WO2014001633A1 - Process for producing hydrocarbons - Google Patents

Abstract

The present invention relates to a process for converting of pyrolysis oil and crude tall oil, comprising the stages where feed comprising pyrolysis oil and crude tall oil is subjected to hydroprocessing under hydroprocessing conditions in the presence of hydrogen and at least one hydroprocessing catalyst whereby an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range is obtained. The invention also relates to hydrocarbon components useful as transportation fuel or as a blending component in transportation fuel, obtainable by said process.

Description

PROCESS FOR PRODUCI NG HYDROCARBONS

Fl ELD OF THE I NVENTI ON

The present invention relates to the converting of pyrolysis oil and crude tall oil, whereby liquid fuels, fine chemicals, solvents and building-block chemicals may be obtained, and particularly the present invention relates to co-processing of pyrolysis oil with crude tall oil under hydroprocessing conditions to yield liquid fuels. The invention also relates to liquid fuels, fine chemicals, solvents and building-block chemicals obtainable by said process.

BACKGROUND OF THE I NVENTI ON

There is an increasing need for biofuels, suitable as liquid fuels as such, and particularly as transportation fuels, or compatible with said fuels. Pyrolysis oils obtainable by conversion of biomass have become an object of growing interest as alternative sources of fuels.

Pyrolysis is generally understood as the chemical decomposition of organic materials by heating in the complete absence or with limited supply of oxidizing agent such as air or oxygen. Pyrolysis can be used for converting biomass materials to pyrolysis oil, which is also sometimes called also bio-oil. Commercial pyrolysis applications are either focused on the production of charcoal (slow pyrolysis) or production of a liquid product (fast pyrolysis), the pyrolysis oil. Both the slow pyrolysis and the fast pyrolysis processes may be used for the manufacture of pyrolysis oil, which is potentially interesting for a substitute for fuel oil and as a feedstock for the production of synthetic fuels, such as gasoline, kerosene, jet fuel and diesel fuel.

During pyrolysis of biomass, for example lignocellulosic material, carried out at temperatures in the range 400-700°C, typically most of the cellulose and hem icellulose and part of the lignin disintegrate to form smaller and lighter molecules which are vapors at the pyrolysis temperature. During cooling some of the vapors condense to form a liquid product, called pyrolysis oil. The remaining part of the biomass, in this example mainly parts of the lignin, is left as a solid i.e. the charcoal.

Several methods have been proposed for the manufacture of pyrolysis oils by the conversion of biomass and waste liquids for producing renewable liquid fuels suitable for use in boilers, gas turbines and diesel engines, as well as for gasoline, kerosene and jet fuel use.

In fast pyrolysis the biomass is rapidly heated and it decomposes to yield vapors, aerosols, and some charcoal-like char. The condensed vapors and aerosols are condensed to form pyrolysis oil that has a heating value that is about half of that of conventional fuel oil.

Depending on the feedstock, fast pyrolysis produces about 60-75 w% of liquid pyrolysis oil, 15-25 w% of solid char and 10-20 w% of non-condensable gases. Slow pyrolysis, carried out at about 500°C for 5 to 30 minutes, produces about 30 w% of pyrolysis liquid, about 35 w% of non-condensable gases and about 35 w% of char. Pyrolysis oil is a chemically complex mixture of compounds, typically comprising water, light volatiles and non-volatiles. Pyrolysis oil is highly acidic, which may lead to corrosion problems, it has substantial water content of approximately 15 to 30 w%, variable viscosity and high oxygen content of around 45 w%. High concentration of oxygenates (oxygen containing compounds) and water have negative impact if pyrolysis oil is used as fuel.

Pyrolysis oil contains insignificant amounts of sulfur if any, but due to its instability pyrolysis oil is often difficult to use as such. It can be used to replace heavy heating oil in, for example, industrial boilers, but in order to be able to use it as transportation fuel it needs to be upgraded or processed further. Therefore several processes for additional processing of pyrolysis oil have been suggested in the art.

Pyrolysis oil is typically upgraded with catalytic hydrodeoxygenation at high hydrogen pressures and temperatures, in the presence of supported sulphided catalysts such as Al₂0₃ supported NiMo and CoMo. These catalysts are sensible to water present and/or generated during the process, and also to alkali metals, and their use requires the addition of sulphur containing compounds to the feed.

US 2011/0119994 relates to catalytic hydrotreatm ent of pyrolysis oil where feed comprising pyrolysis oil is subjected to a hydrodeoxygenation step in the presence of a catalyst. Patent US 7,578,927 discloses diesel production from pyrolytic lignin where pyrolytic lignin is hydrotreated in a hydrocracking unit in the presence of a catalyst. In US 4,795,841 pyrolysate oil is exposed to hydrogen gas and a suitable catalyst at a temperature in the range of 250 to 300°C. A process for converting pyrolysis oil by alcoholysis of pyrolysis oil, followed by hydrotreatment to transportation fuel is presented in US 2012/0035404 A1.

Crude tall oil (CTO) is generally known as a product which is derived from pulping of coniferous wood. Tall oil is the third largest chemical by-product in a Kraft mill. It finds use for example as a component of adhesives, rubbers, inks and emulsifiers, as well as a component in oil drilling fluids. CTO is typically composed of both saturated and unsaturated oxygen-containing organic compounds such as rosins, unsaponifiables, sterols, resin acids, fatty acids, fatty alcohols, sterols and other alkyl hydrocarbon derivatives. The processing of the wood causes break down of the triglyceride structures and hence CTO does not contain any significant amounts of triglycerides. Typically, CTO contains minor amounts of impurities such as inorganic sulphur compounds, residual metals such as Na, K, Ca and phosphorus. The composition of the CTO varies depending on the specific wood species.

Despite of the ongoing research and development of processes for the manufacture and upgrading of pyrolysis oil, there is still a need to provide an improved process for converting pyrolysis oil to liquid fuels and to utilize pyrolysis oil and CTO, originating from renewable sources in the manufacture of liquid fuels. There is also an increasing need for fine chemicals, solvents and building-block chemicals, originating partly or completely from biomass. SUMMARY OF THE I NVENTI ON

The present invention relates to a process for producing hydrocarbons and particularly to converting of pyrolysis oil and crude tall oil, whereby liquid fuels, fine chemicals, solvents and building-block chemicals may be obtained. The invention also relates to, co-processing of pyrolysis oil with crude tall oil under hydroprocessing conditions to yield liquid fuels. Particularly the present invention relates to a process for the manufacture of liquid fuels, where pyrolysis oil is co-processed together with crude tall oil. Said liquid fuels may suitably be used as transportation fuels or as blending stocks or components in said fuels. Further, a process is provided where pyrolysis oil is co-processed with crude tall under hydroprocessing conditions to yield liquid fuels.

The process for converting of pyrolysis oil and crude tall oil comprises the stage where feed comprising pyrolysis oil and crude tall oil is subjected to hydroprocessing under hydroprocessing conditions in the presence of hydrogen and at least one hydroprocessing catalyst whereby an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range is obtained. Further the invention provides a process for producing transportation fuels, such as gasoline, kerosene, jet fuel, diesel oil, or blending component useful in transportation fuels, as well as a process for producing heating oil, solvents, fine chemicals and building-block chemicals. The present invention also relates to products obtainable by said process.

Thus an object of the invention is to provide a process for effectively and economically processing feed comprising pyrolysis oil originating from biomass and crude tall oil, to provide more valuable components, particularly to provide liquid fuels, suitably transportation fuels and blending components for said fuels, as well as heating oil, solvents, fine chemicals and chemical building-blocks.

Another object of the invention is to provide an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range, which may be separated to fractions boiling in the transportation fuel range, in the heating oil range, in the solvent range, and to fractions which may be processed further to other valuable components.

Another object of the invention is to provide thermally stable and fungible liquid fuels based at least partly on renewable starting materials, whereby said fuels are C0₂ neutral and contain only very low amounts of bonded sulfur and nitrogen, if any.

Another object of the invention is to provide thermally stable and fungible solvents, fine chemicals and building-block chemicals based at least partly on renewable starting materials, whereby said components are C0₂ neutral and contain only very low amounts of bonded sulfur and nitrogen, if any.

DEFI NITIONS

The term "hydroprocessing" refers here to catalytic processing of organic material by all means of molecular hydrogen.

The term "hydrotreatment" refers here to a catalytic process, which typically removes oxygen from organic oxygen compounds as water (hydrodeoxygenation, HDO), sulphur from organic sulphur compounds as dihydrogen sulphide (hydrodesulphurisation, HDS), nitrogen from organic nitrogen compounds as ammonia (hydrodenitrogenation, HDN) and halogens, for example chlorine from organic chloride compounds as hydrochloric acid (hydrodechlorination, HDCI), typically under the influence of sulphided NiMo or sulphided CoMo catalysts.

The term "deoxygenation" refers here to the removal of oxygen from organic molecules, such as carboxylic acid derivatives, alcohols, ketones, aldehydes or ethers.

The term "decarboxylation" and/or "decarbonylation" refers here to the removal of carboxyl oxygen as C0₂ (decarboxylation) or as CO (decarbonylation) with or without the influence of molecular hydrogen. The term "hydrocracking" refers here to catalytic decomposition of organic hydrocarbon materials using molecular hydrogen at high pressures.

The term "hydrodewaxing" (HDW) refers here to catalytic treatment of organic hydrocarbon materials using molecular hydrogen at high pressures alter the structure of high molecular weight hydrocarbons by hydroisomerization, hydrodeoxygenation, hydrodearomatization and/or hydrocracking.

The term "hydrogenation" means here saturation of carbon-carbon double bonds by means of molecular hydrogen under the influence of a catalyst.

The term "building-block chemicals" refer to chemical compounds useful as starting materials and intermediates for the manufacture of chemical and pharmaceutical products. Examples of such building-block chemicals are fumaric acid, furfural, glycerol, citric acid, treonin, propanic acid etc.

The term "aqueous media" refers her to water, waste water streams, recirculated aqueous streams from the process of the invention or from another processes, aqueous solutions and aqueous emulsions. Said aqueous media is suitably free of metals and alkali metals and solid particles.

Transportation fuels refer here to fractions or cuts or blends of hydrocarbons having distillation curves standardized for fuels, such as for diesel fuel (middle distillate from 180 to 380°C, EN 590), gasoline (150 - 210°C, EN 228), aviation fuel (160 to 300°C, ASTM D- 1655 j et fuel) , kerosene, naphtha, etc. BRI EF DESCRI PTI ON OF THE DRAWI NGS

Fig. 1 is a schematic flow diagram representing one embodiment of the process, where pyrolysis oil is co-processed with crude tall oil in the hydroprocessing stage.

Fig 2 is a schematic flow diagram representing another embodiment of the process, where pyrolysis oil is subjected to prehydrogenation in two steps prior to the hydroprocessing stage.

Fig 3 is a schematic flow diagram representing another embodiment of the process where pyrolysis oil is subjected to pretreatment with an aqueous media, followed by prehydrogenation in one step prior to the hydroprocessing stage.

Fig 4 is a schematic flow diagram representing another embodiment of the process where pyrolysis oil is subjected to non-catalytic high temperature high pressure pretreatment followed by prehydrogenation in two steps prior to the hydroprocessing stage.

Fig 5 is a schematic flow diagram representing another embodiment of the process where pyrolysis oil is subjected to pretreatment with an aqueous media, followed non- catalytic high temperature high pressure pretreatment and then prehydrogenation in one step prior to the hydroprocessing stage.

Fig 6 illustrates examples (6a, 6b and 6c) of alternative catalyst arrangements in the hydroprocessing stage. Fig 7 presents graphically the water content of pyrolysis oil before and after treatment with an aqueous media.

Fig 8 presents graphically the densities of the aqueous phase and the organic phase after treatment of pyrolysis oil with an aqueous media.

Fig 9 presents graphically results from viscosity measurements of the organic phase after treatment of pyrolysis oil with an aqueous media.

DETAI LED DESCRI PTI ON OF THE I NVENTI ON

It was surprisingly found that pyrolysis oil can be co-processed with crude tall oil in a hydroprocessing stage, thus providing a convenient and efficient way to yield liquid fuels, even though the chemical compositions and properties of these starting materials are very different and further, they may vary to a significant extent from batch to batch. The process of the invention enables to convert compounds comprised in pyrolysis oil and crude tall oil to more valuable components with good yields. The process for converting of pyrolysis oil and crude tall oil comprises the stage where feed comprising pyrolysis oil and crude tall oil is subjected to hydroprocessing under hydroprocessing conditions in the presence of hydrogen and at least one hydroprocessing catalyst whereby an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range is obtained.

Crude tall oil (CTO) is added as co-feed to the hydroprocessing stage and it is co- processed in the hydroprocessing stage with the pyrolysis oil. Said pyrolysis oil may be subjected to one or more pretreatment steps prior to the hydroprocessing stage. Pyrolysis oil and crude tall oil may be fed to a hydroprocessing reactor using one feed inlet; suitably pyrolysis oil and crude tall oil are fed to the reactor using separate feed inlets, each for pyrolysis oil and for crude tall oil.

Hydroprocessing stage In the hydroprocessing stage feed comprising pyrolysis oil and crude tall oil is subjected to hydroprocessing in the presence of at least one hydroprocessing catalyst and hydrogen, whereby an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range is obtained. Said hydroprocessing may be carried out as hydrodewaxing (HDW), or as a combination of hydrodeoxygenation (HDO) and hydrodewaxing (HDW) and/or hydroisomerization. In the combination HDO and HDW/hydroisom erization may be carried out simultaneously, or consecutively where the HDO and HDW/hydroisomerization are performed separately. (This is illustrated in Figure 6) In the hydroprocessing stage mainly hydroisomerization, removal of heteroatoms, hydrodearomatization and/or hydrocracking is carried out.

The hydroprocessing catalyst may be arranged in at least one catalyst bed and/or in at least one reaction zone. The catalyst or catalysts may also be arranged in two or more catalyst beds and/or in two or more reaction zones, arranged in the same reactor or different reactors, or alternatively the catalysts may be mixed or combined and arranged in at least one catalyst bed and/or in at least one reaction zone. The temperatures in each catalyst bed and each reaction zone may be adjusted separately.

The hydroprocessing catalyst is selected from HDO catalysts and HDW catalysts and combinations thereof.

The HDO catalyst can be any hydroprocessing catalyst known in the art for the removal of hetero atoms (0, S, N) from organic compounds. Suitably the HDO catalyst is a supported catalysts comprising at least one metal of Group VIB or Group VIII of the Periodic table of elements. Suitably said metal is selected from cobalt (Co), molybdenum (Mo), nickel (Ni), tungsten (W), chromium (Cr), manganese (Mn), rhenium (Re), iron (Fe), osmium (Os), rhodium (Rh), ruthenium (Ru), copper impregnated chromium oxide (Cu/Cr), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten (NiMoW), nickel copper (NiCu). The support is suitably metal oxide, metal carbide or carbon, such as Al₂0₃, Ti203, Ce0₂, Zr0₂, Ce0₂-Zr0_2i and any combinations thereof. In an embodiment, the HDO catalyst is selected from a group consisting of NiMo, CoMo, and a mixture of Ni, Mo and Co. The support for the HDO catalyst can be an oxide which is typically used in the art as support for HDO catalyst, suitably the support is selected from Al₂0₃, Si0₂, Zr0₂, and mixtures thereof. In one embodiment, solid particles of NiMo/AI₂0₃ are used as HDO catalyst. The HDO catalyst is suitably sulphided prior to start up. Adequate sulphidation during operation is usually provided by adding sulphur in the feed material, however as crude tall oil (CTO) is used as co-feed, the feed itself may contain sufficient sulphur whereby no additional sulphur is needed.

The HDW catalyst may comprise any HDW catalyst known in the art, as well as catalysts used for isomerizing paraffinic hydrocarbons. Suitably the HDW catalyst comprises Group VIB metals, oxides and sulfides, and/or one or more Group VIII metal components and combinations thereof, on a support. Examples of suitable catalysts are catalysts comprising a molecular sieve or zeolite and/or a metal from Group VII and/or a carrier, such as SAPO-11 or SAP041 or ZSM-22 or ZSM-23 or zeolite-beta or Y-zeolite or ferrierite and Pt, Pd or Ni and Al₂0₃ or Si0₂. Examples of noble metal catalysts are Pt/SAPO-11 /Al₂0₃, Pt/ZSM-22/AI₂0₃, Pt/ZSM-23/AI₂0₃ and Pt/SAPO-11 / Si0_2, the use of which require the removal of sulphur compounds from the feed prior to contacting it with the catalyst and they suitably are arranged separated from NiMo and CoMo catalysts.

Also catalysts based on Ni, W and molecular sieves may be used as HDW catalysts. These catalysts require sulphidization. NiW has excellent isomerising and dearomatising properties and it also has the capacity of performing the hydrodeoxygenation and other hydroprocessing reactions of feed materials. The molecular sieves, such as porous refractory oxides comprise alumina, silica, beryllia, chromia, zirconia, titania, magnesia, thoria, also combinations of these refractory oxides such as silica-alumina and silica-titania are suitable support materials for NiW catalysts, optionally combined with zeolites. Group IMA metal-free crystalline silica molecular sieve (silicalite) which may form a portion of the support, may also be used. Another catalyst which can be used as the HDW catalyst is somewhat similar to the catalyst described above except that a crystalline aluminosilicate of the ZSM-5 type, preferably in an acidic form, is substituted in the support for the crystalline silica molecular sieve essentially free of Group IMA metals. The crystalline aluminosilicate zeolite may be ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and the like. Such zeolites are preferably utilized in the acid form by replacing at least some of the ion-exchanged metal cations in the zeolite with hydrogen ions. The support materials in the HDW catalysts may be the same as or different from those of the HDO catalyst. Said support may comprise an intimate mixture of a porous refractory oxide and a crystalline silica molecular sieve essentially free of aluminum and other Group IMA metals of the Periodic table of elements. The support for the HDW catalyst is suitably selected from Al₂0₃, Si0₂, Zr0₂, a zeolite, silica/alumina, and mixtures thereof. Suitably the HDW catalyst is selected from NiW/AI₂0₃ and NiW/zeolite/AI₂0₃. These HDW catalysts are well suited for mixing with the HDO catalyst since they also require sulphiding for proper catalytic activity. Thus hydrogenation, hydroisomerization, hydrodeoxygenation, dearom atization and hydrocracking may take place simultaneously.

In one embodiment, a catalyst bed may comprise a mixture of sulphided HDO and HDW catalysts, wherein the HDO catalyst is NiMo/AI₂0₃ and the HDW catalyst is NiW/zeolite/AI₂0₃. The NiMo/AI₂0₃ catalyst mainly serves the purpose of hydrogenation, hydrodeoxygenation, hydrodesulphurization and hydrodenitrification. The NiW/zeolite/AI₂0₃ catalyst mainly serves the purpose of hydroisomerization, hydrogenation, dearom atization and hydrocracking.NiW has also capacity for some hydrodeoxygenation, hydrodesulphurisation and hydrodenitrification.

The proportions of the catalysts may vary in the reactor e.g. in such a way that the proportion of the HDW catalyst grows towards the outlet end of the reactor/reactors. Some catalyst beds of the reactor may comprise only one or the other of the catalyst types, i.e. they comprise either HDO or HDW catalyst.

The catalysts may also be arranged in several reactors, arranged in consecutively in series.

Optionally one or more catalytically active guard-beds or a guard-bed reactors may be used upstream of the reactors for effecting the removal of metals, such as Al, Na and sulphur and/or phosphorus from the feed. The purpose of the guard bed/beds is to protect the catalyst(s) in the reactor/reactors from poisoning and fouling.

The hydroprocessing conditions refer here to a pressure from 5 to 350 bar and a temperature from 100 to 450°C.

Suitably at least one HDW catalyst is used, or alternatively a combination of HDW and HDO catalysts is used. The reaction conditions suitably include the temperature in the range between 200 and 450°C, particularly suitably between 250 and 390°C. The pressure (total pressure) in the reactor will normally be between about 10 to about 150 bar, suitably between 20 to 110 bar, particularly suitably between 50 to 100 bar. The rate at which the feedstock is passed through the reactor in contact with the catalyst particles is typically set at a LHSV (liquid hourly space velocity) between about 0.1 and about 10 hr¹. The feed rate WHSV (weight hourly spatial velocity) of the feed material varies between 0.1 and 5, and is suitably in the range of 0.2 - 0.7. The hydrogen flow rate is generally between 600 and 4000 Nl/I, suitably in the range of 1300-2200 Nl/I. Particularly suitably the range is 500-2500 Nl/I feed.

Pyrolysis oil is suitably co-processed with crude tall oil in an amount from 5 to 95 wt% of pyrolysis oil and from 95 to 5 wt% of crude tall oil, suitably the amount of pyrolysis oil may range from 5 to 75 wt% and from 95 to 25 wt% of crude tall oil, including the amount of the pyrolysis oil being between two of the following; 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 and 95 wt% ; and the amount of CTO being between two of the following; 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 and 95 wt%.

If the feed comprises a sufficient amount of sulphur compounds, there may be no need to add sulphur to the feedstock. Suitably the content of sulfur compounds in the feed is determined prior to the reaction, for calculating the amount of possibly required additional sulfur compound in the feed.

In order to retain the metal component of the catalyst in the sulphided form (if necessary) instead of converting back into the metal oxide form said feedstock may be contacted with the catalyst composition in the presence of hydrogen sulphide (H₂S) or a precursor thereof, such that said hydrogen sulphide is present in the hydrogen gas in an amount between 10 ppm and 10000 ppm, suitably between 10 ppm and 1000 ppm. This can be achieved for example by adding an organic sulphur compound to the feed, suitably DMDS (dimethyldisulphide) in amounts of 1 to 2 % by weight. The sulphur component may also originate from light gaseous components separated from the process and recycled.

Depending on the HDW catalyst and the catalyst arrangement it may be necessary to remove sulfur from the reaction mixture or effluent or product from the previous process step before subjecting to HDW, for example by stripping with water vapor or a suitable gas such as light hydrocarbon, nitrogen or hydrogen.

If desired, recirculation of at least a portion of the product stream and/or effluent gas provides an efficient means for constraining the exothermic reaction whereby the recycled streams act as media for lowering the temperature of the catalyst beds in a controlled manner.

A gaseous stream from the process, containing hydrogen may be cooled and then carbon monoxide, carbon dioxide, nitrogen, phosphorus and sulphur compounds, other impurities, and gaseous light hydrocarbons can be removed therefrom. After compressing, purified or recycled hydrogen can be returned the process steps needing hydrogen. Water removed from the condensed liquid may be used in the aqueous media in the optional pretreatment step. The liquid product (effluent) may suitably be cooled and directed to a separator. In the separator, water and light gases containing hydrogen, light hydrocarbons, H₂S, CO and C0₂ are separated from the product. Water and gases may also be separated by other means which are well known to those skilled in the art.

The light gases are suitably directed to an amine scrubber, which removes H₂S and C0₂ from the gaseous products. Scrubbed gases, comprising mainly hydrogen and some impurities, may be recycled to the process as feed hydrogen and quench gas. Light hydrocarbons may be directed to further processing to obtain gasoline etc.

The reaction products i.e. the hydrocarbon mixture from the separator, is suitably directed to fractionation, suitably to a fractionation column where different fuel grade hydrocarbon fractions are recovered. From the fractionation column, the heavier hydrocarbons may be recycled back to into the feed of the process if desired. Any suitable fractionation methods, such as distillation etc. may be used.

A middle distillate suitable as diesel fuel is suitably separated and the lighter hydrocarbons are directed to a stabilizer, where a naphtha fraction can be recovered. The middle distillate fraction comprises gas oil, i.e. a hydrocarbon fraction having a boiling point in the diesel range. The boiling range is from 160 to 380°C, meeting the specification of EN 590 diesel. The diesel product is fed to a diesel storage tank. Also hydrocarbon fractions distilling at temperatures ranging from 40 to 210°C and at a temperature of about 370 °C can be recovered. These fractions are useful as high quality gasoline fuel and/or naphtha fuel, or as blending components for these fuels. The hydrocarbon mixture obtained from the reactor system includes fuel grade hydrocarbons having a boiling point of at most 380°C according to ISO EN 3405. Additionally, fraction suitable as solvents, aviation fuels, kerosene etc. may be obtained. The obtained fractions may also be used without limitations as blending components, suitably in fuels derived from crude oil, mineral oil or renewable sources.

Feed

Pyrolysis oil may be obtainable from biomass using any suitable pyrolysis method known in the art. Pyrolysis oil refers here to a product obtained by pyrolysis at a temperature from 300 to 1000°C in the absence or with limited supply of an oxidizing agent, by slow pyrolysis or fast pyrolysis of starting material comprising biomass, which may typically comprise any of virgin materials, by-products and waste materials of plant origin, animal origin, fish origin or microbiological origin, or any combinations thereof. Suitably fast pyrolysis is used. Examples of said starting materials comprise virgin wood, wood residues, forest residues, waste, municipal waste, industrial waste or by-products, agricultural waste or by-products (including also dung or manure), residues or by-products of the wood-processing industry, waste or by-products of the food industry, solid or semi-solid organic residues of anaerobic or aerobic digestion, such as residues from bio-gas production from lignocellulosic and/or municipal waste material, or from bio-ethanol production process, and any combinations thereof. The starting material comprising biomass may optionally additionally comprise any other organic matter, such as polymeric or plastic waste originating from other sources.

Suitably biomass selected from non-edible resources such as non-edible wastes and non-edible plant materials is used for fuel production. Particularly suitably said biomass comprises virgin wood, wood waste and residues, and by-products of the wood-processing industry, such as slash, urban wood waste, lumber waste, wood chips, wood waste, sawdust, straw, firewood, wood materials, paper, by-products of the papermaking or timber processes, where the biomass (plant biomass) is composed of cellulose and hemicellulose, and lignin.

The pyrolysis oil, also called bio-oil, is typically a complex mixture of oxygen containing compounds (oxygenates), comprising typically water, light volatiles and non-volatiles. Pyrolysis oil is acidic, with a pH of 1.5- 3.8, wood based pyrolysis oil typically has pH between 2 and 3. The exact composition of pyrolysis oil depends on the biomass source and processing conditions. Typically pyrolysis oil comprises 20- 30 % of water, 22-36 % of suspended solids and pyrolitic lignin (including low molecular mass lignin and high molecular mass lignin), 8-12 % of hydroxyacetaldehyde, 3-8 % of levoglucosan, 4-8 % of acetic acid, 3-6 % of acetol, 1-2 % of cellubiosan, 1-2 % of glyoxal, 3-4 % of formaldehyde, and 3-6 % of formic acid by weight. Pyrolysis oil may also comprise other ketones, aldehydes, alcohols, furans, pyranes, sugars, organic acids, lignin fragments, phenolics, extractives and small amounts of inorganics. Pyrolysis oil may contain sugar compounds even 35 % by weight. The density of pyrolysis oil is approximately 1.2-1.3 kg/I and usually the water molecules which are split during pyrolysis stay bound within the complex pyrolysis liquid as an emulsion. The pyrolysis oil as such is immiscible in mineral oil and mineral oil derived products and it cannot be blended with solvents or oils having too low polarity. Crude tall oil (CTO) refers to a product which is mainly composed of both saturated and unsaturated oxygen-containing organic compounds such as rosins, unsaponifiables, sterols, resin acids (mainly abietic acid and its isomers), fatty acids (mainly linoleic acid, oleic acid and linolenic acid), fatty alcohols, sterols and other alkyl hydrocarbon derivatives. Typically, CTO contains minor amounts of impurities such as sulphur compounds, residual metals such as Na, K, Ca and phosphorus. The composition of the CTO varies depending on the specific wood species. CTO is derived from pulping of coniferous wood.

CTO is understood to refer here also to tall oil, tall oil components such as tall oil fatty acids (TOFA), tall oil derivatives such as tall oil resin acids, tall oil pitch and tall oil neutral substances, as well as any mixtures thereof. The fatty acids of tall oil include mainly palmitic acid, oleic acid and linoleic acid. Fractional distillation of tall oil provides rosin acids and further reduction of the rosin content provides tall oil fatty acids (TOFA) which consists mostly of oleic acid.

CTO may be purified using any methods, suitably using evaporative methods, where the purification process conditions are controlled in such a way that as much as possible of the neutral components of the tall oil are recovered. The evaporation may be carried out by using a heater and evaporator combination, where CTO is first heated up to a temperature of 150 to 230 °C at a pressure of 40 to 80 mbar. The gas phase containing CST (Crude Sulfate Turpentine) and water is separated and liquid phase is directed to an evaporator for further purification.

The purification may be performed by using two or three evaporators in the purification where the first evaporator is a thin film evaporator that operates at a temperature of 150 to 200 °C, and a pressure of 10 mbar. The gas phase containing CST and water is separated and led to water separation and CST purification.

In a purification using two evaporators, the liquid fraction from the first evaporator is led to a second evaporator. A thin film evaporator or plate molecular still can be used as the second evaporator. The second evaporator operates at a temperature of 300 to 390 °C and a pressure of 0.01 - 15 mbar. The distillate, i.e. purified CTO may be fed to the reactor system for catalytic treatment. In a purification using three evaporators, the liquid fraction from the first evaporator is led to a second evaporator, which is a thin film evaporator or a plate molecular still operating at a temperature of 200 - 280°C and a pressure of 5 mbar, and further to a third evaporator, which is a short path evaporator operating at a temperature of 250 - 300 °C and a pressure of 0.1 mbar. From the last evaporator, the distillate, i.e. purified CTO may be fed to the reactor system.

The content of harmful substances, such as metal ions, sulphur, phosphorus and lignin residues, is typically reduced by the purification. However, the sulphur content of CTO remains typically from 1000 to 5000 ppm after the purification. Light components, such as crude sulphate turpentine and heavy components such as tall oil pitch are removed and may be directed to another process for utilization. Said purified CTO material is particularly suitable for being subjected to catalytic treatment with hydrogen.

In the process of the invention crude tall oil can be co-processed with pyrolysis oil even though they differ significantly with respect to their chemical composition and in practice they are immiscible. Pyrolysis oils and components comprised therein generally have a high tendency to coke formation in hydroprocessing. Therefore catalysts having high activity for coke gasification reactions are used, and thus higher volumes of the pyrolysis oil can be co-processed with crude tall oil. Further, as pyrolysis oil is practically sulfur free it is very convenient to co-process it with crude tall oil comprising sulphur compounds, acting as sulphidizing agents and maintaining the catalyst active.

Co-processing of pyrolysis oil with crude tall oil reduces coking in the reactor. Unstable molecules comprising oxygen are removed from pyrolysis oil. The lignin fragment of pyrolysis oil, mainly comprising oxygen containing aromatics may be converted to a product comprising cyclic hydrocarbons. Oxygen may be completely removed at higher temperatures of 300 to 350°C and aromatic compounds are obtained. At lower temperatures the hydrogen consumption is higher, but the light hydrocarbons present in the feed act as hydrogen donors at said conditions, thus reducing the consumption of external hydrogen. Optional pretreatment of pyrolysis oil

Optionally the pyrolysis oil may be subjected to one or more pretreatment steps prior to the hydroprocessing stage described above. Said pretreatment steps may be selected from treatment with an aqueous media, high temperature high pressure treatment (HTHP), filtering, and extraction and combinations thereof. In the pretreatment steps, at least part of the impurities, such as solid materials and alkali metals may be removed conveniently. In the case the HTHP is used, it is carried out prior to the prehydrogenation steps, and in the case the treatment with an aqueous media is used, it is carried out before the HTHP.

Optional treatment with an aqueous media

Pyrolysis oil may be subjected to treatment with an aqueous media prior to the hydroprocessing stage or prior to any of the other possible pretreatment stages. Pyrolysis oil refers here to the product obtained from the pyrolysis of biomass and it typically contains water. In this pretreatment pyrolysis oil is contacted with an aqueous media whereby a mixture is formed. The aqueous media is suitably selected from water, waste water streams, recirculated aqueous streams, aqueous solutions and aqueous emulsions. The recirculated aqueous streams, aqueous solutions and aqueous emulsions may originate from the process of the invention, or from other processes or sources. The amount of the aqueous media is from 1 to 80 vol-%, suitably from 10 to 75 vol-%, particularly suitably from 30 to 60 vol-% and the amount of pyrolysis oil is from 20 to 99 vol-%, suitably from 25 to 90 vol-%, particularly suitably from 40 to 70 vol-%.

The obtained mixture, suitably having a temperature from 10 to 70°C, particularly suitably from 15 to 50°C, is agitated, suitably for 5 to 60 min and then it is allowed to settle whereby phases are formed. The organic (less polar) phase and the aqueous (more polar) phase are separated. In this step the amount of water in the original pyrolysis oil (prior to the second stage) is reduced, i.e. the pyrolysis oil is dried. The water content of the organic phase (pyrolysis oil treated with aqueous media) is lower than that of the pyrolysis oil used as feed in the second stage. For example, when the water content of original pyrolysis oil was 30 wt%, after the second stage it was 14 wt%. In the aqueous phase water soluble and water miscible organic compounds and inorganic compounds, salts are removed, particularly sugars such as glucose, xylose, arabinose, mannose, and galactose, organic acids, including glucuronic acid and galacturnic acid, aldehydes, ketones and some substituted phenols and cyclopentanones. The aqueous phase may be directed to further processing for converting the compounds therein to more valuable products, such as chemical building blocks, fine chemicals, fuels, or alternatively, it may at least partly be directed to recirculation to the optional pretreatment with aqueous media for use as the aqueous media. The organic phase (the pyrolysis oil treated with the aqueous media) containing organic compounds insoluble or immiscible in water, such as highly aromatic compounds, phenolic compounds, fragments of lignin, furfurals, toluene, substituted phenols, benzene derivatives, etc. may be directed to the hydroprocessing stage or to one or more pretreatment stages of the process.

In the treatment with aqueous media the selected ratio of the aqueous media to pyrolysis oil provides removal of desired amount of water and impurities. If too much of the aqueous media is used the organic phase (pyrolysis oil treated with aqueous media) is almost solid and the handling of it becomes difficult. If too little of the aqueous media is used the organic phase becomes very viscose, additionally the water soluble and water miscible compounds and impurities are not removed very effectively. The selected ratio achieves suitable removal of water, water soluble and water miscible organic compounds and impurities. Reduced water content and reduced levels of impurities are also particularly important for the subsequent hydroprocessing stage, where the hydroprocessing catalyst can thus be maintained active for longer periods of time. Naturally the original water content in the pyrolysis oil is taken into account when adding the aqueous media.

Water bound within the complex pyrolysis oil is separated very efficiently and to desired degree during the process. The separated water phase contains water- miscible and water-soluble compounds, for example formic acids, hydroxyl acids, alcohols, aldehydes, ketones and sugars, which would interfere in the subsequent hydroprocessing stage. Such compounds are now removed and they can be further processed to more valuable compounds.

The hydroprocessing catalysts stay active for longer periods of time and the process is more stable and easier to control.

Filtering and extraction pretreatment methods generally known in the art may also be used for pretreating the pyrolysis oil. During the process also light hydrocarbons such as methane, ethane and propane are removed as gases.

Optional high temperature high pressure treatment (HTHP)

Optionally the pyrolysis oil may be subjected to one or more pretreatment steps selected from treatment with aqueous media, filtering, and extraction prior to the HTHP treatment; thus the pyrolysis oil used as feed (starting material) in the HTHP stage refers also to pyrolysis oil subjected to one or more of said pretreatments. The optional high temperature high pressure treatment (HTHP) is a non-catalytic treatment comprising at least two steps where in the first step (a) of HTHP pyrolysis oil (meaning here also pyrolysis oil treated with aqueous media) is heated in the absence of added catalyst at 100°C to 200°C temperature and 50 bar to 250 bar pressure to yield product of the first step, and in the second step (b) of HTHP heating the product of the first step in the absence of added catalyst at 200°C to 400°C temperature and 50 bar to 250 bar pressure. HTHP-treated pyrolysis oil is obtained. HTHP is carried out prior to the optional prehydrogenation steps, but after optional treatment with aqueous media.

The term "non-catalytic" refers to a process where no heterogeneous or homogeneous catalyst is added to the process and where the reaction(s) take place in the absence of an added catalyst. Typically this means in practice that the reaction(s) take place, only between the materials fed into the reactor(s) and the reagents formed during the reaction(s), without a catalyst.

The temperature of the first step (a) of HTHP is adjusted to a temperature from 100°C to 200°C, suitably from 100°C to 150°C, including the temperature being between two of the following temperatures; 100°C, 105°C, 110°C, 120°C, 125°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C and 200 °C for the heating of the pyrolysis oil. At the same time the pressure is adjusted to a pressure from 50 bar to 250 bar, suitably from 150 bar to 200 bar, including the pressure being between two of the following pressures; 50 bar, 60 bar, 70 bar, 80 bar, 90 bar, 100 bar, 110 bar, 120 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 and 250 bar.

The temperature of a second later step (b) of HTHP is adjusted to a temperature from 200°C to 400°C, suitably from 300°C to 350°C, including the temperature being between two of the following temperatures; 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C and 400°C for the heating of the product of the first step (step a). At the same time the pressure is adjusted to a pressure of 50 bar to 250 bar, suitably 150 bar to 200 bar, including the pressure being between two of the following pressures; 50 bar, 60 bar, 70 bar, 80 bar, 90 bar, 100 bar, 110 bar, 120 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 and 250 bar. Typically the most reactive compounds react during the first step (a), but due to the low temperature during the first step there will be no significant coke formation. In the step for example acids, aldehydes, alcohols and/or sugars are hydrogenated. The higher temperatures of the second step (b) cause the more resistant compounds to react whereby oxygen is removed for example from lignin and/or lignin derived phenolics.

The heating rate of the first and second heating is typically between two of the following rates; 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 °C /min. The heating time of the first and second step depends on the heating rate and varies between two of the following periods of time; 20, 25, 30, 45, 60, 90, 120, 150 and 180 minutes. Heating is carried out using direct heat, heat exchangers etc.

The HTHP treatment may also be carried out under reducing conditions whereby a gas atmosphere comprising at least one of carbon monoxide, hydrogen, nitrogen or mixtures thereof are used. Accordingly at least one of the process steps a) or b) is performed under said a gas atmosphere. The use of CO typically causes decarbonylation and decarboxylation and eventually some hydrogenation and thermal cracking, and acid functionality breaks. Adding H₂ typically leads to the formation of methane and a larger amount of water; also hydrogenation reactions and thermal cracking, carbonylation, and decarboxylation takes place. The use of an inert N₂ atmosphere typically leads to less water being separated and causes thermal cracking and some hydrogenation and eventually decarboxylation and decarbonylation. Although H₂ is not added, the pyrolysis oil itself comprises enough hydrogen donors for enabling the reactions to take place.

The HTHP may optionally be carried out under alkaline conditions in the presence of at least one alkali metal hydroxide compound such as NaOH. The alkali metal compound is added to the feed to the HTHP treatment in an amount of 5 - 55 w%, suitably 10-40 w%, based on the organic material in the feed. This improves the depolymerization of lignin compounds, enhances the yields of the product and minimizes solids formation.

The product obtained from the HTHP pre-treatm ent may be directed to hydroprocessing or it may be subjected to prehydrogenation. Optional prehydrogenation

The optional prehydrogenation of the pyrolysis oil, organic phase (pyrolysis oil treated with an aqueous media) or HTHP-treated pyrolysis oil may be carried out in one step or in at least two steps in the presence of at least one hydrogenation catalyst and hydrogen, the first step under milder conditions and the second step under more severe conditions, whereby a prehydrogenated effluent is obtained. Said prehydrogenation may be carried out in a separate pressure vessel(s) or in the same pressure vessel as the hydroprocessing stage. In the case the prehydrogenation comprises more than one steps, each step may if desired, be carried out in separate pressure vessels.

In the case the prehydrogenation is carried out in one step, it may be carried out under a pressure 10 to 350 bar and at a temperature from 50 to 350°C.

If the prehydrogenation is carried out as a two-step hydrogenation, the first step is carried out under a pressure from 10 to 300 bar and at a temperature from 100 to 250°C, and the second step under a pressure from 100 to 300 bar and at a temperature from 200 to 350°C.

The prehydrogenation catalyst may contain metals from Group VIII and/or VIB of the Periodic System. Suitably the catalyst is a supported catalyst comprising nickel (Ni), NiMo, CoMo noble metal, such as platinum (Pt), palladium (Pd), or rhodium (Rh), ruthenium (Ru), is used, the support being suitably alumina and/or silica.

Suitably a supported catalyst based on CoMo or NiMo on a support selected from Al₂0₃, Si0₂, Zr0₂, and mixtures thereof may be used in the first step.

A catalyst based on noble or transition metals, such as Pt/SAPO- 11 /Al₂0₃, Pt/ZSM- 22/AI₂0₃, Pt/ZSM-23/AI₂0₃ and Pt/SAPO- 11 /Si0₂ can be used for the second step the use of which require the removal of sulphur compounds from the feed prior to contacting it with the catalyst. These catalysts don't tolerate sulfur but at this point the feed is sulfur free. However, HDO catalysts and HDW catalysts such as NiW as defined above in connection with the hydroprocessing stage may also be used. Also CoMo, transition metal catalysts like NiCu, or Ru, Rh, etc. may be used, which are similar or the same catalysts that for the first step. In the prehydrogenation, particularly the lignin fragment in the pyrolysis oil, mainly comprising oxygen containing aromatics, may be converted to a product comprising cyclic hydrocarbons, suitably when using moderate temperatures in the range of 100 to 250°C whereby aromatic compounds are completely hydrogenated. An aqueous fraction cis obtained and it may be recirculated at least partly to the second stage for use as the aqueous media, or it may be directed to further processing to other components. Also a gaseous fraction is obtained, comprising hydrogen, light hydrocarbons (methane, propane, ethane, etc.), CO and C0₂.

The prehydrogenated effluent (prehydrogenated pyrolysis oil) may then be directed to the hydroprocessing stage to be co-processed with CTO.

In the process crude tall oil can be co-processed with pyrolysis oil even though they differ significantly with respect to their chemical composition and in practice they are immiscible. Pyrolysis oils are generally known to have a high tendency to coke formation in hydrogenation. Therefore suitably catalysts having high activity for coke gasification reactions, e.g. non-sulphided transition metal or noble metal catalysts, such as NiCu, Rh, Pd and Pt catalyst are used, and thus higher volumes of pyrolysis oil can be co-processed with crude tall oil. Further, as pyrolysis oil is practically sulfur free it may be necessary to add a sulphiding agent to the feed if very low amounts of CTO are used as co-feed, for maintaining the catalyst active.

Co-processing of pyrolysis oil and crude tall oil reduces coking in the reactor. Unstable molecules comprising oxygen are removed from the pyrolysis oil. The lignin fragment of pyrolysis oil, mainly comprising oxygen containing aromatics may be converted to a product comprising cyclic hydrocarbons when using temperatures in the range of 100 to 200°C whereby aromatic compounds are completely hydrogenated. If desired oxygen may be completely removed at higher temperatures of 300 to 350°C and aromatic compounds are obtained. At lower temperatures the hydrogen consumption is higher, but the light hydrocarbons present in the pyrolysis oil act as hydrogen donors at said conditions, thus reducing the consumption of external hydrogen.

Water bound within the complex pyrolysis liquid is separated during the process. Water is typically separated from the intermediate or final product together with water-soluble compounds together forming a water phase. Such compounds are for example formic acids, hydroxyl acids, alcohols, aldehydes, ketones and sugars. In the process also a gas phase comprising light hydrocarbons such as methane, ethane and propane may be separated for further use.

One or more filtering, hot-filtering and extraction pretreatment methods generally known in the art may also be used prior to the hydroprocessing stage.

The process of the invention may additionally comprise one or more conventional steps, such as separation of gases, washing, cooling, filtering, recovering of intermediates and products, mixing of products with mineral oil or transportation fuel originating from renewable sources or from crude oil or other sources; refining and/or fractionation of effluent. These embodiments can be used in combination with all the different embodiments of the invention.

The process may be batch-type or semi-batch-type or continuous. The process as described above has several advantages. It provides a convenient and efficient means for co-processing pyrolysis oil originating from biomass and crude tall oil to valuable products, such as transportation fuels, solvents, fine chemicals and building-block chemicals. Co-processing of pyrolysis oil with CTO results in that lower temperatures and pressures can be used, which results in reduced consumption of hydrogen, more easily controllable reaction and lower content of aromatic compounds in the product. Thus amount of aromatic compounds in the product may be controlled with the amount of CTO in the hydroprocessing stage.

During the process of the invention also light hydrocarbons such as methane, ethane and propane are removed as gases and they may be directed to further use.

Products, such as transportation fuels and blending components for said fuels, as well as heating oil, solvents, fine chemicals and chemical building-blocks, at least partly or even totally based on renewable starting materials may be obtained.

Water bound within the complex pyrolysis liquid is separated very efficiently and to desired degree during the optional treatment with an aqueous media. The separated water phase contains water-miscible and water-soluble compounds, for example formic acids, hydroxyl acids, alcohols, aldehydes, ketones and sugars, which would interfere in the subsequent hydroprocessing stage. Such compounds are now removed and they can be further processed to more valuable compounds.

The hydroprocessing catalysts stay active for longer periods of time and the process is more stable and easier to control. The process tolerates well variations in the starting materials.

If the aqueous phase in the pretreatment stage is recycled as the aqueous media, less water is needed and several compounds get concentrated in the water phase such is the case of sugars, acids, etc. This aqueous phase with high concentration of chemical compounds has more process alternatives that are more interesting from the economical point of view than diluted solutions; also higher product yields are obtained.

The optional HTHP treatment reduces the amount of water and sugar compounds. HTHP is performed to improve the quality (physical and chemical stability) of the oil and this is achieved by removing (partially or completely) oxygen. Oxygen is usually removed in the form of water therefore H₂ is needed. In the case an inert atmosphere is used (N₂) the molecules present in pyrolysis oil can generate H₂ at the conditions used in the HTHP. Carboxylic acids in pyrolysis oil are the ones that at the reaction conditions give H₂ that can react with oxygen in pyrolysis oil to form water that is separated later.

Oxygen removal is proportional to the amount of H₂ that is generated in the reactor or the H₂ added. By controlling the amount of H₂ one can in principle control the degree of deoxygenation of pyrolysis oil. This also improves the hydroprocessing stage because reactive compounds are removed. Thus the aqueous phase(s) obtained from any of stages of the process may be recirculated or directed for use as starting materials in chemical manufacture. Suitably the product (organic phase) obtained from the optional (HTHP) pretreatment is subjected to one or more pretreatment steps prior to the hydroprocessing stage whereby light acids, aldehydes, sugars and water is removed at least partly. This reduces polymerization and fouling of the reactor in the hydroprocessing stage. The consumption of hydrogen in the hydroprocessing stage may also be reduced with said pretreating steps. The following examples are illustrative of embodiments of the present invention, described above, and they are not meant to limit the invention in any way. invention is illustrated also with reference to the drawings.

Figure 1 presents one embodiment of the process in a schematic diagram. Pyrolysis oil 10 and crude tall oil 20 are fed to hydroprocessing reactor 100, where they are co- processed with at hydroprocessing conditions with hydrogen 30 in the presence of at least one hydroprocessing catalyst. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation and the hydroprocessing effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

Fig 2 is a schematic flow diagram representing another embodiment of the process where crude tall oil is co-processed with prehydrogenated pyrolysis oil in the hydroprocessing stage. Pyrolysis oil 10 is passed to prehydrogenation comprising two steps, first to first prehydrogenation reactor 300 comprising at least one hydrogenation catalyst bed (not shown) where the pyrolysis oil 10 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at mild hydrogenation conditions. An aqueous phase 80 and light gaseous components 90 are passed to purification and recirculation and prehydrogenated effluent 110 is passed to second prehydrogenation reactor 400 comprising at least one hydrogenation catalyst bed (not shown) where the effluent 110 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at hydrogenation conditions. An aqueous phase 120 and light gaseous components 130 are passed to purification and recirculation and prehydrogenated pyrolysis oil 140 is passed to hydroprocessing reactor 100 comprising at least one catalyst bed (not shown) where the prehydrogenated pyrolysis oil 140 is co-processed with crude tall oil 20 at hydroprocessing conditions with hydrogen 30 in the presence of at least one hydroprocessing catalyst. An aqueous phase 40 and light gaseous components 50 are passed to purification and recirculation and the hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any suitable reactor types or configurations and devices may be used. Fig 3 is a schematic flow diagram representing another embodiment of the process where crude tall oil is co-processed in the hydroprocessing stage with pyrolysis oil subjected to treatment with an aqueous media and prehydrogenation carried out in one step. Pyrolysis oil 10 and an aqueous media 150 are passed to reactor 500 to form a mixture which is then agitated, and phases are allowed to form. The formed organic phase (aq-treated pyrolysis oil) 160 and aqueous phase 170 are separated, the aqueous phase 170 is at least partly recirculated to the aqueous media 150, partly to further processing and/or refining. The aq-treated pyrolysis oil 160 is passed to prehydrogenation reactor 400 comprising at least one hydrogenation catalyst bed (not shown) where the aq-treated pyrolysis oil 160 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at hydrogenation conditions. An aqueous phase 120 and light gaseous components 130 are passed to purification and recirculation and prehydrogenated pyrolysis oil 140 is passed to hydroprocessing reactor 100 comprising at least one catalyst bed (not shown) where the prehydrogenated pyrolysis oil 140 is co-processed with crude tall oil 20 at hydroprocessing conditions with hydrogen 30 in the presence of at least one hydroprocessing catalyst. An aqueous phase 40 and light gaseous components 50 are passed to purification and recirculation and the hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

Fig 4 is a schematic flow diagram representing another embodiment of the process where crude tall oil is co-processed with pyrolysis oil subjected to non-catalytic high temperature high pressure pretreatment and two-step prehydrogenation prior to the hydroprocessing stage. Pyrolysis oil 10 is passed to reactor 600 where pyrolysis oil 10 is treated non-catalytically under high pressure and at high temperature, optionally in the presence of one or more gases 180 selected from hydrogen, nitrogen and carbon monoxide. An aqueous phase 190 and light gaseous components 210 are passed to purification and recirculation and the HTHP-treated pyrolysis oil 220 is passed to prehydrogenation comprising two steps. The first step is a mild prehydrogenation step. The HTHP-treated pyrolysis oil 220 is passed to first prehydrogenation reactor 300 comprising at least one hydrogenation catalyst bed (not shown) where the HTHP- treated pyrolysis oil 220 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at hydrogenation conditions. An aqueous phase 80 and light gaseous component 90 are passed to purification and recirculation and the (mildly) prehydrogenated effluent 110 is passed to second prehydrogenation reactor 400 comprising at least one hydrogenation catalyst bed (not shown) where the effluent 110 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at hydrogenation conditions. An aqueous phase 120 and light gaseous component 130 are passed to purification and recirculation and prehydrogenated pyrolysis oil 140 is passed to hydroprocessing reactor 100 comprising at least one catalyst bed (not shown) where the prehydrogenated pyrolysis oil 140 is co-processed with crude tall oil 20 at hydroprocessing conditions with hydrogen 30 in the presence of at least one hydroprocessing catalyst. Alternatively the HTHP-treated pyrolysis oil 220 may be directed to hydroprocessing reactor 100. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation and the hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

Fig 5 is a schematic flow diagram representing another embodiment of the process where crude tall oil is co-processed with pyrolysis oil subjected to treatment with an aqueous media followed with non-catalytic high temperature high pressure pretreatment and one-step prehydrogenation prior to the hydroprocessing stage. Pyrolysis oil 10 and an aqueous media 150 are passed to reactor 500 to form a mixture which is then agitated, and phases are allowed to form. The formed organic phase (aq-treated pyrolysis oil) 160 and aqueous phase 170 are separated, the aqueous phase 170 is at least partly recirculated to the aqueous media 150, partly to further processing and/or refining. The aq-treated pyrolysis oil 160 is passed reactor 600 where the aq-treated pyrolysis oil 160 is treated non-catalytically under high pressure and at high temperature, optionally in the presence of one or more gases 180 selected from hydrogen, nitrogen and carbon monoxide. An aqueous phase 190 and light gaseous component 210 are passed to purification and recirculation and the HTHP-treated pyrolysis oil 220 is passed to prehydrogenation reactor 400 comprising at least one hydrogenation catalyst bed (not shown) where HTHP-treated pyrolysis oil 220 is hydrogenated with hydrogen 30 in the presence of at least one hydrogenation catalyst at hydrogenation conditions. An aqueous phase 120 and light gaseous component 130 are passed to purification and recirculation and prehydrogenated pyrolysis oil 140 is passed to hydroprocessing reactor 100 comprising at least one catalyst bed (not shown) where the prehydrogenated pyrolysis oil 140 is co-processed with crude tall oil 20 at hydroprocessing conditions with hydrogen 30 in the presence of at least one hydroprocessing catalyst. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation and the hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

Fig 6 illustrates alternative arrangements for hydroprocessing pyrolysisi oil and crude tall oil. In Fg 6a an embodiment is shown where pyrolysis oil 10, CTO 20 and hydrogen gas 30 are fed to hydroprocessing reactor 100 where hydrodewaxing is carried out in the presence of a hydrodewaxing catalyst arranged in said reactor. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation. The light gases are directed (not shown in the figure) to an amine scrubber, which removes H₂S and C0₂ from the gaseous products, and scrubbed gases, comprising mainly hydrogen and some impurities, may be recycled to the process as feed hydrogen and quench gas; light hydrocarbons may be directed to further processing to obtain gasoline etc. The hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

In Fig 6b another embodiment is shown where pyrolysis oil 10, CTO 20 and hydrogen gas 30 are fed to hydroprocessing reactor 100 where hydrodewaxing/ hydrodeoxygenation is carried out in the presence of a hydrodewaxing and hydrodeoxygenation catalysts. Said catalysts may be arranged blended, or in separate catalyst beds, in the same reactor. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation. The light gases are directed (not shown in the figure) to an amine scrubber, which removes H₂S and C0₂ from the gaseous products, and scrubbed gases, comprising mainly hydrogen and some impurities, may be recycled to the process as feed hydrogen and quench gas; light hydrocarbons may be directed to further processing to obtain gasoline etc. The hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used. In Fig 6c another embodiment is shown where pyrolysis oil 10, CTO 20 and hydrogen gas 30 are fed to hydroprocessing where hydrodeoxygenation is carried out in the presence of at least one hydrodeoxygenation catalyst in hydroprocessing reactor 101, sulphur 55 is removed before subjecting the effluent from reactor 101 to hydrodewaxing reactor 102 where hydrodewaxing is carried out in the presence of at least one hydrodewaxing catalyst. Said catalysts may be arranged blended, or in separate catalyst beds, in separate reactors whereby said hydroprocessing reactor may comprise more than one reactor. An aqueous phase 40 and light gaseous component 50 are passed to purification and recirculation. The light gases are directed (not shown in the figure) to an amine scrubber, which removes H₂S and C0₂ from the gaseous products, and scrubbed gases, comprising mainly hydrogen and some impurities, may be recycled to the process as feed hydrogen and quench gas; light hydrocarbons may be directed to further processing to obtain gasoline etc. The hydroprocessed effluent 60 comprising hydrocarbons boiling in the liquid fuel range is passed through one or more separation/fractionation devices 200 for separation and fractionation of components to obtain transportation fuels 70. Any reactor types or configurations and devices used in the art may be used.

EXAMPLES The following examples are illustrative of embodiments of the present invention, as described above, and they are not meant to limit the invention in any way.

Example 1 HTHP pre-treatment of pyrolysis oil PO (pyroysis oil) was pre-treated at high temperatures and high pressure. The procedure was performed in two steps. The reactor was packed with the PO and pressurised to 70 bar with N₂ or CO. In some tests also NaOH was mixed with PO in the reactor and the reactor was pressurised to 70 bar with either N₂ or CO. The different tests performed are presented in Table 1.

In the first step of the treatment the target temperature was 150 °C, at this temperature the pressure was expected to be 100 bar. These conditions were kept for 30 minutes and after this the temperature was increased further to target temperature of 300 °C and the expected pressure was 170 bar. Table 1. Experimental conditions in HTHP pre-treatment.

PO + N₂ PO-;- NaOH+ ₂ PO+ aOH-i- CO

Reactor 1 L 1 L 1 L

Pyro lysis oil (g) 400 400 400

T1 151 148 151 10

P1 103 98 88

T2 301 300 303

P2 186 169 188

NaOH (%) 10 10

After the treatment, the reactor was cooled down and gas, liquid, and solid samples were taken. The gas sample was sent for GC analysis.

The solid, liquid, and gas yields (Eq. 1 ) obtained are presented in Table 2.

Table 2. Gas phase composition and product yields in HTHP pre-treatment of PO

PO+ N₂ PO+ NaOH+ N₂ PO+ NaOH+ CO

Gas composition (%)

H₂ 18,3 6,3 3,4

CI - 0,0 0,1

C2 0,2 0,0 0

C2= 0,1 0,1 0

C5+ 9,3 7,6 5,6

C0₂ 72,2 85,9 87,3

CO - - 3,6

Product yields (%)

Solid 35 41 22

Liquid 29 31 35

Gas 6 6 6

Mass balance (%} TO It was not possible to recover all the solids formed during the reactions and some wet solids were left in the reactor thus the mass balance closure is not 100%.

Also tests for PO treatment with CO were made. It was noticed that the liquid yields were similar when the PO is pre-treated using N₂ or CO. However, the pre-treatm ent performed with NaOH addition and in the CO atmosphere gives higher liquid yield product and the less formation of solids.

Example 2. Pretreatment with an aqueous media The effect the treatment of pyrolysis oil with an aqueous media in the process is demonstrated in this example. Pyrolysis oil was obtained by fast pyrolysis from lignocellulosic material.

The treatment (drying of pyrolysis oil (PO)) was performed by adding different amounts of an aqueous media (water) to PO. The solutions prepared are presented in Table 3. The sam pies were m ixed for 15 m inutes and then they were allowed to settle overnight. The phases (aqueous and organic) were separated and analysed. For the organic phase the following determinations were performed: - pH

density

viscosity

GCMS (identify the compounds present)

Karl-Fisher titration (to determine the water content).

- Elemental composition (CHNS/O)

In all cases the results for the organic phase were compared with the result for PO.

For the water phase the following determinations were performed:

- pH

GCMS (identify the compounds present)

Analysis of sugars (quali- and quantitative) Table 3. Treatment of PO with water at room temperature and 50 °C. Sample N° PO (vol-%) PO (ml) Water (ml) Temperature

1 2 room

2 10 room

3 40 80 120 room

4 50 100 100 room

5 60 120 80 room

6 80 160 40 room

7 40 80 120 50

8 50 100 100 50

9 70 140 60 50

10 90 180 20 50

Adding large amounts of water to PO (2% PO and 10% PO in water) yield a large water phase, and a solid organic phase. The organic phase was mainly composed of lignin and all other chemical compounds such as acids, ketones, aldehydes, sugars, etc. were in the water phase. Considering the entire industrial process, drying PO completely in not desired as the organic phase is not fluid or requires high temperatures to be in a fluid form and significant amount of valuable chemicals are discarded in the water phase when the phases are separated.

Adding small about of water like in the case of sample 10 where the concentration of water was only 20% yield only one phase and no phase separation occurred. The water added dissolved in the PO. This is not desired either as more water than the originally present in PO is introduced in the process damaging catalysts in downstream steps and reducing the product yields.

The chemical composition of the organic and aqueous phase was analysed with GCMS, yielding qualitative results. Oxygen containing compounds are present in both phases. In the organic phase substituted phenols, furfurals, some ketones and aldehydes (bezaldehyde) , and alcohols like benzenediols can be found. These compounds are generated during the pyrolysis process (thermal degradation of lignin). The water phase has some acids like butanoic acid, ketones like cyclopentanone, some phenols and substituted phenols (smaller molecules than the ones present in the organic phase), and sugars like levoglucosan. The water content of pyrolysis oil before and after treatment with an aqueous media is presented in Figure 7. The water content of the organic phase after the treatment (drying) was lower than that of PO. The water content of PO was 30% while for the organic phases obtained in samples 3 to 9 the water content was between 15-20%. Densities are compared in Figure 8. The density of the dried organic phase increase as this fraction gets richer in large molecular weight compounds. Light molecular weight compounds are present in the water phase.

The results from viscosity measurements are presented in Figure 9. The viscosity of PO decreases with temperature as expected. However, at temperatures higher than 70 °C the viscosity of PO increases thus the chemical compounds present in PO react at these temperature giving high molecular weight compounds and therefore the viscosities increases. This behaviour is not detected in the dried organic phases. For these samples the viscosity decreases with temperature in the range tested (room temperature to 80 °C). The dried samples have significantly higher viscosity that PO as the concentration of higher molecular weight compounds, mainly lignin, is higher than that of PO.

Based on the results presented above for content, density, and viscosity it can be concluded that the drying temperature doesn't affect the process significantly and for the industrial process the selected temperature for the drying of PO will be room temperature.

Elemental composition of the organic phases is shown in Table 4. Although the elemental compositions for the organic phases are similar, lower oxygen content is achieved when large amounts of water are used (Sample 3 and 4). Based on the results temperatures close to room temperature are suitable as at higher temperatures there is evaporation of light compounds reducing the carbon content of the organic phase. Table 4. Elemental composition of the organic phase.

Sam pie num ber PO

Volume of PO

80 PO + 100 PO + 120 PO + 160 PO + 80 PO + 100 PO + 140 PO + and water (m I)

120 water 100 water 80 water 40 water 120 water 100 water 60 water

Phase Organic Organic Organic Organic Organic Organic Organic

Tern perature

(oC) room room room room 50 50 50

Carbon (wt%) 41.53 58.59 56.28 55.48 52.85 56.70 54.28 53.81

Hydrogen (wt%) 5.92 6.93 6.92 7.08 7.06 6.85 6.79 6.90

Nitrogen (wt%) 0.19 0.26 0.26 0.25 0.24 0.26 0.25 0.24

Sulphur (wt%) 0.00

Oxygen (wt%) 34.68

Water content

30.8 15.1 14.7 17.1 19.6 14.4 15.9 18.4 (wt%)

The pH of pyrolysis oil before the addition of water was 2.5. The organic phase samples have higher pH than PO suggesting that the concentration of acidic compounds is less. However, the pH of the aqueous phase samples was between 2.7 and 2.8, thus large concentrations of organic acids in the aqueous phase are expected. The amount of metals was reduced in the organic phase after the treatment with an aqueous phase. The use of higher content of the aqueous phase resulted in more efficient removal of metals and phosphorus, which were enriched in the aqueous phase.

In following Table 5 the content of sugar components in the aqueous phase after treatment of PO with and aqueous media at RT and 50°C is presented. Table 5.

Sample number 3 4 5 7 8 9

Volume of PO and PO 80 + PO 100 + PO 120 + PO 80 + PO 100 + PO 140 + water (ml) water 120 water 100 water 80 water 120 water 100 water 60

Phase Water Water Water Water Water Water

Temperature (°C) room room room 50 50 50

Galactose,

Methanolysis+ GC mg/l 27,3 33,8 27,7 34,8 43,1 30,3

Glucose,

Methanolysis+ GC mg/l 528 681 525 637 801 587

Mannose,

Methanolysis+ GC mg/l 45,6 57,5 45,6 55,2 68,9 49,1

Arabinose,

Methanolysis+ GC mg/l 31 ,8 40,5 30,2 36,3 45,9 33,3

Xylose,

Methanolysis+ GC mg/l 86,3 109 84,5 104 131 95 Glucuronic acid,

Methanolysis+ GC mg/l 5,1 4,5 5,4 7,1 7,8 5,3

Galacturonic acid,

Methanolysis+ GC mg/l 34,8 39,6 34,1 43,5 52,3 36,2

Carbohydrates,

total,

Methanolysis+ GC mg/l 759 966 753 918 1150 836

Galactose,

monomeric, GC mg/l 4,8 4,2 3,6 4,9 5,5 5,3

Glucose,

monomeric, GC mg/l 6 7 4,4 6,3 8,1 5,6

Mannose,

monomeric, GC mg/l 6,1 8,1 4,2 6,7 8,1 7

Arabinose,

monomeric, GC mg/l 32 35 25,3 32,7 38,6 27,9

Xylose,

monomeric, GC mg/l 29,3 33,4 23,2 30,6 37,1 27,8

Glucuronic acid,

monomeric, GC mg/l 9 9,8 6 10,3 11 7,9

Galacturonic acid,

monomeric, GC mg/l 5,1 4,9 3,9 11 ,9 14,5 9,8

Carbohydrates,

monomeric total,

GC mg/l 92,3 102 70,6 103 123 91 ,3

It was demonstrated that the aqueous treatment (drying) of pyrolysis oil can be achieved by adding water and causing the separation into organic and water phase. The water phase comprises valuable compounds that can be process further e.g. reformed or converted into gasoline or diesel in the upgrading, or in the production of hydroxymethylfurfural which can be utilize as intermediate in gasoline production.

The present invention has been described herein with reference to specific embodiments. It is, however clear to those skilled in the art that the process(s) may be varied within the bounds of the claims.

Claims

Claims

1. A process for converting of pyrolysis oil and crude tall oil, comprising the stages where pyrolysis oil is subjected to one or more pretreatments steps selected from treatment with an aqueous media, high temperature high pressure treatment HTHP, prehydrogenation, and extraction, and combinations thereof to obtain pretreated pyrolysis oil, and a feed comprising the pretreated pyrolysis oil and crude tall oil is subjected to hydroprocessing under hydroprocessing conditions in the presence of hydrogen and at least one hydroprocessing catalyst whereby an effluent comprising one or more hydrocarbons boiling in the liquid fuel hydrocarbon range is obtained.

2. The process according to claim 1, wherein said hydroprocessing is carried out at the temperature from 100 to 450°C, preferably from 200 to 450°C.

3. The process according to claim 1 or 2, wherein said hydroprocessing is carried out under the pressure from 5 to 350 bar, preferably from 10 to 150 bar.

4. The process according to any one of claims 1-3, wherein said hydroprocessing catalyst is a supported catalyst comprising at least one element selected from Group VI 11 and/ or VI B of the Periodic System of El em ents.

5. The process according to any one of claims 1-4, wherein at least one HDW catalyst is used, or alternatively a combination of HDW and HDO catalysts is used.

6. The process according to any one of claims 1-5, wherein the temperature is in the range between 250 and 390°C.

7. The process according to any one of claims 1-6, wherein the pressure is between 50 to 100 bar.

8. The process according to any one of claims 1-7, wherein pretreated pyrolysis oil is co-processed with crude tall oil in an amount from 5 to 95 wt% of pretreated pyrolysis oil and from 95 to 5 wt% of crude tall oil.

9. The process according to any one of claims 1-8, wherein the amount of the pretreated pyrolysis oil ranges from 5 to 75 wt% and the amount of crude tall oil ranges from 95 to 25 wt%.

10. The process according to any one of claims 1-9, wherein the hydroprocessing is carried out as hydrodewaxing, or as a combination of hydrodeoxygenation and hydrodewaxing.

11. The process according to claim 10, wherein the combination is carried out simultaneously or consecutively.

12. The process according to any one of claims 1 -11, wherein in the treatment with an aqueous media the pyrolysis oil is contacted with an aqueous media, followed by separation of an organic phase and an aqueous phase and directing the organic phase to hydroprocessing or one or more pretreatment steps selected from high temperature high pressure treatment, prehydrogenation, and extraction and com binations thereof .

13. The process according to claim 12, wherein the amount of the aqueous media is from 1 to 80 vol-%, preferably from 10 to 75 vol-% ,

14. The process according to claim 12 or 13, wherein pyrolysis oil or organic phase is subjected to a HTHP treatment comprising at least two steps where in the first step (a) pyrolysis oil or organic phase is heated in the absence of added catalyst at 100 to 200°C temperature and 50 bar to 250 bar pressure to yield product of the first step, and in the second step (b) heating the product of the first step in the absence of added catalyst at 200 to 400°C temperature and 50 bar to 250 bar pressure whereby HTHP-treated pyrolysis oil is obtained.

15. The process according to any one of claims 12 - 14, wherein pyrolysis oil or organic phase or HTHP-treated pyrolysis oil is subjected to prehydrogenation comprising one or two steps.

16. The process according to claim 15, wherein the prehydrogenation comprising one step is carried out in the presence of at least one hydrogenation catalyst and hydrogen under a pressure 10 to 350 bar and at a temperature from 50 to 350°C.

17. The process according to claim 15, wherein the prehydrogenation comprises two steps and the first step is carried out in the presence of at least one hydrogenation catalyst and hydrogen under a pressure from 10 to 300 bar and at a temperature from 100 to 250°C, and the second step in the presence of at least one hydrogenation catalyst and hydrogen under a pressure from 100 to 300 bar and at a temperature from 200 to 350°C.

18. The process according to any one of claims 1-17, wherein the effluent is subjected to fractionation to yield hydrocarbon fractions boiling in the transportation fuel ranges.

19. The process according to claim 18, wherein the hydrocarbon fractions comprise fractions boiling in the ranges of gasoline, kerosene, jet fuel, diesel oil, naphtha, blending components for transportation fuels, heating oil and solvents.

20. A product obtainable by the process according to any one of claims 1-19.

21. The product of claim 20, said product being selected from hydrocarbon fractions boiling in the ranges of gasoline, kerosene, jet fuel, diesel oil, naphtha, blending components for transportation fuels, heating oil and solvents, and fine chemicals and building-block chemicals.