 unsupported catalyst.

Results show that hydrogenation rates are higher when using the process according to the invention. Additionally, repolymerisation is limited compared to Ru/C (see Figure 2).

17

Results show that residue tests using a thermogravimetric analysis technique show carbon residues of around 1%. Figure 3 shows the value for the TGA residue versus the remaining oxygen content in the treated oil. It is observed that less 5 residue is formed and the hydrogenation rate with the catalysts according to the present invention ( at 125°C and □ 350°C, respectively) is higher than for Ru/C catalyst. Figure 4 shows the comparison for unsupported catalyst NiCu and Ru/C. Figure 4(A) shows the TGA residue after 10 distillation of the final product (treated biomass) with the catalyst Ru/C and the catalyst according to the invention (NiCu). Figure 4 (B) shows the average molecular weight of the final product (treated biomass), determined by Gel Permeation Chromatography (GPC). Both, the TGA residue and 15 the molecular weight, are plotted as a function of the remaining oxygen content of the treated vegetable biomass.

The treated biomass has a oxygen content varying from almost 10 to up to 40%. In this range for the oxygen content the TGA residue shows a sharp increase in case of Ru/C as 20 catalyst, while in the present invention a constant TGA

residue value of around 5% is measured. Surprisingly, and not expected on basis of test carried out using other catalysts, already at less severe operating conditions, such as the low temperatures of 125°C and lower where the decay in 25 the catalyst and /or support is much less than at the higher temperatures, a significant reduction in the value for the TGA residue can already be achieved.

Also the molecular weight in case of Ru/C shows a significant increase from 400 up to 1000 Da in case of Ru/C 30 as catalyst, but a constant value over the oxygen content interval of 400-450 Da. It can be concluded from figure 4 that treating the biomass over Ru/C leads to significant polymerization next to hydrogenation, while the reaction 18 using the process according to the present invention do not show such a polymerization, indicating that for this unsupported catalyst hydrogenation of the vegetable biomass is the prominent reaction mechanism. Figure 4 (A) shows a 5 constant value for the residue almost independent of the oxygen content arrived at for the treated material, well below 10wt% of the total product weight. In comparison with Ru/C, a lower molecular weight of the plant oil can be observed in Figure 4 (B) when the hydrogenation is carried 10 out with the NiCu catalyst according to the process according to the invention.

Example 4

For the preparation of NiFeCu/Si02 catalyst, the appropriate 15 amounts of commercial NiC03 »mNi (OH) 2 ·ηΗ20, CuC03*mCu(OH)2,

Fe(SO4) 2 *7H20 and 25% NH3 solution were dissolved in water and stirred for 4 hr. Subsequently a solution of ethyl silicate in ethyl alcohol was added to the suspension and the obtained solution was stirred for 4 hr. Then, during 20 stirring, the solution was heated to 80°C until a viscous mixture was formed. This mixture was dried at 120 °C for 4 hr during which a solid was obtained. Next, the resulting catalyst is calcined, while increasing the temperature from room temperature to 400°C with the heating rate of 5°C/min, 25 and keeping it at 400°C for a further 2 hr. After that the material is cooled down to the room temperature. Finally the catalyst is pressed into tablets, with size 10 x 4 mm. The pressure applied was approx 3000 kg for each tablet, yielding the unsupported catalyst being referred to in the 30 latter examples. Then the catalyst was activated by reduction in Ar and H2 mixture (Ar : H2 = 1:1 vol.) at pressures up to 5 bar, and temperatures of 300°C.

19

The catalyst in the amount of 1 g was tested in the batch reactor at a hydrogen pressure of 170 bar, temperature 320° C and a reagent/catalyst ratio = 33 g/ g in the hydrodeoxygenation (HDO) of guaiacol (or 2-methoxyphenol, 5 compound, also designated by the formula CgH^OH)(OCH3) and derived from guaiacum or wood creosote).

The gas analyses (H2, CO, C02, CH4) were carried out using a Hromos GH-1000 GC equipped with a packed columns ('Silohrom" 10 and activated carbon). The liquid products were analysed using a Hromos GH-1000 GC equipped with a capillary column (Zebron ZB-1, stationary phase 100% dimethylpolysiloxane, 0.25 pm x 30 m) and a FID and by GC-MS using "Saturn" (Varian) equipped with the ion trap and capillary column HP-15 5 (stationary phase 5% phenyl - 95% dimethylpolysiloxane, 0.25 pm x 30 m).

Examples 5-13

Catalysts prepared by the same way than in Example 4, were 20 tested in guaiacol HDO in the same conditions.

Data on the composition, activity and selectivity of catalysts after 60 min. of the reaction, as well as their specific surface areas (BET) are given in Table 1.

25 Table 1.

Sbet/· Conversion, HDO,

Example Sample* m2/g % % 60% Ni 5% Fe 5 %Cu / 4 110 95 90 30% Si02 68% Ni 1% Ga 1% Cu / 5 216 97 81 30% Si02 40% Ni 25% Cu 5% T1 / 6 70 70 4 30% Cr203 20 60% Ni 10% Fe 5% Co 5% 7 Cu / 40 97 4 20% Si02 50% Ni 10% Co 10% Fe / 8 80 94 34 30% Ce02-Zr02 70% Ni 10% Cu 10% Co / 9 42 77 62 10% A1203 50% Fe 10% Ni 5% In 5% 10 81 65 35

Ga 10% Cu / 20% Ti02 60% Ni 5% Cu 5% Tl / 11 60 67 15 30% Mo02 60% Ni 9% Cu 1% B / 12 142 86 91 30% Si02 60% Ni 5% Cu 5% Fe/ 13 66 96 82 30% Zr02 - Si02 mass percents

The total conversion of guaiacol (XGUA, %) and HDO degree (HDO, %) were defined as follows: XOUA(%) = η°υΑ ~η°υΑ ·100 = χ·100

nGUA

η«υΑ.χ.2-Σ·νο, r Ση,-aU

HDO (%) =---i--100= 1—2- .100 nGUA ' X ' 2 nGUA ' X ' 2 5 V * where n<3UA and n<3UA- are initial and final concentrations of guaiacol in the liquid probe, ni - the molar concentration of o product i m the liquid probe, 1 - the number of 0 atoms in the molecule of product i in the liquid probe. The same 10 technique was applied to analyse the other model compounds (anisole etc.) .

21

Examples 14-18

The catalyst containing, wt. %: 60 Ni, 8 Cu, 2 Fe and 30 Si02 or Ce02 - Zr02, or Ce02, or Zr02, or Ti02, and Si02, prepared by the same way as described in Example 1) was reduced in a 5 hydrogen (hydrogen flow rate 10 1 / h) by raising the temperature up to 300°C with the heating rate of 10°C/min and kept at that temperature for 2 h. The amount of hydrogen was taken in excess over the amount required for the complete reduction of the active components of the catalyst.

10 The catalyst fraction 0.25 - 0.5 mm in the amount of 0.5 ml was tested in a flow fixed bed reactor at a hydrogen pressure of 10 bar, temperature of 300°C and load of LHSV = 6 h-1 in anisole HDO.

Data on the composition, activity and selectivity of 15 catalysts after 60 min. of the reaction, as well as their specific surface areas (BET) are given in Table 2.

Table2.

Sbet/

Example Sample Conversion, % HDO, % m2/g 14 NiCuFe/Ce02-Zr02 70 36 87 15 NiCuFe/Ce02 74 38 67 16 NiCuFe/ Zr02 73 41 92 17 NiCuFe/Ti02 31 28 56 18 NiCuFe/ Si02 259 65 89 20 The total conversion of guaiacol (Xguaa %) and HDO degree (HDO, %) were defined as in Examples 4-13.

Examples 19-22

The catalyst containing, wt. %: 60 Ni, 9 Cu, 1 Pd and 30 of 25 stabilizer, prepared by the same way as described in Example 4) was reduced in a hydrogen (hydrogen flow rate 10 1/h) by 22 raising the temperature up to 300°C with the heating rate of 10°C/min and kept at that temperature for 2 h. The amount of hydrogen was taken in excess over the amount required for the complete reduction of the active components of the 5 catalyst.

0.4 g of the catalyst was tested in a flow fixed bed reactor at a hydrogen pressure of 10 bar, temperature of 300°C and load of LHSV = 1 tT1 in anisole HDO. The main reaction products were benzene, toluene, methylcyclohexane and 10 cyclohexane.

Data on the composition, activity and selectivity of the catalysts, as well as their specific surface areas (BET) are given in Table 3.

15 Table 3.

Sbet I Conversion,

Example Sample* HDO, % m2/g % 19 NiCuPd / Si02 4ÏÏÖ 97 IÖÖ 20 NiCuPd / W02 ÏÏÖ 92 ÏÖÖ 21 NiCuPd / V205 76 86 79 22 NiCuPd / Mn02 70 72 81

The total conversion of guaiacol (XGUA, %) and HDO degree (HDO, %) were defined as in Examples 4 to 18.

20 Example 23 HDO reaction using pyrolysis oil (provided by VTT, Espoo, Finland) was performed in a batch reactor (Autoclave Engineers, USA) with the volume of 100 mL equipped with the electrical heating system, magnetic stirrer and a 25 temperature control thermocouple. A liquid feed system was applied to fill the reactor with the guaiacol after catalyst activation (without opening of the reactor) to avoid the 23 catalyst deactivation by contact with air. The operating conditions for the catalyst activation (reduction) were the following: the catalyst containing wt. %: 60 Ni, 5 Cu, 5 Fe and 30 Ce02 - Zr02, prepared by the same way as described in 5 Example 1 in the amount of 0.833 g was introduced to the reactor, the reactor was closed and pressurized to 10 bar with H2 at room temperature, then the reactor was heated up to 320°C with the heating rate of about 10 °C/min and the final temperature was kept for 30 min. After the reduction 10 the pressure was released, the reactor was cooled to room temperature and 25 mL of pyrolysis oil was fed through the feeding line. The temperature and hydrogen pressure was increased gradually until the condition 350°C of temperature and 200 bar of H2 pressure was reached. When the temperature 15 and pressure reached the specified values, the stirrer was switched on at 2000 rpm. The HDO reaction was carried out for 1 h in a batch mode (no H2 is fed to the system during reaction). After reaction (4 hr) the reactor was cooled to room temperature, the pressure was released and the liquid 20 and gas products were taken to the analysis. After the reaction the oxygen content in the products decreased from 40 wt. % (in the original oil) to 12 wt. %.

Example 24 25 The catalyst containing, wt. %: 50 Ni, 10 Cu, 10 Co and 30 of Si02, prepared by the same way as described in Example 4, was tested in HDO of pyrolysis oil under the same conditions as described in Example 23. After the reaction, the H/C atomic ratio of the products increased from 1.45 (in the original 30 oil) to 1.48 (in the treated product).

24

Example 25

The catalyst containing, wt. %: 60 Ni, 9 Cu, 1 B and 30 of AI2O3, prepared by the same way as described in Example 4, was tested in HDO of pyrolysis oil under the same conditions 5 as described in Example 23. After the reaction, the H/C atomic ratio of the products increased from 1.45 (in the original oil) to 1.52 (in the treated product).

Example 2 6 10 Hydrotreating of ethylcaprate was performed in a flow fixed bed reactor (internal diameter 5 mm) made of stainless steel, at a temperature of 260°C, H2 pressure of 50 bar. Before the actual reactions, the catalyst was reduced prior to use (T = 300°C under 10 bar H2 for 2h). The catalyst used 15 was wt. %: 55 Ni, 10 Cu, 5 Fe and 30 of Zr02, prepared by the same way as described in Example 1. The HDO degree was 97 %, conversion degree - 100%. The main products were nonane (selectivity 96 %) and decyl alcohol (selectivity 3 %).

As can be seen from the above examples, the proposed 20 catalysts allows to obtain high yields of products with the low oxygen content in the process of treatment of oxygen containing organic materials derived from plant biomass, primarily phenol derivatives - products of fast pyrolysis of wood. Another advantage of the claimed catalyst systems is 25 that the catalysts do not contain sulfur, thus enhancing the stability of these systems in processes of oxygen-containing organic materials with low sulfur content.

Claims

Method for the hydrotreating of a vegetable biomass, comprising contacting the vegetable biomass with a mixed metal oxide or a metal-metallorde oxide catalyst, comprising nickel and at least one other element selected from a group 6 and / or 8 and / or 9 and / or 10 and / or 11 metal and / or at least one group 13 element, in an aqueous medium at a pressure in the range 10 from 10 to 400 bar and at a temperature in the range of 50 ° C to 450 ° C until a predetermined level of hydrotreatment of the biomass is achieved.

The method of claim 1, wherein the mixed metal oxide or metal-metalloid oxide catalyst comprises nickel and at least one element selected from the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In , T1.

The method of claim 1 or 2, wherein the catalyst comprises a stabilizer.

The process according to any of claims 1 to 20, wherein the catalyst comprises a stabilizer in an amount of no more than 30 mass% of the catalyst and / or is selected from the group, Al 2 O 3, SiC> 2, ZrC > 2, CeC> 2, T102, Cr2C> 3, MO2, WO2, V2O5, MnC> 2 in an amount of no more than 30% by mass. 25

The method according to any of claims 1 to 4, wherein the vegetable biomass is pretreated at a temperature in the range of 200 ° C to 800 ° C, preferably in the range of 300 ° C to 700 ° C, more preferably in the range 450 ° C to 650 ° C, mainly in the absence of air.

The method according to any of claims 1 to 5, wherein the vegetable biomass is derived from a material containing wood dust and / or hemi-cellulosic material and / or cellulosic material.

The method of any one of claims 1 to 6, wherein the temperature is in the range of 50 ° C to 5 with 400 ° C.

The method according to any of claims 1 to 7, wherein the pressure is in the range of 10 bar to 350 bar.

A catalyst as defined in any one of claims 1 to 8, comprising nickel and at least one other element selected from a group 6 and / or 8 and / or 9 and / or 10 and / or 11 metal and / or at least one group 13 element, according to the general formula: n Ni ^ M'0 iDl r where Mi is the element other than Ni, η 1 <n ^ 5, and n where the atomic ratio Ni / in the range of iD1 is 0.01 to 99, preferably in the range of 5 to 99, more preferably in the range of 9 to 99.

The catalyst according to claim 9, wherein the catalyst comprises nickel and at least two other elements selected from a group 6 and / or 8 and / or 9 and / or 10 and / or 11 metal and / or at least one group 13 element , with the general formula: 25 γίγ ^ Μ'0 iDl r where Mi is the element other than Ni, where η is 1 ^ n ^ 5 n, and where the atomic ratio Ni / ΣΜ1 is in the range (□ 1 of 0.01 up to and including 99, preferably in the range of 5 to 99, more preferably in the range of 9 to 9 9.

A catalyst according to claim 9 or 10, wherein the at least one element or at least two other elements is / are selected from the group Mo, W, Fe, Co, Pd, Cu, B, Al, Ga, In, Tl.

The mixed metal oxide or metal-metalloid oxide catalyst according to any of claims 9 to 11, wherein the catalyst is an oxide of NiCu, or an oxide of PdNi, or an oxide of NiB, or an oxide of NiMo , or an oxide of NiW, or an oxide of NiCuFe, or an oxide of NiCuGa, or an oxide of NiCuT1, or an oxide or PdNiCu, or an oxide of NiCuB, or an oxide of NiCuFo, or an oxide of NiCoFe, or an oxide of NiMoW, or an oxide of NiCuCoFe, or an oxide of NiFelnGa.

13. Mixed metal oxide or metal-metalloid oxide catalyst according to any one of claims 9 to 12, wherein the catalyst comprises a stabilizer in an amount of no more than 30 mass% of the catalyst and / or is selected from the group comprising Al 2 O 3, SiO 2, ZrO 2, CeO 2, TiO 2, Cr 2 O 3, MoO 2, WO 2, V 2 O 5, MnO 2.

14. Use of the catalyst according to any of claims 9 to 13 for the hydrogenation or hydrodeoxygenation.

Use of the catalyst according to one of claims 9 to 13 for the hydrogenation or hydrodeoxygenation of organic materials.

Use of the catalyst according to any of claims 9 to 13 for the hydrogenation of pyrolyzed organic materials.

Use of the catalyst according to one of claims 9 to 13 for the preparation of biofuels.