WO2015101713A1

WO2015101713A1 - Integrated process for producing hydrocarbons

Info

Publication number: WO2015101713A1
Application number: PCT/FI2014/051063
Authority: WO
Inventors: Janne Asikkala; Andrea Gutierrez; Pekka Jokela; Risto Kotilainen
Original assignee: Upm-Kymmene Corporation
Priority date: 2013-12-31
Filing date: 2014-12-30
Publication date: 2015-07-09
Also published as: FI20136345L

Abstract

The present invention relates to an integrated process for producing hydrocarbons, wherein feedstock comprising biomass is pyrolyzed under reductive gas atmosphere, pyrolysis oil is separated from non-condensable gases, the non-condensable gases are directed to a hydrogen plant and the pyrolysis oil is directed to a hydroprocessing system, where said pyrolysis oil is subjected to catalytic hydroprocessing to yield a hydroprocessing product, a heavy component comprising hydrocarbons having carbon number more than 5 and light hydrocarbons having carbon number from 1 to 5 are separated and the light hydrocarbons are directed to the hydrogen plant for converting to hydrogen, carbon monoxide and carbon dioxide, and carbon monoxide is directed to the pyrolysis reactor and hydrogen is directed to the hydroprocessing system.

Description

INTEGRATED PROCESS FOR PRODUCING HYDROCARBONS

FIELD OF THE INVENTION

The present invention relates to an integrated process for producing hydrocarbons. More particularly the invention relates to a process, where pyrolysis of biomass is integrated with hydroprocessing and hydrogen plant. The present invention relates also to a method for producing hydrocarbons. BACKGROUND OF THE INVENTION

There is an increasing need for hydrocarbons suitable as liquid fuels as such, particularly transportation fuels, or compatible with said fuels. Biofuels are typically manufactured from feedstocks originating from renewable sources including oils and fats from plants, animals, algal materials, fish, and various waste streams and sewage sludge. The common feature in these feedstocks is that they are composed of glycerides and free fatty acids, both of these containing aliphatic carbon chains having from about 8 to about 24 carbon atoms and the aliphatic carbon chains being saturated, or mono-, di- or polyunsaturated. Catalytic hydroprocessing of these materials requires significant quantities of hydrogen, and this is a major operating cost in the production of biomass-derived fuels by catalytic hydroprocessing. Further, it is more difficult to convert lower quality feedstocks of more heterogeneous nature and containing contaminants by catalytic hydroprocessing, or they require more complicated equipment.

Recycling of excess hydrogen to hydroprocessing is commonly used in hydroprocessing. Hydroprocessing of heterogeneous feedstocks, originating typically from renewable sources produces light hydrocarbons as unwanted byproducts. Light hydrocarbons are separated in the course of the process from the process liquid in gas separation, where hydrogen is separated and recycled to the hydroprocessing reactor. Typically in a continuously operating process light hydrocarbons are concentrated in the hydrogen recycle stream, which results in the reduction of hydrogen partial pressure in said stream and, further, via that reduction also the hydrogen partial pressure in the hydroprocessing reactor(s) is reduced. For achieving required product properties, such as specific diesel grade, significant amounts of hydrogen make-up gas are necessary for maintaining required hydrogen partial pressure. Hydrogen is typically supplied to hydroprocessing processes from a hydrogen plant operating most commonly by steam reforming. In hydrogen plants, in the steam reforming process (typically SMR= steam methane reforming) usually natural gas, liquefied petroleum gas (LPG) gas or naphtha is used as starting material, and light hydrocarbons therein react at elevated temperatures with steam to yield synthesis gas containing carbon monoxide and hydrogen, followed by water gas shift reaction at a lower temperature, where said carbon monoxide reacts with water to produce carbon dioxide and hydrogen.

Pyrolysis oils are obtained using various feeds, methods and processes. Biomass pyrolysis represents thermochemical processing for producing pyrolysis oil, which may be used as heating fuels or it may be further converted to liquid transportation fuels and commodity chemicals.

Pyrolysis is generally understood as the chemical decomposition of organic materials by heating in the absence or with limited supply of oxidizing agent such as air or oxygen. Commercial pyrolysis applications are typically either focused on the production of charcoal (slow pyrolysis) or production of liquid products (fast pyrolysis), the pyrolysis oil.

Fast pyrolysis is used currently on commercial scale for producing pyrolysis oil, with up to 70 % liquid product yields. In fast pyrolysis solid biomass is thermally treated at the temperature typically ranging from 300 to 900°C, and the residence time of the biomass in the pyrolyzer can be from a fraction of a second to seconds. Pyrolysis oils are complex mixtures of chemical compounds typically containing oxygen, including reactive aldehydes and ketones. Said reactive compounds react with each other whereby complex molecules are formed and the viscosity of the pyrolysis oil is increased. For example, biomass derived pyrolysis oil typically comprises water, light volatiles and non- volatiles. Further, pyrolysis oil has high acidity, which typically leads to corrosion problems, substantial water content, and high oxygen content.

Wood-based pyrolysis oil is the product of pyrolysis of wood or forest residues and it contains typically carboxylic acids, aldehydes, ketones, carbohydrates, thermally degraded lignin, water, and alkali metals. The oxygen-containing compounds (typically 40-50 wt-%) and water (typically 15-30 wt-%) make pyrolysis oils chemically and physically unstable. Although pyrolysis oils have higher energy density than wood, they are acidic (pH~2) and incompatible with conventional fuels. Furthermore these pyrolysis oils have high viscosity and high solid content. Refining of pyrolysis oils to provide fuel or fuel components is often very challenging due to high oxygen content and the complex mixture of components of said bio-oil. For example pyrolysis oil typically consists of about 1500 compounds, most of which are still unidentified. Said compounds require very different conditions for converting them further to fuel components or precursors to fuel. Often this is carried out by hydroprocessing said pyrolysis oil over a catalyst capable of performing hydroprocessing reactions in the presence of hydrogen. Since pyrolysis oil typically contains even up to 50 wt% of oxygen, complete removal of oxygen from pyrolysis oil requires a substantial amount of external hydrogen, even 1000 L/kg pyrolysis oil. The obtained light components are turned into gaseous products (hydrogen, methane, ethane, etc.), and heavy components are turned into coke and heavy oil. The heavy oil mixture needs further refinement to produce fuel fractions and this procedure requires high amounts of hydrogen and typically various different catalysts for obtaining the desired products.

Despite the ongoing research and development of processes for the manufacture of liquid fuels, there is still a need to provide an improved process for producing hydrocarbons useful as liquid fuels or fuel blending components.

SUMMARY OF THE INVENTION

An object of the invention is to provide an improved process for producing hydrocarbons.

Another object of the invention is to provide an integrated process where pyrolysis is integrated with a hydrogen plant and hydroprocessing.

Another object of the invention is to provide an integrated process where the pyrolysis is carried out under reductive gas atmosphere, whereby the content of oxygen containing compounds in the obtained pyrolysis oil can be decreased and the consumption of hydrogen needed in the hydroprocessing can be decreased.

Another object of the invention is to provide an integrated process where pyrolysis is integrated with heat generation, a hydrogen plant and hydroprocessing.

Another object of the invention is to provide an integrated process where the reductive gases are generated in the process. Another object of the invention is to provide an integrated process where hydrocarbons and heat can be produced effectively, economically and in an environmentally sustainable way. The present invention relates to an improved for producing hydrocarbons.

Particularly, the invention relates to an integrated process for producing hydrocarbons, wherein the process comprises the steps, where

- feedstock comprising biomass is pyrolyzed under reductive gas atmosphere in a pyrolysis reactor to produce pyrolysis products and char,

the pyrolysis products are separated from the char and the pyrolysis products are directed to a condenser where pyrolysis oil is separated from non-condensable gases, the pyrolysis oil is directed to a hydroprocessing system, where it is subjected to catalytic hydroprocessing in the presence of hydrogen to yield a hydroprocessing product,

the hydroprocessing product is directed to a separator, where an aqueous component, a heavy component comprising hydrocarbons having carbon number more than 5, and a light component comprising gases and hydrocarbons having carbon number from 1 to 5 are separated,

hydrocarbons having carbon number from 1 to 5 are directed to a hydrogen plant where they are converted to hydrogen and carbon monoxide and carbon dioxide, hydrogen is separated and directed to the hydroprocessing system and gas stream comprising carbon monoxide and carbon dioxide is directed to the pyrolysis reactor, and

the heavy component comprising hydrocarbons having carbon number more than 5 is directed to fractionation to obtain fractions comprising hydrocarbons.

The invention also relates to a method for producing hydrocarbons, wherein said method comprises the steps of

a) pyrolysing feedstock comprising biomass under reductive gas atmosphere in a pyrolysis reactor to yield pyrolysis products and char,

b) separating the pyrolysis products from the char,

c) condensing the pyrolysis products to form pyrolysis oil and non-condensable gases, d) subjecting the pyrolysis oil to catalytic hydroprocessing in a hydroprocessing system in the presence of hydrogen to yield a hydroprocessing product,

e) separating from the hydroprocessing product an aqueous component, a heavy component comprising hydrocarbons having carbon number more than 5, and a light component comprising gases and hydrocarbons having carbon number from 1 to 5 from the hydroprocessing product, f) directing hydrocarbons having carbon number from 1 to 5 derived in step e) to the hydrogen plant where they are converted to hydrogen, carbon monoxide and carbon dioxide,

g) separating CO, CO2 and H2S from the light component,

h) separating the hydrogen derived in step f) and directing it to the hydroprocessing system of step d) and

i) directing a gas stream comprising carbon monoxide and carbon dioxide derived in step f) to the pyrolysis reactor of step a).

The present invention also provides hydrocarbons obtainable by said process. The present invention also provides the use of recycle gas comprising CO for providing reductive gas atmosphere in pyrolysis process.

Characteristic features of the invention are presented in the appended claims. DEFINITIONS

The term "heat transfer material" refers here to material capable of carrying heat energy, particularly heat energy carrying particles, granules, etc.

The term "hydroprocessing" refers here to catalytic processing of feedstock originating from renewable sources by all means of molecular hydrogen.

The term "hydrotreatment" refers here to a catalytic process, which removes oxygen from organic oxygen compounds as water (hydrodeoxygenation, HDO), sulfur from organic sulfur compounds as dihydrogen sulfide (hydrodesulfurisation, HDS), nitrogen from organic nitrogen compounds as ammonia (hydrodenitrogenation, HDN) and halogens, for example chlorine from organic chloride compounds as hydrochloric acid (hydrodechlorination, HDCI), by the means of molecular hydrogen.

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 "hydrodeoxygenation" (HDO) refers to the removal of carboxyl oxygen as water by the means of molecular hydrogen under the influence of catalyst. The term "decarboxylation" and/or "decarbonylation" refers here to the removal of carboxyl oxygen as CO2 (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" refers here to catalytic treatment of organic hydrocarbon materials using molecular hydrogen at high pressures to reduce the wax content by isomerization and/or cracking.

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

Transportation fuels refer to fractions or cuts or blends of hydrocarbons having distillation curves standardized for fuels, such as for diesel fuel (middle distillate from 160 to 380°C, EN 590), gasoline (40 - 210°C, EN 228), aviation fuel (160 to 300°C, ASTM D-1655 jet fuel), kerosene, naphtha, etc.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic flow diagram representing one embodiment of the integrated process.

Figure 2 is a schematic flow diagram representing another embodiment of the integrated process, where the feedstock is subjected to pretreatment prior to deeding to the pyrolysis reactor.

Figure 3 is a schematic flow diagram representing another embodiment of the integrated process where hydroprocessing is carried out in two steps.

DETAILED DESCRIPTION OF THE INVENTION

It was surprisingly found that several advantageous effects may be achieved when utilizing an integrated process for producing hydrocarbons, wherein pyrolysis under reductive gas atmosphere is integrated with catalytic hydroprocessing and a hydrogen plant. In the present invention hydrocarbons, suitable as high quality transportation fuels, are produced.

According to one embodiment char formed in the pyrolysis may be treated in a char treatment unit, suitably a boiler integrated with the pyrolysis reactor, to additionally produce heat, which may further be converted to power, steam etc. In the integrated process feedstock comprising biomass is subjected to pyrolysis in a pyrolysis reactor under a reductive gas atmosphere whereby pyrolysis products and char are obtained. The pyrolysis products comprise vapors and gases, including water vapor. The pyrolysis products are separated in a suitable separator from solid materials including char. The pyrolysis products are then directed to a condenser where pyrolysis oil is separated from non-condensable gases. Typically the pyrolysis oil comprises water. The pyrolysis oil may be subjected to water removal prior to hydroprocessing. The pyrolysis oil is subjected to catalytic hydroprocessing in a hydroprocessing system in the presence of hydrogen to yield a hydroprocessing product. Ana aqueous component, a heavy component comprising hydrocarbons having carbon number more than 5, and a light component comprising gases and hydrocarbons having carbon number from 1 to 5 may be separated from the hydroprocessing product. Further, the light component may be directed to separation of the light hydrocarbons from CO, CO2 and H2S, which may be directed to the pyrolysis reactor, and the separated light hydrocarbons may be directed to the hydrogen plant, where they are converted to hydrogen, which may be directed to the hydroprocessing system, and to carbon monoxide/carbon dioxide, which may be directed to the pyrolysis reactor. The heavy component may further be fractionated to fractions boiling in the transportation fuel ranges.

Thus, the invention relates to an integrated process for producing hydrocarbons. Said integrated process for producing hydrocarbons comprises the steps, where

feedstock comprising biomass is pyrolyzed under reductive gas atmosphere in a pyrolysis reactor to produce pyrolysis products and char,

the pyrolysis products are separated from the char and the pyrolysis products are directed to a condenser where pyrolysis oil is separated from non-condensable gases, - the pyrolysis oil is directed to a hydroprocessing system, where it is subjected to catalytic hydroprocessing in the presence of hydrogen to yield a hydroprocessing product,

hydrocarbons having carbon number from 1 to 5 are directed to a hydrogen plant where they are converted to hydrogen and carbon monoxide and carbon dioxide, hydrogen is separated and directed to the hydroprocessing system and gas stream comprising carbon monoxide and carbon dioxide is directed to the pyrolysis reactor, and - the heavy component comprising hydrocarbons having carbon number more than 5 is directed to fractionation to obtain fractions comprising hydrocarbons.

b) separating the pyrolysis products from the char,

e) separating from the hydroprocessing product an aqueous component, a heavy component comprising hydrocarbons having carbon number more than 5, and a light component comprising gases and hydrocarbons having carbon number from 1 to 5 from the hydroprocessing product,

f) directing hydrocarbons having carbon number from 1 to 5 derived in step e) to the hydrogen plant where they are converted to hydrogen, carbon monoxide and carbon dioxide,

g) separating CO, CO2 and H2S from the light component,

i) directing a gas stream comprising carbon monoxide and carbon dioxide derived in step f) to the pyrolysis reactor of step a) .

The char formed in the pyrolysis may be treated in a char treatment unit. Suitably said char treatment unit is a boiler. According to a suitable embodiment the pyrolysis reactor is a fluidizing bed reactor and the boiler is any type of boiler, both utilizing particulate heat transfer material, which can be drawn from the boiler to the pyrolysis reactor. According to a particularly suitable embodiment the heat transfer material is looped from the boiler to the pyrolysis reactor. The solid material (comprising char and heat transfer material) separated from pyrolysis output (comprising the pyrolysis products and solid materials, such as char and heat transfer material) is directed to a boiler, where the char is combusted together with fuel fed to the boiler whereby heat (heat energy) and flue gas comprising CO, CO2 and N2 are produced . The heat transfer material is looped from the boiler to the pyrolysis reactor. Figure 1 shows a flow diagram of an embodiment of the integrated process. In an overview, the integrated process is carried out in a pyrolysis reactor 100 integrated with a boiler 200, hydroprocessing system 300 and hydrogen plant 400.

Feedstock comprising biomass 10 is charged to the pyrolysis reactor 100 and heat transfer material 20 is transferred from boiler 200 to the pyrolysis reactor 100. The feedstock is pyrolyzed in the pyrolysis reactor 100 in the presence of the heat transfer material whereby pyrolysis output 30 is obtained. The pyrolysis output 30 comprises pyrolysis vapors, gases (pyrolysis products) and char and heat transfer material (solids). The pyrolysis output 30 is directed to a solids/vapor separator 500, suitably a cyclone, where solids comprising char and heat transfer material are separated and recycled back to the boiler 200 as stream 40, and the pyrolysis gases and vapors are directed as stream 50 to a condenser 600 where pyrolysis oil 60 and non-condensable gases 70 are separated. The non-condensable gases 70 are directed to the hydrogen plant 400, optionally combined with stream 150. Fuel 80 is fed to the boiler 200, where the fuel is combusted together with the char in the presence of heat transfer material, which is looped at least partly, as stream 40 from the separator 500, and heat energy 90 and flue gas 110 are formed.

Starting material 120 selected from natural gas, biogas, naphtha, LPG, and combinations thereof is directed to hydrogen plant 400 comprising a desulfurization unit 101, steam reformer unit 102, water gas shift unit 103 and carbon monoxide/carbon dioxide/water separator unit 104. In the hydrogen plant 400 the starting material 120 and stream 150 are subjected to sulfur removal in the desulfurization unit 101, followed by directing the desulfurized starting material to the steam reformer unit 102, where hydrocarbons are converted to hydrogen and carbon dioxide, followed by carrying out water gas shift reaction in the water gas shift unit 103 and separating in the carbon monoxide/carbon dioxide/water separator unit 104 carbon monoxide/carbon dioxide stream 140 and hydrogen stream 130. Recycle stream 150 comprising hydrogen and light hydrocarbons (C1-C5), obtained from hydroprocessing system 300, particularly from separator 800, is directed to the hydrogen plant 400, to the desulfurization unit 101, where hydrogen acts in the desulfurization reaction, and the light hydrocarbons are converted to hydrogen and CO/CO2 in the hydrogen plant 400.

Pyrolysis oil 60 and hydrogen stream 130 from the hydrogen plant 400 are fed to the hydroprocessing system 300 for enacting catalytic hydroprocessing. Stream 130 may contain sulfur compounds, and pyrolysis oil 60 may contain sulfur compounds. If necessary for the catalytic process, sulfur compounds may be added to stream 130 or 60. The hydroprocessed product, stream 160 from the hydroprocessing reactor system 300 is directed to a separator 700, such as cold separator, where separation of an aqueous component, i.e. stream 170 containing water, a heavy component, i.e. stream 180 and a light component i.e. stream 190 takes place. Stream 180 comprising the heavy component may be directed to fractionation and separation suitably in a fractionator (710) where fractions comprising hydrocarbons boiling in the liquid fuel ranges may be obtained, suitably diesel fraction 213 and gasoline fraction 214. Stream 190 comprising the light component is directed to a separator 800 for the separation of H2S and CO/CO2, suitably an amine scrubber, where stream 150 containing hydrogen and light hydrocarbons and stream 210 containing H2S and CO/CC are separated. Stream 150 is recycled to the hydrogen plant 100. Stream 210 may also be recycled to the pyroiysis reactor 100, suitably combined with stream 140, or a optionally H2S (stream 211) may be separated in a separator 720 from the stream 210, before recycling the CO/CO2 stream 212 to pyroiysis reactor. Any suitable reactor types or configurations and devices may be used. Figure 2 shows a flow diagram of another embodiment of the integrated process. In an overview, the integrated process is carried out in a pyroiysis reactor 100 integrated with a boiler 200, hydroprocessing system 300 and hydrogen plant 400. The feedstock is pretreated in a pretreatment unit 900 prior to feeding it to the pyroiysis reactor 100. Feedstock comprising biomass 10 is pretreated with an acid 220 in pretreatment unit 900. Said pretreatment unit 900 may comprise a mixing vessel and optional drier. An aqueous stream 170 separated from the hydroprocessing product 160 is directed to the pretreatment unit 900. Said stream is typically acidic and provides an additional source of acid. Hot flue gas 110 from the boiler 200 is directed to the pretreatment unit 900 for carrying out drying of the feedstock 10 after acid treatment. The pretreated feedstock 230 is directed to the pyroiysis reactor 100 and heat transfer material 20 is transferred from boiler 200 to the pyroiysis reactor 100.

The pretreated feedstock 230 is pyrolyzed in the pyroiysis reactor 100 in the presence of the heat transfer material whereby pyroiysis output 30 is obtained. The pyroiysis output 30 comprises pyroiysis vapors, gases (pyroiysis products including water vapor)) and char and heat transfer material (solids). The pyroiysis output 30 is directed to a solids/vapor separator 500, suitably a cyclone, where solids comprising char and heat transfer material are separated and recycled back to the boiler 200 as stream 40, and the pyroiysis gases and vapors are directed as stream 50 to a condenser 600 where pyroiysis oil 60 and non- condensable gases 70 are separated. The non-condensable gases 70 are directed to the hydrogen plant 400, optionally combined with stream 150. Fuel 80 is fed to the boiler 200, where the fuel is combusted together with the char in the presence of heat transfer material, which is looped at least partly, as stream 40 from the separator 500, and heat energy 90 and flue gas 110 are formed. Starting material 120 selected from natural gas, biogas, naphtha, LPG, and combinations thereof is directed to hydrogen plant 400 comprising a desulfurization unit 101, steam reformer unit 102, water gas shift unit 103 and carbon monoxide/carbon dioxide/water separator unit 104. In the hydrogen plant 400 the starting material 120 and stream 150 are subjected to sulfur removal in the desulfurization unit 101, followed by directing the desulfurized starting material to the steam reformer unit 102, where hydrocarbons are converted to hydrogen and carbon dioxide, followed by carrying out water gas shift reaction in the water gas shift unit 103 and separating in the carbon monoxide/carbon dioxide/water separator unit 104 carbon monoxide/carbon dioxide stream 140 and hydrogen stream 130. Recycle stream 150 containing hydrogen and light hydrocarbons (C1-C5), obtained from hydroprocessing system 300, particularly from separator 800, is directed to the hydrogen plant 400, to the desulfurization unit 101, where hydrogen acts in the desulfurization reaction, and the light hydrocarbons are converted to hydrogen and CO/CO2 in the hydrogen plant 400. Pyrolysis oil 60 and hydrogen stream 130 from the hydrogen plant 400 are fed to the hydroprocessing system 300 for enacting catalytic hydroprocessing. Stream 130 may contain sulfur compounds, and pyrolysis oil 60 may contain sulfur compounds. If necessary for the catalytic process, sulfur compounds may be added to stream 130 or 60. The hydroprocessed product, stream 160 from the hydroprocessing reactor system 300 is directed to a separator 700, such as cold separator, where separation of an aqueous component, i.e. stream 170 containing water, a heavy component, i.e. stream 180 and a light component i.e. stream 190 takes place. Stream 180 comprising the heavy component may be directed to fractionation and separation suitably in a fractionator (710) where fractions comprising hydrocarbons boiling in the liquid fuel ranges may be obtained, suitably diesel fraction 213 and gasoline fraction 214. Stream 190 comprising the light component is directed to a separator 800 for the separation of H2S and CO/CO2, suitably an amine scrubber, where stream 150 containing hydrogen and light hydrocarbons and stream 210 containing H2S and CO/CC are separated. Stream 150 is recycled to the hydrogen plant 100. Stream 210 may be recycled to the pyrolysis reactor 100, suitably combined with stream 140. Optionally H2S (stream 211) may be separated in a separator 720 from the stream 210, before recycling the CO/CO2 stream 212 to pyroiysis reactor. Any suitable reactor types or configurations and devices may be used.

Figure 3 shows another embodiment of the integrated pyroiysis process. In an overview, the integrated process is carried out in a pyroiysis reactor 100 integrated with a boiler 200, hydroprocessing system 300 and hydrogen plant 400. The feedstock is pretreated in a pretreatment unit 900 prior to feeding it to the pyroiysis reactor 100. The hydroprocessing is carried in a hydroprocessing system 300 comprising a first hydroprocessing reactor 310, a separator 311 arranged downstream the first hydroprocessing reactor and a second hydroprocessing reactor 312 arranged downstream the separator 311.

Feedstock comprising biomass 10 is pretreated with an acid 220 in pretreatment unit 900. Said pretreatment unit 900 may comprise a mixing vessel and optional drier. An aqueous stream 170 separated from the hydroprocessing product 160 is directed to the pretreatment unit 900. Said stream is typically acidic and provides an additional source of acid. Hot flue gas 110 from the boiler 200 may be directed to the pretreatment unit 900 for drying of the acid treated feedstock 10. The pretreated feedstock 230 is directed to the pyroiysis reactor 100 and heat transfer material 20 is transferred from boiler 200 to the pyroiysis reactor 100. The pretreated feedstock 230 is pyrolyzed in the pyroiysis reactor 100 in the presence of the heat transfer material whereby pyroiysis output 30 is obtained. The pyroiysis output 30 comprises pyroiysis vapors, gases (pyroiysis products including water vapor) and char and heat transfer material (solids). The pyroiysis output 30 is directed to a solids/vapor separator 500, suitably a cyclone, where solids comprising char and heat transfer material are separated and recycled back to the boiler 200 as stream 40, and the pyroiysis gases and vapors are directed as stream 50 to a condenser 600 where pyroiysis oil 60 and non- condensable gases 70 are separated. The non-condensable gases 70 are directed to the hydrogen plant 400, optionally combined with stream 150. Fuel 80 is fed to the boiler 200, where the fuel is combusted together with the char in the presence of heat transfer material, which is looped at least partly, as stream 40 from the separator 500, and heat energy 90 and flue gas 110 are formed.

Starting material 120 selected from natural gas, biogas, naphtha, LPG, and combinations thereof is directed to hydrogen plant 400 comprising a desulfurization unit 101, steam reformer unit 102, water gas shift unit 103 and carbon monoxide/carbon dioxide/water separator unit 104. In the hydrogen plant 400 the starting material 120 and stream 150 are subjected to sulfur removal in the desulfurization unit 101, followed by directing the desulfurized starting material to the steam reformer unit 102, where hydrocarbons are converted to hyd rogen and carbon dioxide, followed by carrying out water gas shift reaction in the water gas shift unit 103 and separating in the carbon monoxide/ca rbon dioxide/water sepa rator unit 104 carbon monoxide/carbon dioxide stream 140 and hydrogen stream 130. Recycle stream 150 containing hydrogen and light hydroca rbons (C1-C5), obtained from hydroprocessing system 300, particularly from sepa rator 700, is directed to the hydrogen plant 400, to the desulfurization unit 101, where hydrogen acts in the desulfurization reaction, and the light hydrocarbons are converted to hydrogen and CO/CO2 in the hydrogen plant 400.

Pyrolysis oil 60 and hydrogen stream 130 from the hydrogen plant 400 are fed to the hydroprocessing system 300, to a first hydroprocessing reactor 310 for enacting catalytic hydrotreatment, hydrodesulfurization, hydrodenitrification, hydrodeoxygenation and hydrodewaxing reactions. The first hydroprocessing product 131 from the first hydroprocessing reactor 310 is directed to separator 311, where stream 133 containing hydrogen and light hydrocarbons and stream 132 containing H2S and CO/CC a re separated from stream 134 comprising heavy hydrocarbons. Stream 132, suitably combined with stream 140, may be recycled to the pyrolysis reactor 100. Optionally H2S may be sepa rated as stream 135 in a separator 313 from stream 132 to provide stream 136 containing CO/CO2, which is combined with stream 140 and directed to pyrolysis reactor 100. Stream 133 is recycled, suitably combined with stream 150 to the hydrogen plant 100. Stream 134 and hydrogen stream 130 are directed to a second hydroprocessing reactor 312 for enacting catalytic hydrotreatment and hydrodea romatization. Stream 130 may contain sulfur compounds, and pyrolysis oil 60 may contain sulfur compounds. If necessa ry, sulfur compounds may be added to stream 130 or 60. The hydroprocessed product, stream 160 from the hyd roprocessing reactor system 300 is directed to a separator 700, such as cold sepa rator, where separation of an aqueous component, i .e. stream 170 containing water and a heavy component, i .e. stream 180 takes place. Stream 180 comprising the heavy component may be directed to fractionation and separation suitably in a fractionator (710) where fractions comprising hydroca rbons boiling in the liquid fuel ranges may be obtained, suitably diesel fraction 213 and gasoline fraction 214. Optionally stream 190 comprising light components may also be separated in separator 700 and it may be directed to a sepa rator for the sepa ration of H2S and CO/C02 from hyd rogen and light hydrocarbons as described in Figure 2. Stream 150 is recycled to the hydrogen plant 100. Any suitable reactor types or configurations and devices may be used . Alternatively the hydroprocessed product 160 may be directed to the fractionator 710 directly from the hyd roprocessing system 300. Pyrolysis

The pyrolysis is carried out as non-catalytic thermal pyrolysis, suitably as fast pyrolysis. The pyrolysis may be carried out in any pyrolysis reactor. Suitably a fluidized bed reactor, such as a circulating fluidizing bed reactor, a bubbling bed fluidizing bed reactor, a combination thereof or the like is used.

The fluidizing fluid is suitably selected from inert gases (such as N2, Ar, He, Ne), flue gas (such as flue gas obtained from the boiler), CO, CO2, H2S (particularly obtained from hydroprocessing). Suitably the fluidizing fluid comprises reductive gases selected from CO and H2S and combinations thereof. If necessary, additional fluis, such as N2 and/or CO2 may be used. According to one suitable embodiment the flue gas from the boiler is used as the fluidizing fluid in the pyrolysis reactor. Optionally the flue gas may be mixed with inert gases and gas mixtures. The pyrolysis is carried out under reductive gas atmosphere. Suitably said gas atmosphere comprises CO, H2S or a combination thereof. The amount of the reducing gas is calculated based on the oxygen content of the feedstock to provide at least the needed minimum amount. Suitably the reducing gas is used in amounts of 20-100 % by volume in excess. The reducing gas acts a reagent and removes oxygen from the biomass feedstock.

The pyrolysis is carried out at the temperature of 200-800°C, suitably 300-700°C, more suitably 300-550°C, more suitably 400-500°C.

The pyrolysis is carried out under the pressure of 0-50 bar, suitably 0.1-20 bar, more suitably 0.5-20 bar, more suitably 1-15 bar.

A heat transfer material is typically used for heating the feedstock particles in fluidized bed reactors. Any conventional heat transfer material may be used, such as sand. The residence time of heat transfer material in the pyrolysis reactor is 0.8-2, suitably 0.9- 1.5 times the residence time of the feedstock.

In the pyrolysis reactor the heat transfer material is floating with the fluidizing fluid in the reactor. At least part of the heat transfer material is carried with the fluidizing fluid to the outlet of the reactor, suitably at the top of reactor, wherefrom it is directed to a solids/vapor separator, such as a cyclone. In said solids/vapor separator solid particles are separated from the vapors and gaseous components, said solid particles comprising char and the heat transfer material.

In the embodiment a boiler is integrated with the pyroiysis reactor, where the heat transfer material is looped between the pyroiysis reactor and the boiler. The heat transfer material is conducted from the boiler using a conduit, transfer pipe etc., suitably arranged at the lower half of the boiler, to the fluidized bed pyroiysis reactor, suitably to an inlet at the lower half, particularly suitably arranged at the bottom of the pyroiysis reactor.

The residence time of the feedstock (transported through the pyroiysis reactor) is typically 0.1 - 200 s, suitably 0.1 - 10 s, particularly suitably 0.1 - 5 s.

The feedstock is pyrolyzed suitably in a fluidized bed pyroiysis reactor in the presence of the heat transfer material, whereby pyroiysis output comprising pyroiysis vapors, gases and char and the heat transfer material (solids) is obtained. The pyroiysis output is directed to a solids/vapor separator, such as a cyclone, where the solids comprising char and heat transfer material are separated. In the case the pyroiysis reactor is integrated with a boiler the solids are recycled to the boiler and the gases and vapors are directed to a condenser where pyroiysis oil and non-condensable gases are separated. The non-condensable gases are then directed to the hydrogen plant, where the light hydrocarbons are converted to hydrogen and CO.

Feedstock comprising biomass is subjected to pyroiysis. The biomass may comprise a wide variety of materials of biological origin. Biomass may typically comprise virgin and waste materials of plant, animal and/or fish origin or microbiological origin, such as 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 semisolid organic residues of anaerobic or aerobic digestion, such as residues from bio-gas production from lignocellulosic and/or municipal waste material, residues from bio-ethanol production process, and any combinations thereof. Biomass may include the groups of the following four categories: wood and wood residues, including sawmill and paper mill discards, municipal paper waste, agricultural residues, including corn stover (stalks and straw) and sugarcane bagasse, and dedicated energy crops, which are mostly composed of tall, woody grasses. Suitably the biomass is selected from material originating from non-edible sources such as non-edible wastes and non-edible plant materials. Particularly suitably said biomass comprises waste 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 biomass feedstock may be subjected to size reduction or particularization prior to feeding to the pyrolysis reactor to provide size of the biomass for heat transfer rates suitable for maximal oil production. Any suitable grinder etc. may be used.

The biomass feedstock may be subjected to pretreatment comprising treatment with an aqueous acid. Said acid may be selected from formic acid, acetic acid, sulfurous acid, sulfuric acid and acidic water streams from the process or obtained from as by-product from other processes, such as aqueous acetic acid obtained from thermochemical treatment of wood . Suitably an aqueous stream obtained from the hydroprocessing system or an aqueous stream obtained from the hydrogen plant, particularly from the separation unit, or combinations thereof is used, optionally with added formic acid, acetic acid, sulfurous acid or sulfuric acid. Pretreatment temperatures below 100°C may be used, suitably below the boiling point of the acid. Suitably temperatures between 40 and 80°C are used, with short contact times of minutes.

After the treatment with an acid the biomass feedstock may be subjected to drying for reducing the moisture content therein prior to feeding to the pyrolysis reactor. Suitably the moisture content may be reduced to not more than 15 wt%, more suitably not more than 10 wt%, or even not more than 5 wt%, on dry weight basis. Drying of the biomass reduces char formation. Any driers suitable for drying of biomass can be used, such as drum driers, flash driers, fluidized bed driers etc., where drying may be carried out with a drying gas. Hot flue gas obtained from the boiler is suitably used as the drying gas. Boiler

In the integrated process the pyrolysis reactor is optionally integrated with a boiler. In this embodiment of the integrated process fuel is fed to the boiler, where said fuel is combusted to provide flue gas and thermal energy, which can be converted to electricity, stream etc. Any fuels suitable for use in boilers, particularly in fluidized bed boilers may be used including gases, solids, liquids and mixtures thereof, based on fossil and renewable materials, such as coal, peat, heavy fuel oils, liquid fuels, biomass, waste materials, etc and combinations thereof. Said gases may include natural gas, biogas, light-end of pyrolysis, non-condensable pyrolysis gases, etc. Renewable materials, such as solid wood based material, biomass, etc. may suitably be used as main fuel in the boiler. Co-fuels may suitably be selected from gases and other listed fuels. The solid fuel may optionally be dried with methods known as such prior to feeding to the boiler. Suitably the flue gases may be used for providing necessary heat to drying.

The boiler may be any type of boiler. Suitably a fluidized bed boiler, where solid fuel, char and non-condensed gas can be combusted, and heat transfer material, such as sand etc. is heated. Said fluidized bed boiler may be a circulating fluidized bed boiler, a bubbling fluidized bed boiler, a combination thereof or other fluidized bed boiler known as such. The boiler may be operated at conditions generally used in fluidized bed boilers, the temperature typically being from 700 to 1200°C. Suitably air flow is adjusted to provide the oxygen/fuel ratio necessary for combustion. The hot heat transfer material is suitably recycled or looped from the boiler to the pyrolysis reactor for maintaining the necessary pyrolysis temperature in the pyrolysis reactor.

The fluidized bed boiler has suitably a conduit, feed pipe or the like for transferring the heat transfer material to the pyrolysis reactor. Suitably a pneumatic system is used for transferring the heat transfer material from the boiler to the pyrolysis reactor. The conduit, feed pipe etc. is suitably arranged at the bottom of the fluidized bed boiler or at the side of it.

The inlets of the air flow, fuel, heat transfer material to the boiler and the outlet of the heat transfer material may be selected according to the boiler configuration.

During the start-up of the process the heat transfer material is treated in the boiler first. At least partly the heat transfer material is recycled or looped from the boiler to the pyrolysis reactor, and from the pyrolysis reactor, via a solid/vapor separator to the boiler.

According to one suitable embodiment the flue gas from the boiler is conducted to the fluidized bed pyrolysis reactor where the flue gas stream comprising CO/CO2 acts as a reducing agent and also provides for the fluidizing fluid needed in the pyrolysis reactor. According to one embodiment the flue gas may be used for drying of the biomass feedstock. According to one embodiment the flue gas may be used for drying of the solid feed to the boiler.

Hydroprocessing

The pyrolysis oil may directly be subjected to catalytic hydroprocessing for providing transportation fuels and other chemicals.

Said catalytic hydroprocessing may be carried out in one stage where hydrotreatment, hydrodeoxygenation (HDO), hydrodearomatization (HDA), hydrodenitrification (HDN) hydrodesulfurization (HDS) and hydrodewaxing (HDW) are carried out, or in at least two stages, where in the first stage hydrotreatment, hydrodeoxygenation (HDO), hydrodesulfurization (HDS), hydroisomerization (HI) and/or hydrodewaxing (HDW) is carried out and in the second stage hydrodearomatization (HDA) is carried out; or alternatively where in the first stage hydrotreatment, hydrodeoxygenation (HDO) and hydrodesulfurization (HDS) is carried out, in the second stage hydroisomerization (HI) and/or hydrodewaxing (HDW) is carried out and in the third stage hydrodearomatization (HDA) is carried out.

The HDO catalyst can be any HDO catalyst known in the art for the removal of hetero atoms (0, S, N) from organic compounds. In an embodiment of the invention, the HDO catalyst is selected from a group consisting of NiMo, CoMo, and a mixture of Ni, Mo and Co. Suitably the HDO catalyst is a supported catalyst and the support can be any oxide, typically said oxide is selected from AI2O3, S1O2, Zr02, zeolites, zeolite-alumina, alumina-silica, alumina- silica-zeolite and activated carbon, and mixtures thereof. The HDO catalyst(s) is/are sulphided prior to start up. Adequate sulphidization during operation is usually provided by sulphur compounds contained in the feed material.

In an embodiment of the invention, the HDW catalyst is selected from hydrodewaxing catalysts typically used for isomerising and cracking paraffinic hydrocarbon feeds. Examples of HDW catalysts include catalysts based on Ni, W, and molecular sieves.

NiW has excellent isomerising and dearomatising properties and it also has the capacity of performing the hydrodeoxygenation and other hydrogenation reactions of biological feed materials, which are typically performed by HDO catalysts. Aluminosilicate molecular sieves and especially zeolites with medium or large pore sizes are also useful as HDW catalysts in the present invention. Typical commercial zeolites useful in the invention include for instance ZSM-5, ZSM-11, ZSM-12, ZSM 22, ZSM-23 and ZSM 35. Other useful zeolites are zeolite beta and zeolite Y.

The HDW catalyst is also supported on an oxide support. The support materials may be the same as or different from those of the HDO catalyst. In an embodiment of the invention the HDW catalyst is selected from N 1W/AI2O3 and NiW/zeolite/AI₂03. These HDW catalysts are especially well suited for combining with the HDO catalyst of the invention since they also require sulphidizing for proper catalytic activity.

In an embodiment of the invention, the HI catalyst is selected from hydroisomerizing catalysts typically used for isomerizing paraffinic hydrocarbon feeds. Suitably the HI catalysts contain a Group VIII metal (e.g. Pt, Pd, Ni) and/or a molecular sieve. Preferred molecular sieves are zeolites (e.g. ZSM-22 and ZSM-23) and silicoaluminophosphates (e.g. SAPO-11 and SAPO-41). HI catalysts may also contain one or more of the support materials described above. In one embodiment, the HI catalyst comprises Pt, a zeolite and/or silicoaluminophosphate molecular sieve, and alumina. The support may alternatively or additionally contain silica.

The HDA catalyst is selected from sulphur tolerant dearomatization catalysts and sulphur tolerant isomerization catalysts and their combinations.

The HDA catalyst is selected from catalysts containing metals of the Group VIII of the Periodic table of Elements, Group VIB and the rare earth metals, which catalyst is capable of dearomatizing the feed material. Suitably the metal is selected from Pt, Pd, Ir, Ru, Rh, Re, Ni, Co, Mo, W, CoMo, NiMo or NiW, in elemental, oxide or sulphide form, and mixtures and combinations thereof.

Suitably said catalyst comprises a support selected from oxide supports, such as alumina, titania, silica, magnesia, zirconia, and B2O3, and other supports, such as carbon, charcoal, zeolites, and combinations thereof, suitably AI2O3, AI2O3-S1O2, zeolite Y, AI2O3- B2O3, or S1O2 and combination thereof. The catalyst may be promoted (or acid promoted) by for example fluorine, fluoro-sulfonic acid, trifluorimethanesulfonic acid or hydrogen fluoride as a Bronsted acid, or Friedel-Crafts catalyst selected from the group consisting of boron fluorides, tantalum fluorides and niobium fluorides, for increasing the acidity of the support whereby sulfur tolerance of the catalyst is improved. Examples of suitable sulfur tolerant catalysts, in addition to all metal sulphides are Pd and/or Pt on zeolite Y/AI2O3 , optionally with added Na; Pd and/or Pt on zirconia/silica, optionally with added alumina or alumina-silica; Pd and/or Pt on alumina/alumina-silica, optionally with one or more of titania, silica, magnesia, zirconia; Pd or Pt or Ir on carbon, or charcoal, suitably Pd promoted with tantalum perfluoride and hydrogen fluoride; Pd, Pt, Ir, Ru, Rh and/or Re on silca/alumina, sulphidized CoMo and NiMo catalysts on alumina/alumina-silica; and Pd-Pt on AI2O3 - B2O3. By using suitable modified supports the HDA catalyst containing noble metals, such as Pd, Pt, Ir, Ru, Rh and/or Re, can maintain their activity even in sulphur containing process conditions. The hydroprocessing is carried out under a pressure of 20 - 300 bar. When the hydroprocessing is carried out as a one-step process the pressure is 20 - 180 bar, suitably 50 - 150 bar. When the hydroprocessing is carried out as a two-step process the pressure in the first hydroprocessing step is 50 - 180 bar, suitably 70 - 120 bar and the pressure in the second hydroprocessing step 5 - 110 bar, suitably 10 - 90 bar.

The hydroprocessing is carried out at a temperature in the range of 280 °C to 450 °C, suitably at 300 °C to 400 C. When the hydroprocessing is carried out as a one-step process the temperature is 250-400°C, suitably 300-390°C. When the hydroprocessing is carried out as a two-step process the temperature in the first hydroprocessing step is 100 - 250°C, and the temperature in the second hydroprocessing step is 250 - 400°C.

The hydroprocessing feed rate WHSV (weight hourly spatial velocity) of the pyrolysis oil is proportional to an amount of the catalyst. The WHSV of the feed material in the present invention varies between 0.1 and 5, and is preferably in the range of 0.3 - 0.7.

The ratio of H2/feed in the present invention depends on pyrolysis oil and varies between 600 and 4000 Nl/I, suitably of 1300-2200 Nl/I.

The feed is pumped to the hydroprocessing reactor at a desired speed. Suitably the feed rate LHSV (liquid hourly space velocity) of the feed material is in the range of 0.01-10 h ^_1, suitably 0.1- 5 h ¹.

According to one embodiment of the invention the hydroprocessing is carried out in one step, where the HDO, HDW and HDA reactions are carried out in single phase. The pyrolysis oil is contacted with at least one hydrodeoxygenation catalyst, at least one hydrodewaxing catalyst and at least one hydrodearomatization catalyst in a first hydroprocessing step, to obtain a hydroprocessing product, in the presence of hydrogen, in a hydroprocessing reactor system. It is to be noted that the single phase treatment does not mean that the catalyst beds are packed in a single reactor but they can also be placed in separate reactors arranged in series. In the embodiment where the hydroprocessing is carried out in one step, the HDA catalyst is selected from sulfidized metal catalysts and sulphur tolerant acid promoted noble metal catalysts, such as NiMo, CoMo, and catalysts containing Co or Ni. Suitably the HDA catalyst beds are located in the same reactor and/or in the same pressure vessel.

According to another embodiment, the hydroprocessing is performed in at least two steps. The pyrolysis oil is contacted with at least one hydrodeoxygenation catalyst and at least one hydrodewaxing catalyst in a first hydroprocessing step, and with at least one hydrodearomatization catalyst in a second hydroprocessing step to obtain a hydroprocessing product, in the presence of hydrogen, in a hydroprocessing reactor system. In said embodiment suitably at least two pressure vessels and/or reactors are used. In the first hydroprocessing step the purified and optionally pretreated feedstock is subjected to hydroprocessing in the presence of the HDO and HDW catalysts, and the obtained product, which may comprise a gaseous fraction comprising H2, CO, CO2, H2S, H2O and light gaseous components and an effluent, or at least one fraction of said product, is subjected in the second hydroprocessing step to hydroprocessing in the presence of the HDA catalyst. The hydroprocessing steps are highly exothermic reactions in which the temperature can rise to a level which is detrimental to the stability of the catalyst and/or product quality. In some cases, it may be necessary to control the temperature variations particularly in the catalyst beds. Recirculation of the hydrocarbon product stream and effluent gas provide an efficient means for constraining the exothermic reaction whereby the recycled liquid and gas streams act as media for lowering the temperature of the catalyst beds in a controlled manner.

Additionally the hydrocarbon product may be directed for quench purposes between one or more catalyst beds.

In an embodiment of the invention the light hydrocarbons and/or gaseous fractions separated at one or more locations of the process are directed to an amine scrubber, which removes H2S and CO2 from the gaseous products. The scrubbed gases, comprising mainly hydrogen and some impurities, may be recycled to the process as feed hydrogen and quench gas, and to the hydrogen plant. The product from the hydroprocessing system, or from the first hydroprocessing reactor in the case of two-step hydroprocessing, is drawn off from the bottom of the last reactor. In one embodiment of the invention where the hydroprocessing system comprises one step the product is directed to a separator, such as a ny suitable separator or flashing unit. In the sepa rator, water, the light component comprising hydrogen, light hydrocarbons (CI - C5 hydrocarbons), H2S, CO and CO2 a re sepa rated from the heavy component comprising >C5 hydrocarbons and some CI - C5 hydrocarbons.

In another embodiment where the hyd roprocessing system comprises at least two steps a sepa rator is suitably arranged between the steps where water, light component comprising hydrogen, light hydrocarbons (CI - C5 hyd rocarbons), H2S, CO and CO2 are separated . Thus the hydroprocessing product also encompasses the product obtained from the first hydroprocessing step.

The hydroprocessing product from the hydroprocessing system may be directly subjected to fractionation to provide desired hydrocarbon fractions, or alternatively there may be a sepa rator a rranged after the hyd roprocessing system . Water and gases may also be sepa rated by other means which are well known to those skilled in the art.

The liquid reaction products, i .e. the mixture of higher (> C5) hydrocarbons is subjected to fractionation . Suitably it is fed to a separation column where d ifferent fuel grade hydrocarbon fractions are recovered . The liquid 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. The person skilled in the art is able to vary the distilling conditions and to change the temperature cut point as desired to obtain any suitable hydrocarbon product.

The recovered middle distillate fraction may comprise gas oil, i .e. a hydrocarbon fraction having a boiling point in the diesel range. A typical boiling point is from 160°C to 380°C, meeting characteristics of the specification of EN 590 diesel . The diesel product may be fed to a diesel storage tank. Also hyd rocarbon fractions distilling at temperatures ranging from 40°C 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. Additionally, fraction suitable as solvents, aviation fuels, kerosene etc may be obta ined .

From the fractionator, the heavier hydrocarbons may also be recycled back to the inlet end of the hydroprocessing reactor system and mixed into the feed to the hydroprocessing reactor.

A person skilled in the art is able to vary the fractionation/distilling conditions and to change the temperature cut point as desired to obtain any hydrocarbon product, boiling suitably in the transportation fuel ranges.

In order to function and stay active particularly the HDO and HDW catalysts used in the present invention need sulphur. Therefore when the feed to the hydroprocessing does not in itself contain sulphur or its sulphur concentration is too low, additional sulphur is fed to the step of hydroprocessing. The additional sulphur can be fed to the hydroprocessing step together with the feed or it can be fed separately to the hydroprocessing step. Additional sulphur can be supplied to the process in gaseous form like hydrogen sulphide, or it can be any material that produces hydrogen sulphide in the process, like organic sulphur compounds, such as dimethyl disulphide. The amount of additional sulphur depends on the amount of sulphur contained in the feed . A person skilled in the art is able to determine the amount of needed sulphur without undue burden. Generally, the sulphur content in the feed is suitably maintained at the level of 200-300 ppm, calculated as elemental sulphur.

The hydroprocessing can be carried out in any kind of reactor, column, vessel, container, tube or pipe, which is suitable for hydroprocessing.

Hydrogen plant

The hydrogen plant comprises a steam reformer unit, a desulfurization unit upstream the steam reformer unit, and water gas shift unit. Suitably said hydrogen plant comprises also a carbon monoxide/carbon dioxide/water separator unit downstream the water gas shift unit.

In the hydrogen plant starting material selected from natural gas, biogas, methane, ethane, butane, propane, naphtha, liquefied petroleum gas (LPG) and any combination thereof, in combination with one or more recycle stream from the hydroprocessing system comprising light hydrocarbons (C1-C5) and non-condensable gases separated from the pyrolysis output, is subjected to sulfur removal in the desulfurization unit in the presence of hydrogen and at least one sulfur removal catalyst at conditions effecting sulfur removal. Typically catalysts such as CoMo, NiMo, optionally comprising ZnO or Ni absorbent particularly for low sulfur contents, may be used . Suitable reaction conditions for CoMo and NiMo catalysts include 300-400°C temperatures; when absorbents are used lower temperatures of 200- 300°C are more suitable. Pressures of 5 - 30 bar, suitably ones used also for the steam reforming may be used. The recycle stream obtained from the hydroprocessing system, containing hydrogen and light hydrocarbons (C1-C5) is used for providing hydrogen for sulfur removal. The desulfurization unit comprises one or more sulfur removal reactors arranged upstream the steam reformer unit. Sulfur containing compounds, particularly high molecular weight compounds in the starting material (such as natural gas or LPG) are hydrogenated to hydrogen sulfide, which may be removed by suitable means, and optionally said H2S may be directed to the pyrolysis reactor. If necessary, hydrogen make-up stream may be used to supply additional hydrogen to the desulfurization unit.

The desulfurized starting material from the desulfurization unit is directed to a steam reformer unit for conversion of light hydrocarbons, particularly methane, to carbon monoxide and hydrogen. Any standard steam reforming reactors and catalysts may be used, such as nickel based catalysts. An example of a suitable catalyst is nickel oxide on a low- silica refractory base. High temperatures of 700 - 1100°C and pressures of 5 - 50 bar are typically used.

The gases exiting the steam reformer unit may then be directed to a water gas shift unit comprising at least one water gas shift reactor where the carbon monoxide is reacted with water to produce additional hydrogen. Any standard water gas shift reactors and catalysts may be used, such as copper based catalysts and ferrochromium based catalysts. Pressures of 5-50 bar, suitably the same as in the steam reformer may be used. The temperature may range between 200 and 400°C, depending on the catalyst. Suitably high temperature catalysts, such as ferrochromium catalysts are used, at 300-400°C temperatures.

The gases exiting the water gas shift unit are passed through a carbon monoxide/carbon dioxide/water separator unit. Said unit may comprise a pressure swing absorber unit (PSA) or the like, suitable for removing carbon dioxide, carbon monoxide and water, whereby hydrogen is obtained, suitably in essentially pure form. Separated water may be recycled to the steam reformer unit or to the optional pretreatment of the biomass feedstock and the CO/CO2 stream is directed to the pyrolysis reactor.

The catalysts in the steam reformer and water gas shift units in the hydrogen plant do not tolerate sulfur and thus the desulfurization unit is arranged upstream from the steam reformer. In said desulfurization unit high molecular weight sulfur compounds are hydrogenated to hydrogen sulfide, suitably utilizing the recycle stream from the hydroprocessing system. Hydrogen contained in said recycle stream effects the desulfurization, and the light hydrocarbons in said recycle stream provide for additional starting material source for hydrogen in the subsequent steam reformer unit.

The integrated process provides several advantages. The reductive gas atmosphere in the pyrolysis promotes the removal of oxygen and further oxidation of biomass is prevented, whereby compounds requiring less hydrogen in the subsequent hydroprocessing stage are formed. No hydrogen is needed in the non-catalytic thermal pyrolysis. The thermal pyrolysis can be carried out at lower temperatures and less energy is needed. The reductive gases are generated in the integrated process. The optional pretreatment of the biomass feedstock with an acid increases further the pyrolysis oil yields.

In the integrated process any standard fluidized bed boiler can be used. The boiler also provides the heat required for the pyrolysis reactor, and the flue gases from the boiler may be used as the fluidizing fluid in the pyrolysis reactor and as final reducing gas of the reducing agent.

The integrated process provides the reductive gases necessary for the pyrolysis whereby the pyrolysis may be carried out at lower temperatures, recycle streams of the process are effective utilized for providing hydrogen for the hydroprocessing, aqueous streams may be utilized particularly in the optional pretreatment and flue gases from the boiler may be used for drying and heating purposes.

Claims

An integrated process for producing hydrocarbons, wherein said process comprises the steps, where

CO, CO2 and H2S are separated from the light component and hydrocarbons having carbon number from 1 to 5 are directed to a hydrogen plant where they are converted to hydrogen and carbon monoxide and carbon dioxide, hydrogen is separated and directed to the hydroprocessing system and gas stream comprising carbon monoxide and carbon dioxide is directed to the pyrolysis reactor, and

2. The integrated process according to claim 1, wherein the char is directed to a boiler comprising heat transfer material and said char is combusted together with fuel to produce heat and flue gas.

The integrated process according to claim 1 or 2, wherein the wherein the feedstock comprising biomass is selected from virgin and waste materials of plant, animal and/or fish origin or microbiological origin, preferably the feedstock is selected from virgin wood, wood residues, forest residues, waste, municipal waste, industrial waste or by-products, agricultural waste or by-products, residues or by-products of the wood-processing industry, waste or by-products of the food industry, solid or semisolid organic residues of anaerobic or aerobic digestion, residues from bio-ethanol production process, and any combinations thereof.

4. The integrated process according to any one of claims 1-3, wherein the non- condensable gases are directed to the hydrogen plant.

5. The integrated process according to any one of claims 1-4, wherein the pyrolysis reactor is a fluidized bed reactor.

6. The integrated process according to any one of claims 2-4, wherein the boiler is a fluidized bed boiler.

7. The integrated process according to claim 6 or 7, wherein the heat transfer material is looped between the pyrolysis reactor and the boiler.

8. The integrated process according to any one of claims 1-7, wherein the reductive gas atmosphere comprises CO, H2S or a combination thereof. 9. The integrated process according to any one of claims 1-8, wherein the pyrolysis is carried out at the temperature of 200-800°C, preferably 300-700°C.

10. The integrated process according to any one of claims 1-9, wherein the pyrolysis is carried out under the pressure of 0-50 bar, preferably 0.1-20 bar.

11. The integrated process according to any one of claims 1-10, wherein the residence time of the feedstock in the pyrolysis reactor is 0.1 - 200 s, preferably 0.1 - 10 s.

12. The integrated process according to claim 11, wherein the residence time of the heat transfer material in the pyrolysis reactor is 0.8 - 2 times the residence time of the feedstock.

13. The integrated process according to any one of claims 5-12, wherein the flue gas from the boiler is used as fluidizing gas in the pyrolysis reactor.

14. The integrated process according to any one of claims 1-13, wherein CO, CO2 and H2S separated from the light component are directed to the pyrolysis reactor.

15. The integrated process according to any one of claims 2-14, wherein the flue gas from the boiler is used for drying of the feedstock comprising biomass.

16. The integrated process according to any one of claims 2-15, wherein the flue gas from the boiler is used for drying of fuel.

17. The integrated process according to any one of claims 1-16, wherein the catalytic hydroprocessing is carried out in one stage or in two or more stages.

18. A method for producing hydrocarbons, wherein said method comprises the steps of j) pyrolysing feedstock comprising biomass under reductive gas atmosphere in a pyrolysis reactor to yield pyrolysis products and char,

k) separating the pyrolysis products from the char,

I) condensing the pyrolysis products to form pyrolysis oil and non-condensable gases, m) subjecting the pyrolysis oil to catalytic hydroprocessing in a hydroprocessing system in the presence of hydrogen to yield a hydroprocessing product,

n) separating from the hydroprocessing product an aqueous component, a heavy component comprising hydrocarbons having carbon number more than 5, and a light component comprising gases and hydrocarbons having carbon number from 1 to 5 from the hydroprocessing product,

o) directing hydrocarbons having carbon number from 1 to 5 derived in step e) to the hydrogen plant where they are converted to hydrogen, carbon monoxide and carbon dioxide,

p) separating CO, CO2 and H2S from the light component,

q) separating the hydrogen derived in step f) and directing it to the hydroprocessing system of step d) and

r) directing a gas stream comprising carbon monoxide and carbon dioxide derived in step f) to the pyrolysis reactor of step a).

19. The method for producing hydrocarbons according to claim 18, wherein the non- condensable gases are directed to a hydrogen plant.

20. The method for producing hydrocarbons according to claim 18 or 19, wherein CO, CO2 and H2S are recycled to the pyrolysis reactor.

21. The method for producing hydrocarbons according to any one of claims 18 - 20, wherein the char is directed to a boiler and combusted together with fuel to produce heat and flue gas.

22. The method according to any one of claims 18 - 21, wherein the feedstock comprising biomass is selected from virgin and waste materials of plant, animal and/or fish origin or microbiological origin, preferably the feedstock is selected from virgin wood, wood residues, forest residues, waste, municipal waste, industrial waste or by-products, agricultural waste or by-products, 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, residues from bio-ethanol production process, and any combinations thereof.

23. The method according to any one of claims 18-22, wherein the pyrolysis reactor is a fluidized bed reactor.

24. The method according to any one of claims 21-23, wherein the boiler is a fluidized bed boiler. 25. The method according to claim 23 or 24, wherein the heat transfer material is looped between the pyrolysis reactor and the boiler.

26. The method according to any one of claims 18-25, wherein the reductive gas atmosphere comprises CO, H2S or a combination thereof.

27. The method according to any one of claims 18-26, wherein the pyrolysis is carried out at the temperature of 200-800°C, preferably 300-700°C.

28. The method according to any one of claims 18-27, wherein the pyrolysis is carried out under the pressure of 0-50 bar, preferably 0.1-20 bar.

29. The integrated process according to any one of claims 1-10, wherein the residence time of the feedstock in the pyrolysis reactor is 0.1 - 200 s, preferably 0.1 - 10 s. 30. The method according to claim 29, wherein the residence time of the heat transfer material in the pyrolysis reactor is 0.8 - 2 times the residence time of the feedstock.

31. The method according to any one of claims 21-30, wherein the flue gas from the boiler is used as fluidizing gas in the pyrolysis reactor.

32. The method according to any one of claims 18-31, wherein CO, CO2 and H2S separated from the light component are directed to the pyrolysis reactor.

33. The method according to any one of claims 21-32, wherein the flue gas from the boiler is used for drying of the feedstock comprising biomass.

34. The method according to any one of claims 21-33, wherein the flue gas from the boiler is used for drying of fuel.

35. The method according to any one of claims 18-34, wherein the catalytic hydroprocessing is carried out in one stage or in two or more stages.

36. Use of recycle gas comprising CO for providing reductive gas atmosphere in pyrolysis process.

37. The use according to claim 36, wherein the recycle gas comprises further CO2.

38. The use according to claim 36 or 37, wherein the recycle gas is obtained from hydrogen plant integrated with the pyrolysis process.

39. The use according to any one of claims 36-38, wherein the recycle gas is obtained from flue gas of a boiler integrated with the pyrolysis process.

40. The use according to any one of claims 36-39, wherein the recycle gas is obtained from hydroprocessing system integrated with the pyrolysis process.

41. Arrangement for producing hydrocarbons, said arrangement comprising a pyrolysis reactor (100) comprising an inlet for feedstock, an inlet for reducing gas and inlet for heat transfer material, said pyrolysis reactor (100) being connected with a solids/vapor separator (500) equipped with a conduit for transferring solids to a boiler

(200) and vapors to a condenser (600) equipped with an outlet for non-condensable gases and an outlet for pyrolysis oil, said boiler (200) comprising an inlet for fuel and outlet for flue gas and a conduit for transferring heat transfer material to the pyrolysis reactor (100), said arrangement further comprising a hydrogen plant (400) equipped with an inlet for starting material and recycled light components and an outlet for hydrogen and an outlet for CO/CO2, said arrangement further comprising a hydroprocessing system (300) equipped with an inlet for pyrolysis oil and an inlet for hydrogen, a separator (700) for separating an aqueous component, a light component and a heavy component comprising hydrocarbons.