CA2816353A1

CA2816353A1 - Process for the preparation of a biofuel and/or biochemical

Info

Publication number: CA2816353A1
Application number: CA2816353A
Authority: CA
Inventors: Johannes Antonius Hogendoorn; Sascha Reinier Aldegonda Kersten; Ferran De Miguel Mercader; Colin John Schaverien; Nicolaas Wilhelmus Joseph Way
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2010-11-12
Filing date: 2011-11-11
Publication date: 2012-05-18
Also published as: BR112013011287A2; WO2012062924A1; CN103201357A; JP2013545841A; EP2638127A1

Abstract

A process for the preparation of a biofuel and/or biochemical from a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, comprising the steps of i) contacting the pyrolysis oil with a catalytic cracking catalyst at a temperature of equal to or more than 400°C in the presence of a hydrocarbon co-feed to produce one or more cracked products; ii) fractionating one or more of the cracked products to produce one or more product fractions; iii) using one or more of the product fractions to produce a biofuel and/or biochemical.

Description

PROCESS FOR THE PREPARATION OF A BIOFUEL AND/OR
BIOCHEMICAL
TECHNICAL FIELD OF THE INVENTION
The present invention relates to process for the preparation of a biofuel and/or biochemical. In addition the present invention provides processes to produce one or more cracked products from a pyrolysis oil.
BACKGROUND OF THE INVENTION
With the diminishing supply of crude mineral oil, use of renewable energy sources is becoming increasingly important for the production of fuels and chemicals. These fuels and chemicals from renewable energy sources are often referred to as biofuels, respectively biochemicals. One of the advantages of using renewable energy sources is that the CO2 balance is more favourable as compared with a conventional feedstock of a mineral source.
Biofuels and/or biochemicals derived from non-edible renewable energy sources, such as lignocellulosic material, are preferred as these do not compete with food production.
These biofuels and/or biochemicals are also referred to as second generation biofuels and/or biochemicals.
Lignocellulosic material, such as wood, can be pyrolyized to obtain a pyrolysis oil. It is currently believed, however, that such pyrolysis oil cannot be converted in a simple, direct or economically interesting manner, into biofuels and/or biochemicals.
Ardiyanti et al. in their article titled "Process-product studies on pyrolysis oil upgrading by hydrotreatment with Ru/C catalysts", first presented at the AICHE 2009 spring meeting in April 2009, mentioned that pyrolysis oil is not suitable for the purpose of co-feeding into existing refineries, either in hydrotreating or FCC units, because the oil is not miscible with hydrocarbon feedstocks and shows a high tendency for coking, leading to blockage of feeding lines and reactors. As an alternative a mild hydrotreating process is suggested. The article describes a two step hydrotreatment of a pyrolysis oil, obtained by fast pyrolysis of forest residue. In the product two phases were formed, viz, a black oil floating on top of a clear water layer. The oxygen content of the oil was reduced by hydrodeoxygenation to respectively 12.3 wt% and 11.5wt%. In the conclusion and outlook, it is mentioned that FCC experiments with low-residual product as co-feed are in progress to verify whether the product is indeed suitable as a feedstock for refinery units.
M.C. Samolada et al, in their article titled "Production of a bio-gasoline by upgrading biomass flash pyrolysis liquids via hydrogen processing and catalytic cracking", first published in Fuel, vol. 77, no 14, pages 1667-1675, 1998, describe that results of fluid catalytic cracking (FCC) of biomass flash pyrolysis liquids are not encouraging due to high coking (8-25wt%) and the low quality of the fuels obtained (about 20 wt% phenolics). They further noted that efforts towards blending biomass flash pyrolysis liquids with petroleum feedstocks prior to catalytic cracking were unsuccessful, because of their minor miscibility with hydrocarbons. In the article therefore a two-step process is proposed, including thermal hydrotreatment and subsequent catalytic cracking of biomass flash pyrolysis liquids. Thermal hydrotreatment is said to serve as the stabilization step for the biomass derived feedstock to FCC.
F. de Miguel Mercader et al, in their article titled "Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery units", Journal of Applied Catalysis B: Environmental, volume 96, 2010, pages 57-66, describe that the direct co-processing of pyrolysis oil itself in standard refinery units is problematic.
A. Oasmaa et al, in their article titled "Fast pyrolysis of Forestry Residue 1. Effect of extractives on phase separation of pyrolysis liquids", first published in Energy & Fuels, volume 17, number 1, 2003, pages 1-12, describes that a two-phase product is obtained by fast pyrolysis processes of forestry residues. It is stated that the top phase differs from the bottom phase, containing significant amount of hydrocarbon-soluble extractives and low amount of water-soluble polar compounds. Further the article indicates that the top phase has a significantly higher heating value than the bottom phase.
It would be an advancement in the art if a pyrolysis oil, which essentially has not been pretreated or upgraded by hydrotreatment or hydrodeoxygenation, could be used for the production of biofuels and/or biochemicals.
It would also be an advancement in the art if a process could be provided that allows direct processing of a pyrolysis oil, which essentially has not been pretreated or upgraded by hydrotreatment or hydrodeoxygenation, in an FCC unit.
SUMMARY OF THE INVENTION
Surprisingly such a process has now been found.
Accordingly the present invention provides a process for the preparation of a biofuel and/or biochemical from a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, comprising the steps of i) contacting the pyrolysis oil with a catalytic cracking catalyst at a temperature of equal to or more than 400 C
in the presence of a hydrocarbon co-feed to produce one or more cracked products;

ii) fractionating one or more of the cracked products to produce one or more product fractions;
iii) using one or more of the product fractions to produce a biofuel and/or biochemical.
Step i) can be carried out in various manners and accordingly the current invention also provides several processes for producing the one or more cracked products.
In a first embodiment the present invention provides a process to produce one or more cracked products comprising the steps of la) providing a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, or a part thereof containing in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives;
lb) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.
In a second embodiment the present invention provides a process to produce one or more cracked products comprising the steps of 2a) providing a bottom phase of a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, or a part thereof;
2b) contacting the bottom phase of the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.

In a third embodiment the present invention provides a process to produce one or more cracked products comprising the steps of 3a) providing a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, or a part thereof;
3b) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products; wherein the combination of the pyrolysis oil or part thereof and the hydrocarbon co-feed has an overall molar ratio of hydrogen to carbon (H/C) of equal to or more than 1 to 1 (1/1).
The processes of the invention advantageously allow for direct processing of pyrolysis oil, which essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, in a catalytic cracking unit, such as for example an FCC unit. The process of the invention advantageously allows the pyrolysis oil to be processed in a catalytic cracking unit without the necessity of such a hydrotreatment and/or hydrodeoxygenation to substantially lower the oxygen content.
Surprisingly it has been found that in the processes according to the invention the pyrolysis oil is sufficiently miscible with a hydrocarbon co-feed such that co-processing has been shown to be feasible.
In addition the hydrocarbon co-feed can advantageously provide the hydrogen necessary to convert the oxygen in the pyrolysis oil into water.
Further it has surprisingly been found that catalytic cracking of a pyrolysis oil in the presence of a hydrocarbon co-feed as explained below leads to a synergistic effect, where the coke make during the catalytic cracking step is less than what would be expected on the basis of the sum of the coke make for each feed when catalytically cracked separately.
The process is further advantageous in that going from the pyrolysis oil feed to the catalytic cracking products an extensive reduction in Total Acid Number (TAN) is obtained.
As no upgrading via any hydrotreatment is needed a more simple and more economic process is obtained than the processes of the prior art. Hence, the processes according to the invention advantageously allow a simple, direct and economically interesting route towards the conversion of pyrolysis oil into biofuels and/or biochemicals.
DETAILED DESCRIPTION OF THE INVENTION
In step i) a pyrolysis oil is contacted with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.
By a pyrolysis oil is herein understood an oil obtained by pyrolysis. By such pyrolysis oil is preferably further understood an oil obtained by pyrolysis that has essentially not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation. An hydrotreatment and/or hydrodeoxygenation to substantially reduce the oxygen content of the pyrolysis oil can advantageously be avoided in the processes according to the invention.
By a pyrolysis oil is further understood a "whole" pyrolysis oil or a part thereof. As illustrated below, in certain embodiments it is preferred to use specific parts of a pyrolysis oil.

Preferably the pyrolysis oil is derived from a renewable energy source, that is, preferably the pyrolysis oil is obtained by pyrolysis of a renewable energy source.
Any renewable energy source known to the skilled person to be suitable for providing pyrolysis oil may be used. Preferably the renewable energy source comprises a cellulosic material, more preferably a lignocellulosic material. Hence, preferably the pyrolysis oil is a pyrolysis oil derived from a cellulosic material, more preferably a lignocellulosic material.
Any suitable cellulose-containing material may be used as renewable energy source in the pyrolysis. The cellulosic material may be obtained from a variety of plants and plant materials including agricultural wastes, forestry wastes, sugar processing residues and/or mixtures thereof. Examples of suitable cellulose-containing materials include agricultural wastes such as corn stover, soybean stover, corn cobs, rice straw, rice hulls, oat hulls, corn fibre, cereal straws such as wheat, barley, rye and oat straw; grasses;
forestry products such as wood and wood-related materials such as sawdust; waste paper; sugar processing residues such as bagasse and beet pulp; or mixtures thereof. In a more preferred embodiment the pyrolysis oil is obtained by pyrolysis of wood and/or a wood-related material, such as forestry residue, wood chips and/or saw dust. In another preferred embodiment, the wood and/or wood-related material contains bark and/or needles. Most preferably the pyrolysis oil is obtained by pyrolysis of wood and/or a wood-related material containing pine wood or forestry residue.
By pyrolysis is herein understood the thermal decomposition of a, preferably renewable, energy source at a pyrolysis temperature of equal to or more than 350 C. The concentration of oxygen is preferably less than the concentration required for complete combustion. More preferably the pyrolysis is carried out in the essential absence of non-in-situ-generated oxygen. A limited amount of oxygen may be generated in-situ during the pyrolysis process. Preferably pyrolysis is carried out in an atmosphere containing equal to or less than 5 vol.%
oxygen, more preferably equal to or less than 1 vol.% oxygen and most preferably equal to or less than 0.1 vol.% oxygen.
In a most preferred embodiment pyrolysis is carried out in the essential absence of oxygen.
The pyrolysis temperature is preferably equal to or more than 350 C, more preferably equal to or more than 400 C and most preferably equal to or more than 450 C. The pyrolysis temperature is further preferably equal to or less 800 C, more preferably equal to or less than 700 C and most preferably equal to or less than 650 C.
The pyrolysis pressure may vary widely. For practical purposes a pressure in the range from 0.1 to 5 bar (0.01 to 0.5 MegaPascal), more preferably in the range from 1 to 2 bar (0.1 to 0.2 MegaPascal) is preferred. Most preferred is an atmospheric pressure (about 1 bar or 0.1 MegaPascal).
In a preferred embodiment the pyrolysis oil is provided by so-called fast or flash pyrolysis of the renewable energy source. Such fast or flash pyrolysis preferably comprises rapidly heating the renewable energy source for a very short time and then rapidly reducing the temperature of the primary products before chemical equilibrium can occur.
In a preferred embodiment the pyrolysis oil is provided by pyrolysis of the renewable energy source comprising the steps of - heating the renewable energy source in the essential absence of oxygen to a temperature equal to or more than 350 C, preferably equal to or more than 400 C, and preferably equal to or less than 800 C within 3 seconds, preferably within 2 seconds, more preferably within 1 second and most preferably within 0.5 seconds;
- maintaining the renewable energy source at a temperature equal to or more than 350 C, preferably equal to or more than 400 C, and preferably equal to or less than 800 C for between 0.03 and 2.0 seconds, preferably between 0.03 and 0.60 seconds, to produce one or more pyrolysis products;
- cooling the pyrolysis products to below 350 C within 1 second, and preferably within 0.5 seconds;
- obtaining the pyrolysis oil from the pyrolysis products.
Examples of suitable fast or flash pyrolysis processes to provide the pyrolysis oil are described in A. Oasmaa et al, "Fast pyrolysis of Forestry Residue 1. Effect of extractives on phase separation of pyrolysis liquids", Energy & Fuels, volume 17, number 1, 2003, pages 1-12; and A. Oasmaa et al, Fast pyrolysis bio-oils from wood and agricultural residues, Energy & Fuels, 2010, vol. 24, pages 1380-1388; US4876108;
US5961786; and US5395455, which are herein incorporated by reference.
After pyrolysis of the renewable energy source, pyrolysis products are obtained that may contain gas, solids (char), one or more oily phase(s), and optionally an aqueous phase.
The oily phase(s) will hereafter be referred to as pyrolysis oil. The pyrolysis oil can be separated from the pyrolysis products by any method known by the skilled person to be suitable for that purpose. This includes conventional methods such as filtration, centrifugation, cyclone separation, extraction, membrane separation and/or phase separation.
The pyrolysis oil may include for example carbohydrates, olefins, paraffins, oxygenates (such as aldehydes and/or carboxylic acids) and/or optionally some residual water.
Preferably, the pyrolysis oil comprises carbon in an amount equal to or more than 25 wt%, more preferably equal to or more than 35wt%, and preferably equal to or less than 70 wt%, more preferably equal to or less than 60 wt% (on a dry basis).
The pyrolysis oil further preferably comprises hydrogen in an amount equal to or more than 1 wt%, more preferably equal to or more than 5wt%, and preferably equal to or less than 15 wt%, more preferably equal to or less than 10 wt% (on a dry basis).
The pyrolysis oil further preferably comprises oxygen in an amount equal to or more than 25 wt%, more preferably equal to or more than 35wt%, and preferably equal to or less than 70 wt%, more preferably equal to or less than 60 wt%. Such oxygen content is preferably defined on a dry basis. By a dry basis is understood excluding water.
The pyrolysis oil may also contain nitrogen and/or sulphur.
If nitrogen is present, the pyrolysis oil preferably comprises nitrogen in an amount equal to or more than 0.001 wt%, more preferably equal to or more than 0.1 wt%, and preferably equal to or less than 1.5 wt%, more preferably equal to or less than 0.5 wt% (on a dry basis).
If sulphur is present, the pyrolysis oil preferably comprises sulphur in an amount equal to or more than 0.001 wt%, more preferably equal to or more than 0.01 wt%, and preferably equal to or less than 1 wt%, more preferably equal to or less than 0.1 wt% (on a dry basis).
If present, the pyrolysis oil preferably comprises water in an amount equal to or more than 0.1 wt%, more preferably equal to or more than lwt%, still more preferably equal to or more than 5 wt%, and preferably equal to or less than 55 wt%, more preferably equal to or less than 45 wt%, and still more preferably equal to or less than 35 wt%, still more preferably equal to or less than 30 wt%, most preferably equal to or less than 25 wt%.

Preferably, the pyrolysis oil of the present invention comprises aldehydes in an amount equal to or more than 5 wt%, more preferably equal to or more than lOwt%, and preferably equal to or less than 30 wt%, more preferably equal to or less than 20 wt%.
Preferably, the pyrolysis oil comprises carboxylic acids in an amount equal to or more than 5 wt%, more preferably equal to or more than lOwt%, and preferably equal to or less than 25 wt%, more preferably equal to or less than 15 wt%.
Preferably, the pyrolysis oil comprises carbohydrates in an amount equal to or more than 1 wt%, more preferably equal to or more than 5wt%, and preferably equal to or less than 20 wt%, more preferably equal to or less than 10 wt%.
Preferably, the pyrolysis oil comprises phenols in an amount equal to or more than 0.1 wt%, more preferably equal to or more than 2wt%, and preferably equal to or less than 10 wt%, more preferably equal to or less than 5 wt%.
Preferably, the pyrolysis oil comprises furfurals in an amount equal to or more than 0.1 wt%, more preferably equal to or more than lwt%, and preferably equal to or less than 10 wt%, more preferably equal to or less than 4 wt%.
By a hydrocarbon co-feed is herein understood a co-feed that contains one or more hydrocarbon compounds (i.e.
compounds that contain both hydrogen and carbon). The hydrocarbon co-feed is preferably a liquid hydrocarbon co-feed. By a liquid hydrocarbon co-feed is understood a hydrocarbon co-feed which is fed to a catalytic cracking unit essentially in the liquid phase.
The hydrocarbon co-feed can be any hydrocarbon feed known to the skilled person to be suitable as a feed for an catalytic cracking unit. The hydrocarbon co-feed can for example be obtained from a conventional crude oil (also sometimes referred to as a petroleum oil or mineral oil), an unconventional crude oil (that is oil produced or extracted using techniques other than the traditional oil well method) or a renewable oil (that is oil derived from a renewable source).
Preferably the hydrocarbon co-feed is derived from a, preferably conventional, crude oil.
In one embodiment the hydrocarbon co-feed is derived from a, preferably conventional, crude oil. Examples of conventional crude oils include West Texas Intermediate crude oil, Brent crude oil, Dubai-Oman crude oil, Midway Sunset crude oil or Tapis crude oil.
More preferably the hydrocarbon co-feed comprises a fraction of a, preferably conventional, crude oil or renewable oil. Examples of fractions of a crude oil that can be used as a hydrocarbon co-feed include straight run (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO), coker gas oils, atmospheric residue ("long residue") and vacuum residue ("short residue") and/or mixtures thereof. In one preferred embodiment the hydrocarbon co-feed comprises comprises a long residue and/or a vacuum gas oil.
In one embodiment the hydrocarbon co-feed has an Initial Boiling Point (IBP) as measured by means distillation based on ASTM D2887-06a at a pressure of 1 bar absolute (0.1 MegaPascal) of equal to or more than 100 C, preferably equal to or more than 150 C. An example of such a hydrocarbon co-feed is vacuum gas oil.
In a second embodiment the hydrocarbon co-feed has an Initial Boiling Point (IBP) as measured by means of distillation based on ASTM D2887-06a at a pressure of 1 bar absolute (0.1 MegaPascal) equal to or more than 220 C, more preferably equal to or more than 240 C. An example of such a hydrocarbon co-feed is long residue.

In a further preferred embodiment equal to or more than 70 wt%, preferably equal to or more than 80 wt%, more preferably equal to or more than 90 wt% and still more preferably equal to or more than 95 wt% of the hydrocarbon co-feed boils in the range from equal to or more than 150 C to equal to or less than 600 C, as measured by means of a simulated distillation by gas chromatography based on ASTM D2887-06a.
The composition of the hydrocarbon co-feed may vary widely. The hydrocarbon co-feed may for example contain paraffins, olefins and aromatics.
In a preferred embodiment the hydrocarbon co-feed comprises equal to or more than 8 wt% elemental hydrogen, more preferably more than 12 wt% elemental hydrogen. A high content of elemental hydrogen, such as a content of equal to or more than 8 wt%, allows the hydrocarbon co-feed to act as a cheap hydrogen donor in the catalytic cracking process.
Without wishing to be bound by any kind of theory it is further believed that a higher weight ratio of hydrocarbon co-feed to pyrolysis will enable more upgrading of the pyrolysis oil by hydrogen transfer reactions.
In another embodiment at least part of the hydrocarbon co-feed comprises a paraffinic hydrocarbon co-feed. Examples of such paraffinic hydrocarbon co-feeds include so-called Fischer-Tropsch derived hydrocarbon streams such as described in W02007/090884 and herein incorporated by reference, or a hydrogen rich feed like hydrotreater product. The Fischer-Tropsch hydrocarbon stream may optionally have been obtained by hydroisomerisation of hydrocarbons directly obtained in a Fischer-Tropsch hydrocarbon synthesis reaction.
The hydrocarbon co-feed according to the invention preferably comprises equal to or more than 1 wt%

paraffins, more preferably equal to or more than 2 wt%
paraffins, and most preferably equal to or more than 5 wt%
paraffins, and preferably equal to or less than 99 wt%
paraffins, more preferably equal to or less than 50 wt%
paraffins, and most preferably equal to or less than 20 wt% paraffins, wherein by paraffins both normal-, cyclo-and branched-paraffins are understood.
In an especially preferred embodiment the hydrocarbon co-feed contains:
1) a fraction of a crude oil, such as for example (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO), coker gas oils, atmospheric residue ("long residue") and vacuum residue ("short residue"); in combination with 2) a Fischer-Tropsch derived hydrocarbon stream and/or a hydrotreater product.
In an especially preferred process the total feed comprises - from equal to or more than 0 wt% to equal to or less than 99 wt%, preferably from equal to or more than 0 wt%
to equal to or less than 20 wt% of a Fischer-Tropsch derived hydrocarbon stream and/or a hydrotreater product;
- from equal to or more than 0 wt% to equal to or less than 99 wt%, preferably from equal to or more than 0 wt%
to equal to or less than 79 wt% of a fraction of a crude oil, such as for example (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO), coker gas oils, atmospheric residue ("long residue") and vacuum residue ("short residue") - from equal to or more than 1 wt% to equal to or less than 35 wt%, preferably from equal to or more than 1 wt%
to equal to or less than 20 wt% of a pyrolysis oil or a part thereof as described herein.

The weight ratio of the pyrolysis oil to hydrocarbon co-feed may vary widely. For ease of co-processing the hydrocarbon co-feed and the pyrolysis oil are preferably being fed to a catalytic cracking unit in a weight ratio of hydrocarbon co-feed to pyrolysis oil of equal to or more than 50 to 50 (5:5), more preferably equal to or more than 70 to 30 (7:3), still more preferably equal to or more than 80 to 20 (8:2), even still more preferably equal to or more than 90 to 10 (9:1). For practical purposes the weight ratio of hydrocarbon co-feed to pyrolysis oil is preferably equal to or less than 99.9 to 0.1 (99.9:0.1).
Hence, the amount of pyrolysis oil present, based on the total weight of pyrolysis oil and hydrocarbon co-feed, is preferably equal to or less than 30 wt%, more preferably equal to or less than 20 wt%, most preferably equal to or less than 10 wt% and even more preferably equal to or less than 5 wt%. For practical purposes amount of pyrolysis oil present, based on the total weight of pyrolysis oil and hydrocarbon co-feed, is preferably equal to or more than 0.1 wt%.
Preferably step i) is carried out in a catalytic cracking unit, more preferably in a fluidized catalytic cracking (FCC) unit.
The hydrocarbon co-feed and the pyrolysis oil can be mixed prior to entry into a catalytic cracking unit or they can be added separately, at the same location or different locations to the catalytic cracking unit.
In one embodiment the hydrocarbon co-feed and the pyrolysis oil are not mixed together prior to entry into a catalytic cracking unit. In this embodiment the hydrocarbon co-feed and the pyrolysis oil may be fed simultaneously (that is at one location) to the catalytic cracking unit, and mixed upon entry of the catalytic cracking unit; or, alternatively, the hydrocarbon co-feed and the pyrolysis oil may be added separately (at different locations) to the catalytic cracking unit.
Catalytic cracking units can have multiple feed inlet nozzles. The pyrolysis oil and the hydrocarbon co-feed can therefore be processed in the catalytic cracking unit even if both components are not miscible by feeding each component through a separate feed inlet nozzle.
It was, however, advantageously found that the pyrolysis oil can be mixed with a, preferably liquid, hydrocarbon co-feed. When mixing the pyrolysis oil with the, preferably liquid, hydrocarbon co-feed, the pyrolysis oil preferably comprises less than 25wt% n-hexane extractives;
comprises a bottom phase of a pyrolysis oil; and/or is a pyrolysis oil which when combined with a, preferably liquid, hydrocarbon co-feed provides a combination that has a molar ratio of hydrogen to carbon of at least 1 to 1. In another preferred embodiment therefore the hydrocarbon co-feed and the pyrolysis oil are mixed together prior to entry into a catalytic cracking unit to provide a feed mixture comprising the hydrocarbon co-feed and the pyrolysis oil. In this embodiment the hydrocarbon co-feed and the pyrolysis oil are preferably mixed at a temperature in the range between equal to or more than 10 C, more preferably equal to or more than 20 C, still more preferably equal to or more than 30 C and most preferably preferably equal to or more than 40 C, and equal to or less than 80 C, more preferably equal to or less than 70 C and most preferably equal to or less than 60 C. When the feed mixture contains VG0 as a hydrocarbon co-feed, a slightly lower temperature of equal to or more than 10 C may be preferred, whereas when the feed mixture contains Long Residue a slightly higher temperature of equal to or more than 30 may be preferred. Most preferably, when the feed mixture contains VG0 as a hydrocarbon co-feed, a temperature in the range from 10 C
to 25 C is preferred, whereas when the feed mixture contains Long Residue a temperature in the range from 30 C
to 50 C is preferred.
The hydrocarbon co-feed and the pyrolysis oil may be mixed in any manner known to be skilled person to be suitable for such purpose. Preferably the hydrocarbon co-feed and the pyrolysis oil are mixed by means of static mixing, shaking and/or stirring.
The feed mixture may optionally be held in a stirred or non-stirred feed vessel before being forwarded to a catalytic cracking unit. It is one of the advantages of the process according to the present invention that also a non-stirred feed vessel may be used, thereby obtaining a more simple operation process and/or saving upon construction, energy and/or maintenance costs. In addition experiments indicate that use of a non-stirred feed vessel may surprisingly increase yields and reduce coking.
Preferably the feed mixture is held in such a stirred or non-stirred feed vessel at a temperature in the range between equal to or more than 10 C, more preferably equal to or more than 20 C, still more preferably equal to or more than 30 C and most preferably preferably equal to or more than 40 C, and equal to or less than 80 C, more preferably equal to or less than 70 C and most preferably equal to or less than 60 C.
When the feed mixture contains VG0 as a hydrocarbon co-feed, a slightly lower temperature of equal to or more than 10 C may be preferred, whereas when the feed mixture contains Long Residue a slightly higher temperature of equal to or more than 30 may be preferred. Most preferably, when the feed mixture contains VG0 as a hydrocarbon co-feed, a temperature in the range from 10 C
to 25 C is preferred, whereas when the feed mixture contains Long Residue a temperature in the range from 30 C
to 50 C is preferred.
Preferably the feed mixture is injected into the catalytic cracking unit, optionally after being held in a stirred or non-stirred feed vessel, at a temperature in the range between equal to or more than 10 C, more preferably equal to or more than 20 C, still more preferably equal to or more than 30 C and most preferably preferably equal to or more than 40 C, and equal to or less than 80 C, more preferably equal to or less than 70 C and most preferably equal to or less than 60 C. When the feed mixture contains VG0 as a hydrocarbon co-feed, a slightly lower temperature of equal to or more than 10 C may be preferred, whereas when the feed mixture contains Long Residue a slightly higher temperature of equal to or more than 30 may be preferred. Most preferably, when the feed mixture contains VG0 as a hydrocarbon co-feed, a temperature in the range from 10 C to 25 C is preferred, whereas when the feed mixture contains Long Residue a temperature in the range from 30 C to 50 C is preferred.
Subsequently the feed mixture may be contacted with the catalytic cracking catalyst in a catalytic cracking unit.
The catalytic cracking catalyst can be any catalyst known to the skilled person to be suitable for use in a cracking process. Preferably, the catalytic cracking catalyst comprises a zeolitic component. In addition, the catalytic cracking catalyst can contain an amorphous binder compound and/or a filler. Examples of the amorphous binder component include silica, alumina, titania, zirconia and magnesium oxide, or combinations of two or more of them.
Examples of fillers include clays (such as kaolin).
The zeolite is preferably a large pore zeolite. The large pore zeolite includes a zeolite comprising a porous, crystalline aluminosilicate structure having a porous internal cell structure on which the major axis of the pores is in the range of 0.62 nanometer to 0.8 nanometer.
The axes of zeolites are depicted in the 'Atlas of Zeolite Structure Types', of W.M. Meier, D.H. Olson, and Ch.
Baerlocher, Fourth Revised Edition 1996, Elsevier, ISBN 0-444-10015-6. Examples of such large pore zeolites include FAU or faujasite, preferably synthetic faujasite, for example, zeolite Y or X, ultra-stable zeolite Y (USY), Rare Earth zeolite Y (= REY) and Rare Earth USY (REUSY).
According to the present invention USY is preferably used as the large pore zeolite.
The catalytic cracking catalyst can also comprise a medium pore zeolite. The medium pore zeolite that can be used according to the present invention is a zeolite comprising a porous, crystalline aluminosilicate structure having a porous internal cell structure on which the major axis of the pores is in the range of 0.45 nanometer to 0.62 nanometer. Examples of such medium pore zeolites are of the MFI structural type, for example, ZSM-5; the MTW type, for example, ZSM-12; the TON structural type, for example, theta one; and the FER structural type, for example, ferrierite. According to the present invention, ZSM-5 is preferably used as the medium pore zeolite.
According to another embodiment, a blend of large pore and medium pore zeolites may be used. The ratio of the large pore zeolite to the medium pore size zeolite in the cracking catalyst is preferably in the range of 99:1 to 70:30, more preferably in the range of 98:2 to 85:15.

The total amount of the large pore size zeolite and/or medium pore zeolite that is present in the cracking catalyst is preferably in the range of 5 wt% to 40 wt%, more preferably in the range of 10 wt% to 30 wt%, and even more preferably in the range of 10 wt% to 25 wt% relative to the total mass of the catalytic cracking catalyst.
The pyrolysis oil is preferably contacted with the catalytic cracking catalyst in the presence of the hydrocarbon co-feed in a reaction zone, which reaction zone is preferably an elongated tube-like reactor, preferably oriented in an essentially vertical manner. The pyrolysis oil, the hydrocarbon co-feed and the cracking catalyst may each independently flow in an upward direction or downward direction.
Preferably, however, the pyrolysis oil and the hydrocarbon co-feed flow co-currently in the same direction. The catalytic cracking catalyst can be contacted in a cocurrent-flow countercurrent-flow or cross-flow configuration with such a flow of the pyrolysis oil and the hydrocarbon co-feed. Preferably the catalytic cracking catalyst is contacted in a cocurrent flow configuration with a cocurrent flow of the pyrolysis oil and the liquid hydrocarbon cofeed.
In a preferred embodiment step i) comprises:
- a catalytic cracking step wherein the pyrolysis oil and the hydrocarbon co-feed are cracked in a reaction zone in the presence of the catalytic cracking catalyst to produce one or more cracked products and a spent catalytic cracking catalyst;
- a regeneration step, wherein spent catalytic cracking catalyst is regenerated to produce a regenerated catalytic cracking catalyst; and - a recycle step, wherein the regenerated catalytic cracking catalyst is recycled to the catalytic cracking step.
The temperature in the catalytic cracking step preferably ranges from equal to or more than 450 C to equal to or less than 650 C, more preferably from equal to or more than 480 C to equal to or less than 600 C, and most preferably from equal to or more than 480 C to equal to or less than 560 C.
The pressure in the catalytic cracking step preferably ranges from equal to or more than 0.5 bar to equal to or less than 10 bar (0.05 MPa-1 MPa), more preferably from equal to or more than 1.0 bar to equal to or less than 6 bar (0.15 MPa to 0.6 MPa).
The residence time of the catalytic cracking catalyst in the reaction zone, where the catalytic cracking takes place, preferably ranges from equal to or more than 0.1 seconds to equal to or less than 15 seconds, more preferably from equal to or more than 0.5 seconds to equal to or less than 10 seconds.
Preferably, the mass ratio of the catalytic cracking catalyst to the total feed of pyrolysis oil and hydrocarbon co-feed ranges from equal to or more than 3 to equal to or less than 20. Preferably, the mass ratio of the catalytic cracking catalyst to the total feed of pyrolysis oil and hydrocarbon co-feed is at least 3.5. The use of a higher catalyst to feed mass ratio results in an increase in conversion.
In a preferred embodiment, the catalytic cracking step further comprises a stripping step. The spent catalyst may be stripped to recover the products absorbed on the spent catalyst before the regeneration step. These products may be recycled and added to the product stream obtained from the catalytic cracking step.
The regeneration step preferably comprises burning off of coke, deposited on the catalyst as a result of the catalytic cracking reaction, to restore the catalyst activity by combusting the cracking catalyst in the presence of an oxygen-containing gas in a regenerator. The heat generated in the exothermic regeneration step is preferably employed to provide energy for the endothermic catalytic cracking step. The process according to the invention advantageously allows for a sufficient amount of coke deposited on the catalytic cracking catalyst such that the exothermic regeneration step can be carried out without supplying additional heat.
The regeneration temperature preferably ranges from equal to or more than 575 C to equal to or less than 900 C, more preferably from equal to or more than 600 C to equal to or less than 850 C. The pressure in the regenerator preferably ranges from equal to or more than 0.5 bar to equal to or less than 10 bar (0.05 MPa to 1 MPa), more preferably from equal to or more than 1.0 bar to equal to or less than 6 bar (0.1 MPa to 0.6 MPa).
The regenerated catalytic cracking catalyst can be recycled to the catalytic cracking step. In a preferred embodiment a side stream of make-up catalyst is added to such a recycle stream of regenerated catalytic cracking catalyst to make-up for loss of catalyst in the reaction zone and regenerator.
As indicated above, step i) can be carried out in various manners.
In a first embodiment the part of or whole pyrolysis oil in step i) comprises a pyrolysis oil or a part thereof containing equal to or less than 25 wt% n-hexane extractives.
In a first embodiment step i) therefore comprises a process to produce one or more cracked products comprising the steps of la) providing a pyrolysis oil or a part thereof containing in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives;
lb) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.
By n-hexane extractives are herein understood compounds extractable from the pyrolysis oil into n-hexane (normal-hexane) at a temperature of about 20 C and a pressure of about 1 bar absolute (0.1 MegaPascal). n-Hexane extractives can be determined according to Oasmaa et al, in their article titled "Fast Pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis Liquids, volume 17, number 1, January /February 2003, page 5 and page 11 as herein incorporated by reference.
Examples of such n-hexane extractives include rubbers, tannins, flavonoids, lignin monomers (such as guaiacol and catechol derivatives), lignin dimers (stilbenes), resin, waxes, sterols, vitamins and fungi.
Preferably the pyrolysis oil or a part thereof contains in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives, more preferably in the range from equal to or more than 0 wt% to equal to or less than 20 wt% n-hexane extractives, still more preferably in the range from equal to or more than 0 wt%
to equal to or less than 15 wtt n-hexane extractives, still more preferably in the range from equal to or more than 0 wt% to equal to or less than 10 wt% n-hexane extractives, even still more preferably in the range from equal to or more than 0 wt% to equal to or less than 6 wt%
n-hexane extractives, and most preferably in the range from equal to or more than 0 wt% to equal to or less than 3 wt% n-hexane extractives. For practical purposes a lower limit of equal to or more than 0.01 ppm by weight may be considered more preferably in the above ranges, and a lower limit of equal to or more than 0.1 ppm by weight may be considered most preferably in the above ranges.
In another, especially preferred embodiment the pyrolysis oil or part thereof contains essentially no n-hexane extractives.
The pyrolysis oil or part thereof, containing equal to or less than 25 wt% n-hexane extractives, can be obtained in any manner known by the skilled person to be suitable for this purpose.
In one embodiment the pyrolysis oil or part thereof, containing equal to or less than 25 wt% n-hexane extractives, may be obtained by solvent extraction of the n-hexane extractives from a pyrolysis oil or part thereof, containing more than 25 wt% n-hexane extractives. Solvents suitable in such solvent extraction include n-hexane but also other hexanes, heptanes, pentanes, octanes, nonanes or decanes. In addition, the use of solvents such as acetone and or dichloromethane may be helpful.
In another embodiment the pyrolysis oil or part thereof may be phase separated as described in more detail below, to produce a bottom phase pyrolysis oil containing in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives, preferably in the range from equal to or more than 0 wt% to equal to or less than 20 wt% n-hexane extractives, more preferably in the range from equal to or more than 0 wt% to equal to or less than 15 wt% n-hexane extractives, still more preferably in the range from equal to or more than 0 wt% to equal to or less than 10 wt% n-hexane extractives and most preferably in the range from equal to or more than 0 wt% to equal to or less than 6 wt% n-hexane extractives; and a top phase pyrolysis oil preferably containing more than 25 wt% n-hexane extractives, more preferably containing more than 30 wt% n-hexane extractives more preferably containing more than 35 wt% n-hexane extractives and most preferably containing more than 40 wt% n-hexane extractives, and preferably containing equal to or less than 100 wt% n-hexane extractives.
An example of how the pyrolysis oil or part thereof, containing equal to or less than 25 wt% n-hexane extractive can be obtained is provided by A. Oasmaa et al, in their article titled "Fast pyrolysis of Forestry Residue 1. Effect of extractives on phase separation of pyrolysis liquids", first published in Energy & Fuels, an American Chemical Society journal, volume 17, number 1 January-February 2003, pages 1-12.
In a second embodiment the part of or whole pyrolysis oil in step i) comprises only a bottom phase pyrolysis oil or a part thereof.
In a second embodiment step i) therefore comprises a process to produce one or more cracked products comprising the steps of 2a) providing a bottom phase of a pyrolysis oil or a part thereof;
2b) contacting the bottom phase of the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.
In step 2a) a bottom phase of a pyrolysis oil is provided.
By the bottom phase of a pyrolysis oil is understood the lowest of the phases that can be obtained when phase separating a pyrolysis oil. Such phase separation may take place because of significant polarity, solubility and density differences of extractives and the highly hydrophilic pyrolysis liquid compounds. The bottom phase of a pyrolysis oil is sometimes also referred to as bottom phase pyrolysis oil. The bottom phase pyrolysis oil can be obtained from a pyrolysis oil that is suitable for phase separation into at least a top phase and a bottom phase.
By a pyrolysis oil that is suitable for phase separation into at least a top phase and a bottom phase is also understood a pyrolysis oil that can be separated into at least a top phase and a bottom phase with the help of a separation agent.
Preferably, however, the pyrolysis oil is a pyrolysis oil that can be separated into at least a top phase and a bottom phase without requiring the pyrolysis oil to be contacted with a separation agent.
Preferably the pyrolysis oil is phase separated into at least a top phase and a bottom phase to produce a top phase pyrolysis oil and a bottom phase pyrolysis oil.
Hence, in a preferred embodiment the invention provides a process to produce one or more cracked products comprising the steps of a) providing a pyrolysis oil or part thereof, which pyrolysis oil or part thereof has essentially not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation;

b) phase separating the pyrolysis oil or part thereof into at least a top phase and a bottom phase to produce a top phase pyrolysis oil and a bottom phase pyrolysis oil;
c) contacting the bottom phase pyrolysis oil or part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products.
Such a process to produce one or more cracked products can subsequently conveniently be used as step i) in the above described process for the preparation of a biofuel and/or a biochemical from a pyrolysis oil. As indicated above, in one embodiment the phase separation can be brought about by contacting the pyrolysis oil with a separation agent.
By a separation agent is understood a compound that assists in the separation of the pyrolysis oil into one or more phases. In a preferred embodiment such separation agent is an alcohol. Examples of alcohols that can be used as a separation agent include ethanol and isopropanol. An example of how isopropanol can be used as a separation agent is provided by Oasmaa et al in their article titled "Fast Pyrolysis of Forestry Residue and Pine. 4.
Improvement of the Product Quality by Solvent Addition", Energy and Fuels 2004, volume 18, pages 1578 to 1583. If an alcohol is used as a separation agent, such an alcohol is preferably present in an amount of equal to or more than 0.25 wt%, more preferably equal to or more than 0.5 wt%, still more preferably equal to or more than 1 wt% and most preferably equal to or more than 2 wt%, based on the total combination of alcohol and pyrolysis oil; and preferably in an amount of equal to or less than 10 wt%, more preferably equal to or less than 7 wt% and most preferably equal to or less than 5 wt%, based on the total combination of alcohol and pyrolysis oil.
In another embodiment the phase separation can be brought about by lowering the temperature (cooling) of the pyrolysis oil after production. If phase separation is brought about by cooling, the pyrolysis oil is preferably cooled to a temperature equal to or above 15 C, more preferably equal to or above 25 C and preferably equal to or below 50 C, more preferably equal to or below 45 C. An example of how cooling can be used to separate phases is provided by Oasmaa et al in their article titled " Fast Pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis Liquids", Energy and Fuels 2003, volume 17, pages 1 to 12.
The bottom phase pyrolysis oil can subsequently be separated from the top phase of the pyrolysis by any method known to the skilled in the art to be suitable for this purpose. Examples of phase separation methods include settling, decantation, centrifugation, cyclone separation, extraction and membrane techniques.
In the processes according to the invention the bottom phase pyrolysis oil, which is being contacted with the catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products, may be contaminated with minor amounts of other phases than the bottom phase pyrolysis oil. These minor amounts of the other phases may for example be dispersed or dissolved in the bottom phase pyrolysis oil. Preferably the total amount of pyrolysis oil, which is being contacted with the catalytic cracking catalyst in the process of the invention, consists for equal to or more than 90 wt%, more preferably for equal to or more than 95 wt%, even more preferably equal to or more than 99 wt%, still more preferably equal to or more than 99.9 wt% and most preferably equal to or more than 99.99 wt% of bottom phase pyrolysis oil, based on the total weight of pyrolysis oil being contacted with the catalytic cracking catalyst.
Preferably the amount of any other phase pyrolysis oils (i.e. not being bottom phase pyrolysis oil, also referred to as non-bottom phase pyrolysis oils) is equal to or less than 10 wt%, more preferably equal to or less than 5 wt%, even more preferably equal to or less than 1 wt%, still more preferably equal to or less than 0.1 wt% and most preferably equal to or less than 0.01 wt%, based on the total weight of pyrolysis oil being contacted with the catalytic cracking catalyst. Most preferably any pyrolysis oil being contacted with the catalytic cracking catalyst in the process of the invention consists essentially only of bottom phase pyrolysis oil. That is, most preferably the catalytic cracking is carried out in the essential absence of any non-bottom phase pyrolysis oil.
An example of a non-bottom phase pyrolysis oil is the top phase pyrolysis oil.
In a preferred embodiment the bottom phase pyrolysis oil contains in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives, more preferably in the range from equal to or more than 0 wt%
to equal to or less than 20 wt% n-hexane extractives, still more preferably in the range from equal to or more than 0 wt% to equal to or less than 15 wt% n-hexane extractives, still more preferably in the range from equal to or more than 0 wt% to equal to or less than 10 wt% n-hexane extractives, even still more preferably in the range from equal to or more than 0 wt% to equal to or less than 6 wt% n-hexane extractives, and most preferably in the range from equal to or more than 0 wt% to equal to or less than 3 wt% n-hexane extractives.
Further the bottom phase pyrolysis oil may contain water (preferably in the range from 20-35 wt%), carboxylic acids (preferably in the range from 5-15 wt%), alcohols (preferably in the range from 0-5 wt%), carbohydrates (preferably in the range from (25-40 wt%), and/or lignin compounds (preferably in the range from 5-30wt%).
In a third embodiment the part of or whole pyrolysis oil in step i) is a pyrolysis oil or part thereof which when combined with a, preferably liquid, hydrocarbon co-feed provides a combination that has a molar ratio of hydrogen to carbon of at least 1 to 1. In a third embodiment step i) therefore comprises a process to produce one or more cracked products comprising the steps of 3a) providing a pyrolysis oil or a part thereof;
3b) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400 C in the presence of a hydrocarbon co-feed to produce one or more cracked products; wherein the combination of the pyrolysis oil or part thereof and the hydrocarbon co-feed has an overall molar ratio of hydrogen to carbon (H/C) of equal to or more than 1 to 1 (1/1).
The combination of the pyrolysis oil or part thereof and the, preferably liquid, hydrocarbon co-feed preferably has an overall molar ratio of hydrogen to carbon (H/C) of equal to or more than 1.1 to 1 (1.1/1), more preferably of equal to or more than 1.2 to 1 (1.2/1), most preferably of equal to or more than 1.3 to 1 (1.3/1).
In a preferred embodiment an effective molair ratio of hydrogen to carbon (H/Ceff) is used. By the effective molair ratio of hydrogen to carbon (H/Ceff) is understood the molair ratio of hydrogen to carbon after the theoretical removal of all moles of oxygen, present in the oil on a dry basis, via water production with hydrogen originally present, presuming no nitrogen or sulphur present (H/Ceff = (H-2*0)/C).
Preferably the combination of the pyrolysis oil or part thereof and the, preferably liquid, hydrocarbon co-feed has an overall effective molair ratio of hydrogen to carbon (H/Ceff) of equal to or more than 1 to 1, more preferably of equal to or more than 1.1 to 1 (1.1/1), even more preferably of equal to or more than 1.2 to 1 (1.2/1), most preferably of equal to or more than 1.3 to 1 (1.3/1).
In one embodiment the desired molar ratio of hydrogen to carbon (H/C) or desired effective molar ratio of hydrogen to carbon (H/Ceff) can be obtained by using a specific hydrocarbon co-feed. Examples of suitable hydrocarbon co-feeds are listed above. A most preferred hydrocarbon co-feed in this respect is a Long Residue.
In another embodiment the desired molar ratio of hydrogen to carbon (H/C) or desired effective molar ratio of hydrogen to carbon (H/Ceff) can be obtained by using a specific weight ratio of the pyrolysis oil to the hydrocarbon co-feed. Examples of suitable weight ratios of the pyrolysis oil to the hydrocarbon co-feed are listed above. Most preferred weight ratios of the hydrocarbon co-feed to the pyrolysis oil in this respect lie in the range from 7:3 to 9:1.
In step i) of the process according to the invention one or more cracked products are produced. These one or more cracked products can be further processed in any manner known to the skilled person to be suitable for further processing these products. Such further processing may for example include fractionating and/or hydrotreating (such as for example hydrodesulphurization, hydrode-nitrogenation, hydrodeoxygenation and/or hydroisomerization) the one or more cracked products.
Preferably, the one or more cracked products are fractionated into one or more product fractions. Examples of such product fractions include drygas (including carbon monoxide, carbon dioxide, methane, ethane, ethene, hydrogen sulfide and hydrogen), LPG (including propane and butanes with small amounts of propene and butenes),), gasoline (boiling in the range from C5 to 221 C), light cycle oils (LCO; boiling in the range from 221 C to 370 C), heavy cycle oil (HCO; boiling in the range from 370 C to 425 C) and/or slurry oil (boiling above 425 C) In a preferred embodiment the one or more cracked products contain in the range from equal to or more than 20 wt% to equal to or less than 90 wt% of gasoline and LCO, more preferably in the range from equal to or more than 30 wt%
to equal to or less than 80 wt% of gasoline and LCO.
In a preferred embodiment the product fractions, obtained after fractionating the one or more cracked products, can be used to produce a biofuel and/or a biochemical. For example one or more product fractions can be blended with one or more other components to produce a biofuel and/or a biochemical.
By a biofuel respectively a biochemical is herein understood a fuel respectively a chemical that is at least partly derived from a renewable energy source.
Examples of one or more other components with which the one or more product fractions may be blended include anti-oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components.
The present invention further comprises combinations of the embodiments described in the description above.

The invention is illustrated by the following non-limiting examples.

Example 1: Mixing bottom phase pyrolysis oil derived from forest residue and a hydrocarbon feed.
A pyrolysis oil derived from forest residue was obtained from VII. Pyrolysis of the forest residue was carried out using a 20kg/h capacity process development unit (PDU) as described by Oasmaa et al in their article "Fast pyrolysis of Forestry Residue.l. Effect of Extractives on Phase Separation of Pyrolysis liquids" in Energy & Fuels 2003, 17, pages 1 - 12.
A bottom phase pyrolysis oil and a top phase pyrolysis oil were obtained as described in this article.
Subsequently mixtures were prepared of:
= 20 wt% top phase pyrolysis oil from forest residue with 80 wt% vacuum gas oil (VGO).
= 20 wt% bottom phase pyrolysis oil from forest residue with 80 wt% Heavy feed mixture.
In order to determine miscibility the following visual test was carried out. Each mixture was heated in a glass bottle to approximately 65 C and shaken intensively. Hereafter the glass bottle was allowed to stand for 30 minutes at 65 C.
Subsequently the glass bottle was turned upside down to see if there were two separate layers of liquid visible. When allowing the glass bottle to stand for 30 minutes at 65 C
and then turning it upside down, a dark brown sticky material on the bottom of the glass bottle indicates non-miscibility of the pyrolysis oil fraction.
Details on the composition of the top phase pyrolysis oil, the bottom phase pyrolysis oil, VG0 and Heavy feed mixture can be found in table 1.
Further details on the composition of the VG0 and the Heavy feed mixture are provided in tables 2 and 3 respectively.
Table 4 shows the visual test results of the miscibility of 20% top phase pyrolysis oil from forest residue with VG0 and of 20% bottom phase pyrolysis oil from forest residue with Heavy feed mixture.

Table 1. Feed compositions (a = on a wet basis, b = calculated on a dry basis) Feed properties MCR* C H 0 N S
Water H/C ratio H/Ceff w o ,.., w (wt%) (wt%) (wt%) (wt%) ** (ppm (1313m content (mol/mol) (mol/mol) 'a c., w vD
wt) wt) (wt %) w .6.
Heavy feed mixture 2.0 86.65 12.8 0 2220 3360 0 1.77 1.77 Vacuum gasoil 0.2 85.4 12.8 0 n.d.
n.d. 0 1.80 1.80 Bottom phase of 19.1 40.5 7.76 51.7 2420 168 24.5 n.d. n.d.
forestry residue n pyrolysis oil' I.) CO
H
Bottom phase of n.d. 53.6 6.7 39.6 n.d.
n.d. n.d. 1.49 0.94 m w in w forestry residue I.) H
pyrolysis oilb w a, Top phase of 19.6 n.d. n.d. n.d. n.d.
n.d. n.d. n.d. n.d. 1 I.) m forestry residue pyrolysis oil' * Micro Carbon Residue ** Oxygen content calculated by difference, i.e. by subtracting carbon content and hydrogen Iv n ,-i content from 100 wt%.
m Iv w n.d. = not determined.
o ,.., ,.., 'a c., vD
vD
m v, Table 2: Composition of the VG0 Hydrogen, %wt 12.25 Carbon, %wt 85.64 Nitrogen, %wt 0.08 Sulphur, %wt 1.77 Basic Nitrogen, 237 ppmw Nickel, ppmw 0.1 Vanadium, ppmw 0.4 Iron, ppmw 0.3 Sodium, ppmw 0.2 Bromine Number, 6.1 gram Br/100gram Micro-Carbon 0.2 Residue, %wt Non-vaporizable 0.37 Coke, %wt Mono Aromatics, 5.72 %wt Di Aromatics, %wt 3.35 Tri Aromatics, %wt 3.41 Tetra+ Aromatics, 2.8 %wt Total Aromatics, 15.27 %wt Density @ 60F, 0.8961 g/cc API Gravity (60F) 25.8 Molecular Weight, 309 g/g-mole Kinematic 13.69 Viscosity @ 100F, cst Kinematic 2.91 Viscosity @ 210F, cst Pitch (1000F+), 2.5 %wt Table 3: Composition of the heavy feed mixture Micro-Carbon Residue, 2.0 %wt *
Density D70/4 0.8720 Mol. weight 385 Melting point 35-40 C
Aromatics via UV-analyses SMS-2783 (wt %):
MONO aromatics 4.27 DI aromatics 3.23 TRI aromatics 3.61 TETRA aromatics 1.69 TETRA+ aromatics 3.35 PENTA+ aromatics 1.66 HEXA+ aromatics 0.92 HEPTA+ aromatics 0.63 PYREN aromatics 0.00 Total aromatics 14.46 Table 4. Visual observation of the miscibility of the bottom phase and the top phase of the pyrolysis oil in VG0 and Heavy feed mixture.
VG0 Heavy feed mixture Top phase of the Poor Moderate pyrolysis oil Bottom phase Poor Moderate pyrolysis oil Example 2: Catalytic cracking of a mixture of top phase pyrolysis oil from forest residue with VG0 in a non-stirred feed vessel.
The mixture of 20 wt% top phase pyrolysis oil from forest residue with 80 wt% vacuum gas oil (VGO) as prepared under example 1 was transferred as a feed mixture to the feed vessel of a MAT-5000 fluidized catalytic cracking unit. The feed vessel was kept at 60 C during transfer. The feed vessel was not stirred. A first test run was started immediately after transfer of the feed mixture into the feed vessel.
The first test run included the 7 experiments with 7 catalyst to oil ratios, namely catalyst/oil ratios of 3, 4, 5, 6, 6.5, 7 and 8.
Each experiment was conducted as follows:
10 g of FCC equilibrium catalyst containing ultra stable zeolite Y, was constantly fluidized with nitrogen. A precise and known amount of feed was injected, and subsequently flushed through a tube with nitrogen to the fluidized catalyst bed during runtime of 1 minute. The fluidized catalyst bed was kept at 500 C. The liquid FCC products were collected in glass receivers at minus 18-19 C.
Subsequently the FCC catalyst was stripped with nitrogen during 11 minutes. The gas produced during such stripping was weighted and analyzed online with a gas chromatograph (GC).
Hereafter the FCC catalyst was regenerated in-situ at 650 C
for 40 minutes in the presence of air. During such regeneration the coke was converted to 002, which was quantified by on-line infrared measurement. After regeneration the reactor was cooled to the cracking temperature and a new injection was started. One cycle including all catalyst to oil ratios took approximately 16 hours.

The results of example 2 are reflected in below table 5.
Table 5. Cracked products obtained by catalytic cracking of 20 wt % top phase of pyrolysis oil from forest residue with 80 wt % VG0 at 500 C
Yields at 100 % 20% top phase 20% top phase Average of 60% VG0 pyrolysis oil pyrolysis oil 1st and conversion + 80 wt% VG0 + 80 wt% VG0 2nd run*
1st run* 2nd run*
Drygas ** 1.4 2.4 2.4 2.4 LPG 9.6 9.7 14.3 12.0 Gasoline 45.3 35.3 43.4 39.3 Light Cycle 32.2 23.1 25.4 24.2 Oil (LCO) Heavy Cycle 5.0 3.8 3.8 3.8 Oil (HCO) Slurry oil 2.7 2.4 2.1 2.2 (SO) Coke 3.7 19.1 8.4 13.8 CO 0.0 2.5 0.1 1.3 CO2 0.0 1.8 0.1 0.9 * The above results have been normalized and calculated on a dry basis , i.e. without 11.1 wt% H20 As illustrated in table 5, the LPG, gasoline and coke make in the 1st and 2nd run show substantial differences. The poor reproducibility for the 1st and 2nd test run in example 2 indicates a poor miscibility of the top phase pyrolysis oil and the VG0. The process in example 5 may therefore be less robust when upscaling to a commercial scale.
As further illustrated in table 5, a substantial amount of gasoline is prepared, allowing this gasoline to be used for the production of a biofuel.

Example 3: Catalytic cracking of a mixture of bottom phase pyrolysis oil from forest residue with Heavy feed mixture in a non-stirred feed vessel.
The mixture of 20 wt% bottom phase pyrolysis oil from forest residue with 80 wt% Heavy feed mixture as prepared under example 1 was transferred as a feed mixture to the feed vessel of a MAT-5000 fluidized catalytic cracking unit. A
process identical to that described for example 2 was carried out except that for example 3 the fluidized catalyst bed during catalytic cracking was kept at 520 C instead of 500 C.
The results of example 3 are reflected in below table 6.
Table 6. Cracked products obtained by catalytic cracking of of a mixture of 20 wt% bottom phase pyrolysis oil from forest residue and 80wt% Heavy feed mixture .
Heavy feed Heavy feed Heavy feed Average of mixture mixture + mixture +
Yields at 2 (wt%) 20% bottom 20% bottom 60% consecutiv phase (1st phase (2nd conversion e runs run) run) (wt %) (wt) (wt) Water 0 10.9 10.9 10.9 Cat/Oil 2.9 4.2 3.9 4.1 ratio Drygas 1.5 2.5 2.1 2.3 LPG 8.4 12.7 13.1 12.9 Gasoline 43.4 42.9 44.7 43.8 Light Cycle Oil 25.1 21.2 21.5 21.4 (LCO) Heavy Cycle Oil 8.0 5.4 5.6 5.5 (HCO) Slurry oil 6.9 4.8 4.9 4.8 (SO) Coke 6.6 9.1 7.7 8.4 CO 0 0.8 0.2 0.5 CO2 0 0.5 0.2 0.3 The good reproducibility for the 1st and 2nd test run in example 3 indicates a good miscibility of the bottom phase pyrolysis oil and the Heavy feed mixture. The process in example 5 therefore is sufficiently robust to allow upscaling to a commercial scale. In addition, coke yield is considerably lower than the coke yield obtained in example 2 with the top phase of pyrolysis oil and using VG0 as a co-feed.
Further, Elemental analysis of the Total Liquid Products shows a large reduction in the amount of remaining oxygen, as illustrated in table 7. Without wishing to be bound to any kind of theory, it is therefore believed that direct co-processing of the bottom phase of pyrolysis oil and a heavy feed mixture in an FCC unit, in line with the process according to the invention, also leads to a large reduction in the Total Acid Number. Hence the process according to the invention may also advantageously enable further downstream processing of the catalytically cracked pyrolysis oil in a refinery.
Table 7: Elemental analysis of Total liquid Products in example 3(at Cat/Oil = 3) (wt %) (wt %) (wt %) (Mol/Mol) 1st run 87.1 11.28 1.6 1.55 2nd run 87.9 11.72 0.4 1.60 As further illustrated in table 6, a substantial amount of gasoline is prepared, allowing this gasoline to be used for the production of a biofuel.

Example 4: Mixing bottom phase pyrolysis oil derived from pine and a liquid hydrocarbon feed.
A pyrolysis oil derived from pine was obtained from VII.
Pyrolysis of the pine was carried out as described by Oasmaa et al in their article "Fast pyrolysis of Forestry Residue.l.
Effect of Extractives on Phase Separation of Pyrolysis liquids" in Energy & Fuels 2003, 17, pages 1 - 12. A top phase pyrolysis oil from pine and a bottom phase pyrolysis oil from pine were obtained as described in that same article. Subsequently a mixture was prepared of:
= 20 wt% bottom phase pyrolysis oil from pine with 80 wt%
Heavy feed mixture.
Details on the composition of the bottom phase pyrolysis oil from pine and Heavy feed mixture can be found in table 8.

Table 8. Feed compositions (a = on a wet basis, b = calculated on a dry basis) Feed properties MCRT* C H 0 N S
Water H/C ratio H/Ceff w o ,.., w (wt%) (wt%) (wt%) (wt%) ** (ppm (1313m content (mol/mol) (mol/mol 'a c., w vD
wt) wt) (wt %) ) w .6.
Heavy feed mixture 2.07 86.65 12.8 0 2220 3360 0 1.77 1.77 Bottom phase of 21.8 39.8 7.8 52.4 496 42 23.9 n.d. n.d.
pine' Bottom phase of n.d. 52.3 6.8 40.2 n.d.
n.d. n.d. 1.55 0.98 n pineb I.) CO
H
* Micro Carbon Residue Test m w in w ** Oxygen content calculated by difference, i.e. by subtracting carbon content and hydrogen I.) H
content from 100 wt%.
w a, n.d. = not determined.

I.) m Iv n ,-i m ,-;
w =
'a c., m u, Example 5: Catalytic cracking of a mixture of bottom phase pyrolysis oil derived from pine and Heavy feed mixture in a non-stirred and in a stirred feed vessel.
A process identical to that described for example 3 was carried out except that for example 5 the mixture as prepared in example 4 was used; the feed vessel was kept at 50 C; and the process was carried out in a stirred and in a non-stirred feed vessel. The feed vessel was stirred by an overhead stirrer with 4 blades immersed in the feed vessel. The results are summarized in table 9.
As can be seen in table 9 both in a non-stirred feed vessel as well as in a stirred feed vessel consistent and reproducible results can be obtained during the complete time of one run cycle (about 16 hours). This illustrates that the process according to the invention advantageously allows for the process to be carried out without stirring the feed vessel. As a result the process is more easily scaled up.
Table 9. Cracked products obtained by catalytic cracking of a mixture of 80wt% Long Residue with 20wt% bottom phase oil from pine (PBPO) at 520 C
With 20 With 20 With 20 With 20 Yields Heavy feed wt% PBPO wt% PBPO wt% PBPO wt% PBPO
at 60%
mixture with with without without convers only stirring stirring stirring stirring ion st rd st n 2d 1 run 3 run 1 run run Water 0.0% 10.4 10.5 10.6 11.0 Cat/oil 2.8 4.4 4.5 4.5 4.4 ratio Drygas 1.5 2.9 2.7 2.6 2.4 LPG 8.7 12.6 12.8 12.9 13.2 Gasolin 45.3 43.1 43.3 43.8 45.3 e LCO 25.1 21.3 21.4 21.2 21.3 HCO 8.0 5.3 5.4 5.4 5.5 Slurry 6.9 4.6 4.9 4.7 4.7 oil Coke 4.5 8.4 8.3 7.8 6.4 CO 0.1 1.0 0.9 0.9 0.6 CO2 0.0 0.8 0.8 0.8 0.5 As further illustrated in table 9, a substantial amount of gasoline is prepared, allowing this gasoline to be used for the production of a biofuel.
Example 6 Catalytic cracking of a mixture of bottom phase pyrolysis oil and Heavy feed mixture on a pilot scale.
Two experiments were performed using:
1) a feed containing 100 wt% conventional crude oil fraction;
and 2) a feed consisting of a blend of 9.5 wt% bottom phase pyrolysis oil, 1 wt% surfactant and 89.5 wt% of a conventional crude oil fraction.
The above feed, respectively the above blend, was heated to 82 C and transferred as a feed mixture to the feed vessel of a pilot-scale fluidized catalytic cracking unit. The pilot-scale fluidized catalytic cracking unit consisted of six sections including a feed supply system, a catalyst loading and transfer system, a riser reactor, a stripper, a product separation and collecting system, and a regenerator. The riser reactor was an adiabatic riser having an inner diameter of 11 mm and a length of about 3.2 m. The riser reactor outlet was in fluid communication with the stripper that was operated at the same temperature as the riser reactor outlet flow and in a manner so as to provide essentially 100 percent stripping efficiency. The regenerator was a multi-stage continuous regenerator used for regenerating the spent catalyst. The spent catalyst was fed to the regenerator at a controlled rate and the regenerated catalyst was collected in a vessel. The catalytic cracking catalyst cntained ultra stable zeolite Y.
Material balances were obtained during each of the experimental runs at 30-minute intervals. Composite gas samples were analyzed by use of an on-line gas chromatograph and the liquid product samples were collected and analyzed overnight. The coke yield was measured by measuring the catalyst flow and by measuring the delta coke on the catalyst as determined by measuring the coke on the spent and regenerated catalyst samples taken for each run when the unit was operating at steady state.
Properties of the feed are provided in below table 10. The results are summarized in table 11.

Table 10: Feed properties conventional Bottom phase Feed Description crude oil Pyrolysis Oil fraction Hydrogen, %wt 7.8 11.9 Carbon, %wt 39.8 87.5 Oxygen, %wt 55.3 0.12 Nitrogen, ppmw 496 296 Sulfur, ppmw 42 166 Basic Nitrogen, ppmw 395 926 Nickel, ppmw < 0.2 < 0.3 Vanadium, ppmw < 0.2 < 0.3 Iron, ppmw 2 < 0.2 Sodium, ppmw 3.2 <0.2 Mono-Aromatics, %wt 4 7.8 Di-Aromatics, %wt 0.9 3.0 Tri-Aromatics, %wt 1 2.5 Tetra+ Aromatics, %wt 2.8 3.1 Total Aromatics, %wt 8.7 16.4 Micro-Carbon Residue' 21.8 <0.1 %wt Molecular Weight, g/g-mole Kinematic Viscosity @ Unable to 7.1 100 C, cst determine Bromine Number, 14.7 7 gBr/100g Pitch (538 C+), %wt Unable to 2 determine Table 11: Cracked products obtained by catalytic cracking of a conventional crude oil fraction with bottom phase oil and a surfactant at 528 C
Yields at constant Blend 100wt % conventional conversion crude oil fraction Reactor Temp., C 528 528 Gas Residence time, sec 2.3 2.4 C/O Ratio 18.6 10.2 Conversion, %wt 70.5 70.4 C5-450F Naphtha, %wt 48.2 50.5 YIELDS, %wt C2 & Lighter 1.8 2.7 C5-232 C Naphtha, %wt 48.2 50.5 LPG, %wt. 18.0 17.2 232-343 C, LCO 21.1 18.0 343-399 C, HCO 4.7 5.9 399 C+, CLO 3.6 5.7 Coke 4.6 2.6 Comparative example 7 An experiment was carried out as described above for example 6, except that the feed contained 100 wt% bottom phase pyrolysis oil. The experiment failed as the feed line to the riser and the feed nozzle suffered rapid plugging due to coke formation within 10 minutes from starting of the feed pump.

Claims

1.A process for the preparation of a biofuel and/or biochemical from a pyrolysis oil, which pyrolysis oil essentially has not been pretreated or upgraded by hydrotreatment and/or hydrodeoxygenation, comprising the steps of i) contacting the pyrolysis oil with a catalytic cracking catalyst at a temperature of equal to or more than 400°C
in the presence of a hydrocarbon co-feed to produce one or more cracked products;
ii) fractionating one or more of the cracked products to produce one or more product fractions;
iii) using one or more of the product fractions to produce a biofuel and/or biochemical.

2. A process according to claim 1, wherein step i) comprises a process to produce one or more cracked products comprising the steps of la) providing a pyrolysis oil or a part thereof containing in the range from equal to or more than 0 wt% to equal to or less than 25 wt% n-hexane extractives;
lb) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of more than 400°C in the presence of a hydrocarbon co-feed to produce one or more cracked products.

3. A process according to claim 1 or 2, wherein step i) comprises a process to produce one or more cracked products comprising the steps of 2a) providing a bottom phase of a pyrolysis oil or a part thereof;
2b) contacting the bottom phase of the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400°C in the presence of a hydrocarbon co-feed to produce one or more cracked products.

4.A process according to claim 1, 2 or 3, wherein step i) comprises a process to produce one or more cracked products comprising the steps of 3a) providing a pyrolysis oil or a part thereof;
3b) contacting the pyrolysis oil or the part thereof with a catalytic cracking catalyst at a temperature of equal to or more than 400°C in the presence of a hydrocarbon co-feed to produce one or more cracked products; wherein the combination of the pyrolysis oil or part thereof and the hydrocarbon co-feed has an overall molar ratio of hydrogen to carbon (H/C) of equal to or more than 1 to 1 (1/1).

5. The process according to anyone of claims 1 to 4, wherein the pyrolysis oil is derived from a lignocellulosic material.

6.The process according to claim 5, wherein the lignocellulosic material is selected from the group consisting of wood, a wood-related material and/or mixtures thereof.

7. The process according to anyone of claims 1 to 6, wherein the hydrocarbon co-feed is derived from a conventional crude oil.

8. The process according to anyone of claims 1 to 7, wherein the hydrocarbon co-feed is chosen from the group consisting of straight run gas oils, flashed distillate, vacuum gas oils, coker gas oils, atmospheric residue and vacuum residue.

9. The process according to anyone of claims 1 to 8, wherein the hydrocarbon co-feed comprises equal to or more than 8 wt% elemental hydrogen.

10. The process according to anyone of claims 1 to 9, wherein the hydrocarbon co-feed has an Initial Boiling Point (IBP) as measured by means of distillation based on ASTM D2887-06a at a pressure of 0.1 MegaPascal of equal to or more than 220°C.

11. The process according to anyone of claims 1 to 10, wherein the hydrocarbon co-feed and the pyrolysis oil or bottom phase of the pyrolysis oil are mixed together, to provide a feed mixture comprising the hydrocarbon co-feed and pyrolysis oil or the bottom phase of the pyrolysis oil, prior to entry into a catalytic cracking unit.

12. The process according to claim 11, wherein the hydrocarbon co-feed is mixed with the pyrolysis oil or with the bottom phase of the pyrolysis oil by means of stirring.