METHODS AND APPARATUS FOR THE PRODUCTION OF FUEL
BACKGROUND TO THE INVENTION
Field of the Invention
The present invention relates to a reaction method and apparatus, suitable for
producing fuel by reaction of bio-oil with oil and/or melt.
Related Art
Cracking is the process of breaking down large molecules into smaller ones, typically
through a thermal or catalytic method. Typically, the term "cracking" is used with
reference to the breakdown of large hydrocarbon molecules into smaller ones.
However, the term is applicable to the breakdown of any large molecule, for example
the breakdown of polymers, oils and waxes.
Cracking is typically employed in the petrochemicals industry, to "upgrade" heavy oil
(e.g. heavy fractions of crude oil produced from fractionating crude oil) to lighter
products, useful in fuel applications. For example, these heavy fractions, such as
bituminous residue, may be cracked to provide liquid petroleum gas, petrol and
diesel. Heavy oils (including heavy oil fractions and heavy crude oil) are typically
unsuitable for use as fuels, at least in some applications, and are typically difficult to
handle and process, due to their high viscosity.
Cracking can also be employed to break polymers down into smaller molecules. For
example, synthetic polymers may be cracked, and in this way it is possible to break
down plastics waste.
Typical cracking methods require high temperatures, high pressures and/or the
presence of a catalyst. Thermal cracking methods have largely been replaced by
catalytic cracking methods, such as fluid catalytic cracking.
Biomass pyrolysis is the thermal decomposition of biomass (e.g. plant material such
as wood and wood bark) substantially in the absence of oxygen. Biomass is typically
a mixture of hemicellulose, cellulose, lignin and small amounts of other organics.
These components typically pyrolyse or decompose at different rates and by different
mechanisms and pathways.
As a consequence, biomass pyrolysis results in a complex mixture of products. Solid
products include char and ash. Typically, after cooling the pyrolysis products include
a substantial portion of liquid, and some permanent gases such as H2, CO, C0 2 and
CH . These gas products are useful in combined heat and power (CHP)
applications, where the gas may be used to produce heat and electricity. This is
useful, for example, in rural locations and for on-site generation of heat and power,
for example in a biomass processing plant. The gas products may also be useful as
starting material in synthetic chemical manufacture, for example for synthesising
synthetic natural gas, in the production of ammonia and methanol, and in producing
synthetic petroleum (e.g. using the Fischer-Tropsch process).
The liquid phase product of biomass pyrolysis is typically a dark brown liquid, which
has a heating value that is around one half of the heating value of conventional fuel
oil, and is typically referred to as bio-oil. Bio-oil can be a vaiuabie product of
pyrolysis, as it can be easily stored for later use, such as for heat and/or electricity
generation. However, it is not suitable for all fuel applications, for example due to its
high water content, and presence of elements other than carbon and hydrogen, such
as oxygen.
Attempts have been made to co-process liquid products derived from biomass
pyrolysis with more traditional sources of fuel, in order to produce "second
generation" bio-fuels. For example, Reference 1 describes upgrading bio-oil by
hydrodeoxygenation to produce "HDO-oil" and co-processing this HDO-oil with
vacuum gas oil in a fluid catalytic cracking (FCC) unit, to product a gasoline fuel
product. Similarly, reference 2 describes co-processing HDO-oil and long residue oil
in an FCC unit. Reference 3 reviews methods of catalytic hydroprocessing of bio-oil
to produce upgraded oils, and reference 4 suggests methods of catalytic
deoxygenation of bio-oil to produce oil suitable for processing in petroleum refineries.
Reference 5 proposes co-processing HDO-oil with excess fossil fuel feeds in catalytic
cracking and catalytic hydrodesulfurisation units.
In these co-processing methods, the biomass-derived oil is provided to the
processing unit as a liquid. Typically, char forms on heating the oil in the processing
unit. The heavy oil cracking feedstock may then accumulate on the surface of the
char, leading to agglomeration of the char into larger particles, which can build up on
the reactor walls and may clog the reactor. Accumulation of the heavy oil on the
surface of the char in this way can make subsequent processing of the char more
difficult, and the energy content of the heavy oil accumulated on the surface of the
char may be lost. Furthermore, in order to produce fuel products from co-processing
with heavy oils, these methods employ catalysts to crack the heavy oils.
SUMMARY OF THE INVENTION
The present inventors have devised the present invention in order to address one or
more of the above problems.
The present inventors have found that bio-oil vapour can be useful in the production
of fuels by cracking oils or melts. Surprisingly, where bio-oil vapour is flowed into a
reaction zone and heated together with oil/melt (e.g. hydrocarbon oil/melt), a product
useful as a fuel (e.g. as a diesel fuel) can be produced. This provides a particularly
convenient method for cracking oil/melt. Advantageously, by providing the bio-oil as
a vapour, the formation and accumulation of char in the reaction chamber can be
reduced or avoided. Furthermore, in some instances, bio-oil may be immiscible with
the oil and/or melt present in the reactor. In these cases, the interaction between the
bio-oil and the oil and/or melt is enhanced by flowing bio-oil vapour into the reaction
zone.
Surprisingly, where bio-oil vapour is flowed into the reaction zone, it is not necessary
to use a catalyst to promote cracking of the oil/melt. Additionally, the cracking
reaction proceeds at a useful rate at lower temperatures than those typically required
for thermal cracking methods.
Furthermore, without wishing to be bound by theory, it is believed that the fuel
product includes "fragments" derived both from the oil/melt, and from the bio-oil
vapour. Accordingly, a portion of the energy content of the fuel product can be
considered to be bio-derived energy, and so the fuel product can be seen as a
"second generation" bio-fuel.
Accordingly, in a first preferred aspect, the present invention provides a method for
the production of fuel, the method comprising
flowing bio-oil vapour into a reaction zone; and
heating together in the reaction zone (i) the bio-oil vapour and (ii) oil and/or melt, to
produce reaction products. The method may comprise extracting reaction products.
The bio-oil vapour may be flowed, from externally of a reactor, into a reaction zone of
the reactor.
It will be understood that the bio-oil vapour and the oil and/or melt may be heated
together without the addition of a catalyst, such as without the addition of a catalyst
comprising metal atoms and/or metal ions. For example, the bio-oil vapour and the
oil and/or melt may be heated together without the separate step of adding a
separate catalyst, e.g. substantially in the absence of catalyst.
As used herein, the term "bio-oil vapour" is understood to include vapour of oil
products derived from biomass pyrolysis. For example, the term bio-oil vapour is
understood to include the condensable vapour product of biomass pyrolysis and/or
vapour of the liquid product of pyrolysis. However, the term "bio-oil vapour" is also
understood to include vapour of oil produced by processing this liquid and/or
condensable vapour product of biomass pyrolysis, such as vapour of HDO-oil.
However, preferably the condensable vapour product of biomass pyrolysis and/or
vapour of the liquid product of pyrolysis is used. For example, bio-oil may be
produced in a pyrolysis reactor and flowed into the reaction zone as a vapour directly
from the pyrolysis reactor. Of course, the bio-oil may be subjected to physical
processing steps before it is flowed into the reaction zone as a vapour. Such
physical processing steps include filtration (e.g. to remove solid contaminants),
distillation (e.g. to reduce its water content) and reheating liquid bio-oil to produce a
bio-oil vapour (as described in more detail below),
It will be understood that the term "melt" as used herein includes substances which
are typically solid at room temperature and pressure, but which are typically liquid
under the conditions in the reaction zone.
The present invention is particularly applicable to cracking of hydrocarbons, such as
polyolefins and petroleum (e.g. petroleum fractions), to provide reaction products
useful as fuel oil, such as diesel. Accordingly, the oil and/or melt may be a
hydrocarbon oil and/or melt. For example, a preferred method according to the
present invention comprises:
flowing bio-oil vapour, from externally of a reactor, into a reaction zone of the
reactor;
heating together in the reaction zone (i) the bio-oil vapour and (ii)
hydrocarbon oil and/or melt, to carry out cracking; and
extracting cracked reaction products.
Some documents describe co-pyrolysis of biomass with petroleum residue or
polyolefins (such as synthetic polymers and plastics waste). For example,
references 6 to 8 describe co-pyrolysis of sugar case bagasse and petroleum
residue. Reference 9 describes co-pyrolysis of wood biomass/polyolefin mixtures.
Reference 0 describes co-pyrolysis of pine cone with synthetic polymers.
Reference 1 describes co-pyrolysis of wood and synthetic polymer blends with the
addition of zinc chloride. Reference 1 describes co-pyrolysis of biomass and
plastics waste. References 3 to 16 describe co-pyrolysis of wood biomass and
synthetic polymer mixtures. WO2006/015804 describes a method of producing
hydrocarbon-containing oils by heating biomass in the presence of a "contact oil".
However, on pyrolysis of biomass, significant quantities of char are produced in the
reaction chamber, resulting in the disadvantages described above. As explained
above, flowing bio-oil vapour directly into the reaction chamber reduces or avoids
these problems.
Furthermore, where biomass is co-pyrolysed with petroleum or polyolefin, the
selection of suitable biomass feedstock is somewhat limited. For co-pyrolysis,
typically biomass must be milled to a small particle size. Additionally, co-pyrolysis
typically requires low ash biomass feedstock. In contrast, in the methods of the
present invention, the biomass feedstock is not limited in this way. Since bio-oil
vapour, rather than biomass, is introduced to the reaction chamber, the bio-oil may
be produced by different biomass pyrolysis reaction methods, depending on the
nature of the feedstock. The preferred embodiments of the invention therefore
broaden the range of suitable biomass that may be used.
It will be understood that in the methods of the present invention, the bio-oil vapour
and oil and/or melt may be heated together substantially in the absence of biomass
feedstock.
The present inventors have realised that the invention provides a further advantage.
On heating together bio-oil vapour and oil and/or melt, some permanent gases, such
as H2, CO, C0 2 and CH are produced, which are useful for example in CHP
(combined heat and power) applications as described above. Compared with typical
bio-oil gasification methods, the methods of the present invention operate at a lower
temperature, and do not require catalyst.
In a second preferred aspect, the present invention provides apparatus for fuel
production, comprising
a reaction zone for heating together (i) bio-oil vapour and (ii) oil and/or melt,
to produce reaction products; and
a bio-oil inlet port arranged to flow bio-oil vapour into the reaction zone.
The features of any aspect of the invention may be combined, singly or in
combination, with any other aspect, unless the context demands otherwise. Any
preferred or optional features may be combined, either singly or in combination, and
may be combined with any aspect of the invention, unless the context demands
otherwise.
BRIEF DESCRIPTION OF THE DRAWING
Preferred embodiments of the invention will be described, with reference to the
accompanying drawing in which:
Fig. 1 illustrates schematically apparatus according to an embodiment of the
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS AND FURTHER
OPTIONAL FEATURES
Further preferred and optional features of the invention will now be set out.
In the method of the present invention, bio-oil vapour and oil and/or melt are heated
together, to produce a fuel product. Without wishing to be bound by theory, the
present inventors believe that on heating, radicals deriving from the bio-oil vapour are
formed. These radicals are understood to initiate cleavage of bonds in the oil and/or
melt, and to initiate hydrogen abstraction from the oil and/or melt, destabilising the
bonds in the oil and/or melt and promoting cracking. The bio-oil vapour may also act
as a hydrogen source in bond cleavage. This interaction of bio-oil radicals with the
oil and/or melt is thought also to promote breakdown of the bio-oil vapour, into
fragments which can react with cracked fragments of the oil and/or melt, and into
gasification products. In this way, the interaction of the bio-oil vapour with the oil
and/or melt promotes both formation of a fuel product by cracking the oil and/or melt
(and incorporation of bio-oil fragments), and gasification of the bio-oil vapour.
The present invention is particularly useful in the production of a fuel product, as
discussed above. However, it will be apparent to the skilled person on reading this
disclosure that the present invention may also provide a useful gasification process,
e.g. a process for the gasification of bio-oil vapour. Where the primary aim is
gasification, the nature of the oil and/or melt is not particularly limited, and can be any
suitable substance which is typically liquid at the temperature and pressure of the
reaction chamber. (It will be understood that as used herein, the term gasification
refers to the production of permanent gas products such as CO, C0 2 H2 and CH .)
It may be preferable that the oil and/or melt comprises substances having carboncarbon
bonds and/or carbon-hydrogen bonds, since such substances are believed to
be particularly suitable for interaction with the bio-oil radicals. Particularly suitable
are substances comprising one or more chains of carbon atoms linked by carboncarbon
bonds, for example chains comprising 2 or more, 3 or more, 4 or more, 5 or
more, 10 or more, 15 or more, or 20 or more carbon atoms.
For example, the oil and/or melt may comprise one or more substance selected from
the group consisting of biologically derived oils and fats; polymers; hydrocarbons;
and silicone oils. It will be understood that the present invention is suitable for
cracking mixtures of oils and/or melts, for example mixtures of the substances
described herein.
The nature of the polymers suitable as the oil and/or melt is not particularly limited in
the present invention. Particularly suitable are polymers comprising one or more
chains of carbon atoms linked by carbon-carbon bonds, for example chains
comprising 2 or more, 3 or more, 4 or more, 5 or more, 0 or more, 15 or more, or 20
or more carbon atoms. Example polymers comprising chains of carbon atoms linked
by carbon-carbon bonds include polyolefins (including polyethylene, polypropylene,
polybutylene, polybutadiene, and so on), polystyrene and polyvinyl chloride. For
example, waste plastics material may be used.
Particularly preferred as the oil and/or melt are hydrocarbons. Hydrocarbons include
petroleum, petroleum fractions and synthetic (e.g. polymeric) hydrocarbons such as
polyolefins (including polyethylene, polypropylene, polybutylene, polybutadiene, and
so on, and polystyrene). Particularly preferred are oils and/or melts comprising
hydrocarbons having at least 20 carbon atoms. For example, at least 30%, 40% or
50% by weight of the oil and/or melt may be hydrocarbons having at least 20 carbon
atoms. There is no particular upper limit on the number of carbon atoms in the
hydrocarbon. However, the substance should typically be liquid at the temperature
and pressure of the reaction chamber. For example, C20 to C o or C20 to C o
hydrocarbons may be suitable. The oil and/or melt may comprise predominantly C
to C 0 or C2o to C hydrocarbons.
The nature of petroleum suitable as the oil and/or melt is not particularly limited in the
present invention. For example, the oil and/or melt may be crude oil. The present
invention is particularly suited to processing "heavy crude oil". The term heavy crude
oil will be understood by the skilled person. For example, it may be a crude oil
having a density of 750 g m 3 or more, for example having a density of 800, 900 or
1000 g m 3 or more.
Alternatively or additionally, the petroleum may be a petroleum fraction, obtainable
through fractionation of crude oil, such as fractionation of heavy crude oil, light crude
oil or sweet crude oil. Petroleum residue, which is the residue remaining after
fractionation of crude oil, may be used. Other heavy petroleum or petroleum
fractions may be used, such as petroleum or petroleum fractions comprising
predominantly molecules having at least 20 carbon atoms, for example C 0 to C o or
20 to C 0 fractions. For example, heavy fuel oils, such as number 4 fuel oil, number
5 fuel oil and number 6 fuel oil are suitable, the fuel oil grade being determined
according to ASTM D396.
Preferably, the oil and/or melt is supplied to the reaction zone as a liquid. It may be
supplied to the reaction zone via an oil and/or melt inlet port, for example by
pumping.
The bio-oil vapour suitable for flowing into the reaction zone is not particularly limited,
and may be derived from any suitable pyrolysis method, and from any suitable
biomass feedstock. Suitable feedstocks include plant biomass such as wood, bark
and straw, biomass-based residue, sewage sludge, paper and lignin, High ash
and/or low ash feedstock may be used. The biomass particle size also is not
particularly limited. Both coarse and fine particles, and mixtures thereof, are suitable.
Typically, most CI, S and N deriving from the biomass is retained in the char
produced in the pyrolysis process, and is not present in the bio-oil vapour which
passes to the reaction zone. Similarly, the char may retain other components of the
biomass, advantageously keeping them from passing into the reaction zone with the
bio-oil vapour.
Bio-oil vapour may be flowed from a pyrolysis reactor into the reaction zone, for
example directly from a pyrolysis reactor into the reaction zone. For example, bio-oil
vapour produced in the pyrolysis reactor may be flowed directly into the reaction
zone, without condensing the bio-oil. It will be understood that the methods of the
present invention may comprise pyrolysing biomass and flowing bio-oil vapour
produced by said pyrolysis into the reaction zone.
The bio-oil vapour flowed into the reaction zone may also comprise permanent gases
produced in the pyrolysis reactor, and also may contain water derived from water
present in the biomass feedstock and/or produced during the pyrolysis reaction. It
will be understood that an inlet conduit, connected to the inlet port, may provide a
flow path for bio-oil vapour from a pyrolysis reactor to the reaction zone.
The pyrolysis reactor may be a reactor as described in WO2009/1 38757, which is
hereby incorporated by reference in its entirety and for all purposes, but in particular
for the purpose of describing and defining a pyrolysis reactor.
Alternatively or additionally, the bio-oil vapour may be supplied to the reaction zone
from a reservoir of bio-oil. In this way, bio-oil which has been produced at another
location and/or stored for a period of time can be used. Bio-oil from the reservoir is
vaporised before it is flowed into the reaction zone. It will be understood that the
apparatus may include a bio-oil reservoir, which may be in fluid communication with
the reaction zone.
It will be understood that a small amount of liquid bio-oil may inevitably be present in
bio-oil vapour flowed into the reaction zone. However, the skilled person will
understand that the bio-oil is preferably flowed into the reaction zone predominantly,
for example substantially entirely, as a vapour.
The apparatus may further comprise a liquid port/conduit for transferring liquid (e.g.
oil and/or melt) from the reaction zone to the bio-oil input port. In this way, oil and/or
melt from the reaction zone may pass along the inlet conduit and be returned to the
reaction chamber. Preferably, the oil and/or melt is atomised before it enters the biooil
inlet port, and accordingly it will be understood that an atomiser may be provided
for atomising the oil and/or melt. The flow of oil and/or melt (e.g. atomised oil and/or
melt) from the reaction zone along the inlet conduit can help to reduce the build up of
solid residue (e.g. char) from the bio-oil vapour on the walls of the inlet conduit, by
purging it. For example, oil and/or melt may be pumped from the reactor to the biooil
inlet conduit, or oil and/or melt may overflow from the reactor into the liquid
port/conduit.
The bio-oil vapour and oil and/or melt are heated together in the reaction zone to
produce reaction products. Preferably, the reaction zone is a reaction chamber.
Preferably, the reaction zone is provided with agitation means, for agitating the bio-oil
vapour and the oil and/or melt, to promote mixing of these substances. For example,
the reaction zone may be provided with stirring means or a mixer pump to cycle the
reaction zone contents around the reaction zone. The reaction zone may be
provided with one or more augers. However, providing agitation is not essential. In
some cases, supplying the bio-oil vapour to the reaction zone may provide sufficient
mixing. For example, bio-oil vapour may be provided at the base of the reaction
zone, and bubbled through the oil and/or melt in the zone.
The reaction zone may have a settling unit, for capturing settling solid reaction
products.
A typical temperature in the reaction zone is 450°C. At this temperature, the
reactions proceed at a useful rate. Preferably, the temperature in the reaction zone
is at least about 300°C, more preferably at least about 310°C, at least about 320°C,
at least about 330°C, at least about 340°C, at least about 350°C, at least about
360°C, at least about 370°C, at least about 380°C, at least about 390°C, or at least
about 400°C. At lower temperatures, the oil and/or melt tends to have too high a
viscosity (although, of course, this depends on the nature of the oil and/or melt).
Furthermore, both the oil and/or melt and the bio-oil vapour tend to be insufficiently
reactive at lower temperatures. Preferably, the temperature in the reaction zone is
about 600°C or less, preferably about 550°C or less, more preferably 540°C or less,
530°C or less, 520°C or less, 510°C or less or 500°C or less. At higher temperatures,
the cracking reaction tends to progress at a very high rate, which leads to smaller
molecules being formed. This increases the yield of gases, and reduces the yield of
useful liquid products. Additionally, at high temperatures, large amounts of carbon
may be produced, which can accumulate in the reactor and cause clogging.
Typically, when oil and/or melt is heated alone, it is not cracked, or is cracked very
slowly, within the above temperature ranges. (Similarly, typically when bio-oil vapour
is heated alone, it is not gasified, or is gasified very slowly, within the above
temperature ranges.) Thus, in the preferred embodiments of the invention, the useful
products of the process are significantly increased by heating a combination of the oil
and/or melt with the bio-oil compared with the same oil and/or melt alone (or the
same bio-oil alone) under the same physical conditions of temperature and pressure.
The products of the reactions occurring in the reaction zone are preferably removed
from the reaction zone as a vapour (or as a mixture of non-condensable gases and
vapour, in the manner explained below). Preferably, the vaporous products are
transferred to a condenser which is in fluid communication with the reaction zone.
Permanent gases, such as Cm, C0 2, CO and H2 are not condensed in the
condenser. The permanent gases may be transferred to a combined heat and power
unit (CHP), which may be used to provide heat and/or power for the processes
described herein.
The remaining vapours may be condensed to provide liquid products. Typically, the
liquid products are separated into separate phases in the condenser. Typically, the
phases include an aqueous phase containing predominantly water, a bio-oil phase
containing bio-oil (e.g. which has not been fully reacted in the reaction zone), and a
cracked reaction product phase.
This bio-oil phase may be returned to the pyrolysis reactor to vaporise it, from where
it is flowed as a vapour into the reaction zone for further reaction. Alternatively, the
bio-oil may be put to an alternative use, for example as a fuel.
Typically, the cracked reaction product phase includes hydrocarbon molecules. The
present inventors have realised that hydrocarbon products, such as linear
hydrocarbon products such as alkanes and alkenes, can be produced even where oil
or melt which is not a hydrocarbon oil and/or melt is used, such as non-hydrocarbon
bio-derived oils and fats, and polyvinyl chloride. Without wishing to be bound by
theory, this is believed to be due to destabilisation of bonds to atoms other than
carbon and hydrogen by the bio-oil radicals.
For example, the cracked reaction product may include at least 50%, at least 60%, at
least 70%, at least 80%, at least 90% or at least 95% by weight hydrocarbon
molecules, such as alkane, alkene and/or aromatic molecules. Preferably, at least
30%, at least 40%, least 50%, at least 55%, at least 60%, at least 65%, at least 70%,
at least 80%, at least 90% or at least 95% by weight hydrocarbon molecules are
alkane and/or alkene molecules.
Typically, the hydrocarbon molecules each have at least about 0 carbon atoms, for
example at least about 12 carbon atoms. Typicady, the hydrocarbon molecules each
have about 20 carbon atoms or fewer. For example, at least 40%, at least 50%, at
least 55%, at least 60%, at least 65%, at least 70%, at least 80%, at least 90% or at
least 95% by weight of the hydrocarbon molecules may have at least about 10 or at
least about 12 carbon atoms, and may have about 30 carbon atoms or fewer, more
preferably 25 or 20 carbon atoms or fewer. Typically, hydrocarbon molecules having
a higher number of carbon atoms are not vaporised in the reaction zone and so are
not removed from the reaction zone.
In a further preferred aspect, the present invention provides a cracked reaction
product, preferably comprising hydrocarbon molecules. The cracked reaction
product may be obtained or obtainable by a method according to the present
invention. It will be understood that the term "cracked reaction product" includes
products produced in the reaction zone as described herein, and also includes
products which have been further refined, for example as described herein. The
cracked reaction product may be, for example, a fuel, such as a diesel fuel.
Typically, the cracked reaction product phase is useful as a fuel, e.g. a fuel oil. It
may be used as it is, or may be further refined. For example, it may be fractionated,
in a similar way to crude oil. In this way, fuel oil fractions each having a narrower
range of molecular weights may be obtained.
The present inventors have found that the cracked reaction product phase typically
includes alkene molecules (having one or more carbon-carbon double bonds). This
can be undesirable, since typically fuels such as diesel contain mostly saturated
hydrocarbons, along with some aromatic hydrocarbon compounds. Accordingly, the
cracked reaction product may be hydrogenated e.g. to reduce its alkene content, in a
hydrogenation reactor. For example, the cracked reaction product may be
transferred from the condenser to the hydrogenation reactor, which may be in fluid
communication with the condenser via a cracked reaction product port.
Suitable hydrogenation methods will be known to the skilled person. Any suitable
hydrogenation method may be used, such as catalytic hydrogenation for example
with a nickel-based or platinum catalyst.
Conveniently, hydrogen for the hydrogenation may at least in part be provided by
(incomplete) gasification of char produced in the methods of the present invention.
As described above, the reaction zone may be connected to a pyrolysis reactor,
which provides bio-oil by pyrolysis of biomass. This biomass pyrolysis also produces
char. This char may be gasified or reformed in a char gasification reactor. Typically,
char from the pyrolysis reactor is transferred to the char gasification reactor and
gasified in the presence of air and steam, to produce ash, CO and H2. The hydrogen
may be transferred to the hydrogenation reactor via a hydrogen port. Producing the
hydrogen for hydrogenation on site is convenient and may lower the costs and
improve the efficiency of the overall process.
Conveniently, the steam for the gasification of the char may be provided from the
aqueous phase produced in the condenser.
Production of hydrogen from char produced from biomass pyrolysis and steam
produced in the reaction zone can significantly reduce the amount of waste produced
by the process. The present inventors have realised that this in situ production of
hydrogen from (waste) products of other processes is a novel process in itself.
Accordingly, the present invention provides a hydrogen generating process
comprising
pyrolysing biomass to produce char and bio-oil;
processing the bio-oil to produce products including water and/or steam; and
combusting the char in the presence of the water and/or steam to produce
hydrogen.
It will be understood that the hydrogen may be used to hydrogenate reaction
products, e.g. reaction products of the bio-oil processing step.
The CO (and any hydrogen not used for hydrogenation) produced in the char
gasification reactor may be transferred to a CHP unit, to provide heat and power, via
a gas port. Alternatively or additionally, it may be used to synthesise fuel.
Hydrogen (and optionally CO), e.g. produced in the char gasification reactor, may be
introduced into the pyrolysis reactor. This can help to refine the fuel product
produced in the reaction zone, for example by increasing its hydrogen content (e.g.
the fuel products have fewer Carbon-carbon double bonds). Alternatively or
additionally, hydrogen (and optionally CO) may be introduced into the bio-oil vapour
inlet conduit and/or into the reaction zone itself.
Ash, produced for example in the char gasification reactor, may be useful as a
fertilizer. In this way, it will be understood that the total waste products of the
process may be very low, for example approaching zero.
In order to provide increased control of the reactions occurring in the reaction zone, a
reflux column may be provided, to return some vapours to the reaction zone as
liquids. For example, molecules with boiling point above a predetermined level may
condense in the reflux column and be returned to the reaction zone. In this way, for
example, the average size of molecules in the cracking reaction product can be
reduced, as larger cracking reaction products (and "un-cracked" molecules) are
returned to the reaction zone for (further) cracking. Vapours not returned to the
reaction zone by the reflux column may pass to the condenser for condensing, for
example to produce the liquid product phases described above. The reflux column
may be, for example, a fractional distillation column.
In the above discussion, the cracking reaction products are sometimes referred to as
products of oil and/or melt cracking. However, it will readily be understood that some
components of the bio-oil vapour will likely be present in the cracking reaction
product. For example, alkane, alkene and alcohol fragments from molecules in the
bio-oil may be present in the cracking reaction product phase. This may be
advantageous. The presence of bio-oil derived fragments in the cracking reaction
product means that where it is used as a fuel, a proportion of the energy of the fuel is
bio-derived energy. For example, up to about 25% of the energy in the fuel may be
bio-derived energy. Accordingly, the fuel can be considered to be relatively
environmentally friendly. This bio-derived energy content is larger than the residual
bio-derived energy for example in petrol, diesel and natural gas synthesised from
syngas.
It will also be understood that some of the oil and/or melt may be cracked into
gaseous molecules, such as methane or ethane.
A preferred embodiment of the invention will now be described, with reference to
Figure .
Figure 1 shows fuel production apparatus according to an embodiment of the present
invention. The apparatus has a reaction chamber 1 filled with oil 2. Oil is supplied to
the reaction chamber by a feed port 3. The reaction zone further has a settling unit 4
and mixing units 5. Bio-oil vapour is supplied to the reaction chamber via a bio-oil
inlet conduit 6, which is an elongate passage.
A liquid conduit 7 is provided. Oil 2 from the reaction chamber 1 overflows into the
liquid conduit 7, and is transferred to the bio-oil inlet conduit 6 at a position distal from
the reaction chamber 1. An atomiser is provided to atomise the oil/melt from the
reaction chamber as it enters the inlet conduit. In this way, oil 2 from the reaction
chamber 1 flows along the bio-oil inlet conduit, to reduce or prevent build-up of solid
residue in the bio-oil inlet conduit 6.
A pyrolysis reactor 8 is provided, for producing the bio-oil vapour. Biomass
feedstock 9 is supplied to the pyrolysis reactor 8 via a port 10.
A condenser 11 is provided, which is connected to the reaction chamber by a
condenser conduit 12. The condenser conduit 2 is positioned near the top of the
reaction chamber , for removal of vaporous reaction products from the reaction
chamber 1.
Non-condensable gases are transferred to a combined heat and power unit 3, to
provide power and heat to the apparatus.
The vapour is condensed to provide a cracked reaction product 14, bio-oil 15 and
water 16.
The bio-oil 15 is transferred back to the pyrolysis reactor 8. It is then transferred
back to the reaction chamber 1 as a vapour.
The cracked reaction product 14 contains mostly hydrocarbons, which are typically
unsaturated. The cracked reaction product 1 is transferred to a hydrogenation
reactor 7. Hydrogen for the hydrogenation reactor is supplied from a char
gasification reactor . Char from the pyrolysis reactor 8 is transferred to the char
gasification reactor 1 . The char is gasified in the char gasification reactor 8 in the
presence of air and steam. The steam is provided to the char gasification reactor
via a steam conduit 19, which carries water 16 from the condenser 12 . The water is
heated to form steam via a coil 20 surrounding the bio-oil inlet conduit 6.
Gases produced in the char gasification reactor 18 are transferred to the
hydrogenation reactor 17, the CHP unit 3 and optionally the pyrolysis reactor 8.
Ash is removed from the char gasification reactor 18.
Hydrogenated cracked reaction product is removed from the hydrogenation
reactor 1 . Typically, this product is suitable for use as diesel fuel.
In the methods of the present invention, typically, about 80% of the biomass
feedstock added to the pyrolysis reactor is gasified or incorporated into the cracked
reaction product as described above. (This includes products of bio-oil processing in
the reaction zone, and the gaseous products of char gasification in the char
gasification reactor.) The remainder of the biomass is typically ash and water.
Typically, about 30% of the oil and/or melt is converted into cracking reaction
product, while about 0% forms a solid residue and the remainder forms gas, which
can be used in the CHP unit.
The preferred embodiments have been described by way of example only.
Modifications to these embodiments, further embodiments and modifications thereof
will be apparent to the skilled person on reading this disclosure and as such are
within the scope of the present invention.
All references cited herein are hereby incorporated by reference in their entirety and
for all purposes.
REFERENCES
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2. de Miguel Marcader, F. et al, App. Cat. B: Environ. 96 (2010) 57-66
3. Elliot, D., Energy & Fuels 2007 2 1 1792-1815
4. Balduaf, W. et al, Biomass and Bioenergy Vol. 7 Nos. 1-6 237-244, 1994
5. de Miguel Marcader, F. et al, Energy Environ. Sci. Jan 201 1
(DOI: 10.1039/c0ee00523a)
6. Darmstadt, H. et al, Carbon 39 (2001) 815-825
7. Garcia-Perez, M. et al, Fuel 8 1 (2002) 893-907
8. Garcia-Perez, M. et al, Fuel 80 (2001) 1245-1258
9. Kuznetsov, B.N. et al, Int. J. Hydrogen Energy 34 (2009) 7051-7056
10. Brebu, M. et al, Fuel 89 (2010) 191 1-1918
I I . Rutkowski, P., Waste Management 29 (2009) 2983-2993
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13. Sharypov, V.I. et al, J. Ana. & App. Pyrolysis 64 (2002) 15-28
14. Marin, N. et al, J. Ana. & App. Pyrolysis 65 (2002) 41-55
15. Sharypov, V.I. et al, J. Ana. & App. Pyrolysis 67 (2003) 325-340
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CLAIMS
. A method for the production of fuel, the method comprising:
flowing bio-oil vapour, from externally of a reactor, into a reaction zone of the
reactor;
heating together in the reaction zone (i) the bio-oil vapour and (ii)
hydrocarbon oil and/or melt, to carry out cracking; and
extracting cracked reaction products.
2. A method according to claim 1 wherein the bio-oil vapour and hydrocarbon oil
and/or melt are heated together without the addition of catalyst.
3. A method according to any one of the preceding claims wherein the bio-oil
vapour and hydrocarbon oil and/or melt is heated to a temperature in the range from
350°C to 550°C.
4. A method according to any one of the preceding claims wherein the
hydrocarbon oil and/or melt is selected from petroleum, a petroleum fraction, a
synthetic hydrocarbon and mixtures thereof.
5. A method according to any one of the preceding claims wherein the
hydrocarbon oil and/or melt comprises predominantly C2oto C50 hydrocarbons.
6. A method according to any one of the preceding claims, further comprising
pyrolysing biomass and flowing bio-oil vapour produced by said biomass pyrolysis
into the reaction zone via a bio-oil input port.
7. A method according to any one of the preceding claims, comprising producing
a cracked reaction product comprising alkenes and hydrogenating the cracked
reaction product to produce a hydrogenated product.
8. A method according to claim 7 wherein hydrogen for the hydrogenation of the
cracked reaction product is at least partially produced by gasification of char.
9. A method according to claim 8 wherein said char is at least partially produced
by biomass pyrolysis, for example a biomass pyrolysis process used to produce said
bio-oil vapour.
10. A cracked reaction product obtained or obtainable by a method according to
any one of claims 1 to 9 , said cracked reaction product comprising hydrocarbon
molecules.
1 . Apparatus for fuel production, comprising
a reaction zone for heating together (i) bio-oil vapour and (ii)
hydrocarbon oil and/or melt, to produce reaction products; and
a bio-oil inlet port arranged to flow bio-oil vapour into the reaction
zone.
12. Apparatus according to claim 11 further comprising a pyrolysis reactor,
wherein the inlet port provides a flow path for bio-oil vapour from the pyrolysis reactor
to said reaction zone.
13. Apparatus according to claim 12 further comprising a char gasification reactor
arranged to gasify char produced in the pyrolysis reactor to produce products
including hydrogen.
14. Apparatus according to claim 3, further comprising a hydrogenation reactor,
said hydrogenation reactor being connected to the char gasification reactor by a
hydrogen port for supplying hydrogen produced in the char gasification reactor to the
hydrogenation reactor.
5. Apparatus according to claim 1 , further comprising a bio-oil reservoir,
wherein the input port is arranged to flow bio-oil, such as bio-oil vapour, from the
bio-oil reservoir into the reaction zone.
16. Apparatus according to any one of claims 11 to 15, comprising a combined
heat and power unit for providing heat and power to the apparatus by combustion of
gas produced by the apparatus.