Improvement of the Flash-Pyrolysis Process and Pilot Plant for Bio-Oils

Upgrading
Summary
The project has the overall objective of studying different methods of upgrading fast pyrolysis liquids
in order to overcome anticipated problems of utilising crude fast pyrolysis liquid derived from
biomass !t the time that the project "as proposed and agreed# there "as considerable interest in
the production of liquid fuels and a belief that the crude biomass derived fast pyrolysis liquid $bio-oil%
"as too unstable to be used directly in po"er and thermal applications There had already been
some success in upgrading bio-oil to hydrocarbons by hydrotreating on a laboratory scale to produce
a naphtha type product "hich could be upgraded by conventional refinery operations to diesel and
light fuel oil& and also 'eolite crac(ing to produce crude aromatics that could li(e"ise be upgraded to
gasoline by conventional refinery operations
The project therefore aimed to develop and evaluate t"o chemical upgrading processes
hydrotreating and 'eolite crac(ing !n assessment of upgrading through chemicals recovery "as
included )uring the contract negotiation stage an opportunity arose to participate in a bio-oil fired
gas turbine test programme in *anada and this "as included to gain first hand e+perience of the
problems arising from not upgrading
!ll of the initial objectives e+cept the construction of a dedicated bio-oil hydrotreating pilot plant
have been satisfactorily completed )ue to ban(ruptcy of the major project contractor# this element
could not be completed and this "as replaced by tests on an e+isting unit and detailed design
studies These have enabled the aims of providing a robust technical and economic evaluation to be
completed
)uring the course of the project# it became clear that the crude fast pyrolysis liquid - or bio-oil - could
be satisfactorily used in gas turbines $also in engines in parallel projects%# and the need for upgrading
"as thus obviated It is also clear that the costs of producing transport fuels are far too high# even
"ith major fiscal incentives Of the t"o main routes studied# the 'eolite crac(ing route "hich is
integral "ith the fast pyrolysis process seems to offer substantial economic benefits# although it is
less developed than hydrotreating It is recommended that attention be focused on stabilising the
crude liquid to ma(e it more amenable to "ider usage and to study the upgrading processes as a
means of deriving higher value chemicals
Introduction
,hen this contract "as a"arded in -../# there "as considerable interest in the production of liquid
fuels and a belief that the crude biomass derived fast pyrolysis liquid "as too unstable to be used
directly in po"er and thermal applications There had already been some success in upgrading bio-oil
to hydrocarbons by hydrotreating on a laboratory scale and the trials on 'eolite crac(ing for
aromatics production appeared promising This project therefore aimed to e+plore these upgrading
technologies by utilising both the e+isting industrial and academic e+pertise in 0urope and also by
commissioning "or( "ith leading organisations in 1orth !merica in order to provide the most
efficient and effective "ay of progressing the technologies
Objectives
The primary objective of the project is the design# construction# testing and evaluation of a pilot plant
to hydrotreat fast pyrolysis bio-oils for the production of hydrocarbon fuels *omplementary
objectives include an assessment of the performance and production cost of Robinia and s"eet
sorghum# evaluation of 'eolites as an alternative upgrading route# gas turbine testing on crude bio-
oils and an evaluation of the recovery of high value chemicals The structure of the project sho"ing
the activities and contributions as "ell as the interactions and relationships is summarised in the
Figure belo" This has been modified from the original plan to account for the consequences of the
retirement of Fochi# but is other"ise largely unchanged from the original plan
Progress
The problems met by the project are "ell documented in interim reports# but the most serious "as
the "ithdra"al of the lead contractor# Fochi# due to their liquidation The resultant time delay and
inability of finding another company to provide the necessary e+pertise and financial resources
"ithin the time constraints of the project meant that one of the primary objectives of the project to
build a hydrotreating plant became increasingly difficult to realise It "as also appreciated that there
"ere e+isting hydrotreating facilities at several centres in 0urope# "hich# coupled to the success of
other projects in using the crude bio-oil "ithout upgrading# and the severe shortage of funds in the
project# mitigated against pursuing construction of the pilot plant
In -..2 it "as agreed by all the partners and the *ommission to modify the "or( programme and
substitute construction of the hydrotreating pilot plant by tests and detailed design studies of
hydrotreating pilot plants "ith cost estimates
Activities
!ll objectives of the contract have been successfully completed apart from not building a
hydrotreating pilot plant ,ith the present (no"ledge of pyrolysis liquids# this is no" seen to be not
necessary# -so does not detract from the from the project The rest of the "or( can be summarised
on a tas( by tas( basis# as follo"s3
Test on growing, harvesting, chipping and storing Robinia and sweet sorghum, economic analysis of the
biomass production systems, market analysis of biomass availability and analysis of integrated supply
systems. Tests have been completed on s"eet sorghum and Robinia gro"ing# harvesting# drying and
transport ! linear programming model of biomass supply systems has been constructed !n analysis
of biomass supply sources and systems has been carried out The conclusions of this part of the "or(
"ere that results for production of sorghum "ere valuable the cultivars "ere not as satisfactory as
others tested else"here 4arvesting of 5obinia "as successful "ith the machine tested but the
equipment needs strengthening The model suggests that Cynara is the most promising biomass
crop# follo"ed by Arundo Donax. *ombined crops provide year round supply "hich has implications
for conversion plant specifications and design Biomass supplies have been identified in the Umbria
region "hich "ill provide a methodology and results for other areas
Characterisation of pyrolysis liuid and the upgraded products, evaluation of the hydrotreating plant and
supply of bio!oil. !s the hydrotreating plant "as not built some objectives could not be met *hemical
and physical properties "ere measured on bio-oil supplied by 0nsyn and Fenosa# and on partially
upgraded bio-oil from 6assari# and on fully upgraded oil from the )7T tests Upgrading processes
"ere revie"ed and it "as concluded that fast pyrolysis of biomass is not yet a "ell proven
technology# bio-oils from different sources e+hibit significantly different characteristics# the )7T
upgraded product consisted mostly of paraffinic hydrocarbons "hile there is a "ide variation in
upgraded product costs
Delivery of bio!oil from the "enosa pilot plant and techno!economic assessments of the #"$$ system
with a fluid bed pyrolyser operating at %&&'C and atmospheric pressure. This part of the project resulted
in samples of oil being delivered to . organisations *apital costs have been estimated for pyrolysis
processes from 89 7"e to :8 7"e "hich range from :298 0*U;(,e output for the pyrolysis plant
alone $no engine% at 89 7,e to /-:8 0*U;(,e at :8 7,e 7ass balances and electricity outputs
have been reported for pyrolysis processes from 89 7,e to :8 7,e It "as concluded that the
brea(-even for a -2< I55 is achieved at around = 7,e based on bio-oil as the product The "ater
content of the biomass has a significant effect on the production costs 6mall projects can only be
justified if there is a social credit >arge projects may be financially viable for lo" cost biomass feed
such as forestry residues
(ydrotreating on a laboratory scale unit and design of pilot plant. The laboratory scale process "as
successfully operated on bio-oil for the first stage of processing ! detailed pilot plant design "as
produced It "as concluded that full de-o+ygenation of bio-oil is possible by several routes Feasible
designs have been produced for hydrotreating pilot plants *omparisons "ith bio-diesel are
favourable "ith respect to hydrocarbon yield per ha and similar "ith respect to production cost If
bio-diesel is considered economically acceptable# then bio-naphtha is equally acceptable
Techno!economic assessments of the upgrading systems and evaluation of opportunities for recovering
chemicals. *apital cost estimates of seven processes for fast pyrolysis and upgrading have been
provided on a consistent basis at -88 t;h dry "ood input Production costs of crude and upgraded
products have been estimated on a consistent basis ! thorough revie" of chemicals recovery
processes has been completed It "as found that none of the pyrolysis or upgrading processes gives
a product that is economic currently *rude bio-oil and 'eolite crac(ing offer the best short term
prospects for a competitively priced fuel 4ydrotreating is very costly in terms of investment and
hydrogen requirement# even for partial upgrading Future "or( should focus on improving the crude
bio-oil and adapting applications to the crude bio-oil# as "ell as developing integrated processing
such as the 'eolite crac(ing process *hemicals recovery is feasible but the economics "ill depend
very much on mar(et evaluation and development
)xploratory research into existing and new catalysts for hydrotreating bio!oil to produce hydrocarbons
and*or improved stability oil. ! /-: (g;h laboratory unit "as successfully modified to operate "ith a
separate fi+ed catalytic bed and "ith replacement of the sand by catalyst# "ith four catalysts tested
The product proportions changed "ith increased gas and char;co(e production and "ith reduced
liquid yields The liquid "as generally in t"o phases and sho"ed substantially different
characteristics in particular being more distillable and "ith higher hydrocarbon levels It "as
concluded that 'eolite type catalysts can be successfully introduced into an 0nsyn 5TP pyrolysis
system Use of catalysts generally gives a significantly different product range >o"er temperatures
gave higher liquid yields The liquid had much higher levels of hydrocarbons of around .< compared
to -< in bio-oil "ithout catalyst
Tests on a +.% ,#e gas turbine on bio!oil with subsidiary ob-ectives of characterising bio!oil and testing
it for combustibility and effect on turbine components. The tests "ere successfully completed for a total
duration of -8 hours 0missions "ere measured and found to be belo" corresponding values for
diesel apart from particulates Flame tunnel testing of components "as carried out "ith some
deposition found# particularly on the first stage blade and first stage no''le It "as concluded that
there is a potential for bio-oil fired gas turbines 6ome deposition "as found on turbine components
from flame tunnel tests but these are not necessarily representative The emissions "ere entirely
acceptable for *O# 1O+# methane# equivalent total hydrocarbons and 68/- particulates "ere higher
than diesel
Development of hydrotreating using conventional hydrotreating catalysts to achieve low severity upgrading.
! laboratory scale unit "as successfully operated in do"nflo" mode and good mass balances
achieved ! revised pilot plant specification and design "ith capital cost estimate "as provided It
"as concluded that lo" severity hydrotreating is an alternative to full de-o+ygenation for improving
the properties of crude bio-oil# but still requires many of the features of full hydrotreating# but at a
lo"er capital cost The use of nic(el catalysts at lo" temperatures leads to alcohol formation giving a
more stable but o+ygenated product
Conclusions
)uring the course of the project# it "as found that the crude fast pyrolysis liquid - or bio-oil - could be
satisfactorily used in gas turbines $also in engines in parallel projects%# and the need for upgrading to
hydrocarbons "as thus obviated The costs of producing transport fuels is too high# even "ith major
fiscal incentives# Of the t"o main routes studied# the 'eolite crac(ing route "hich is integral "ith the
fast pyrolysis process seems to offer substantial economic benefits# although it is less developed
than hydrotreating It is recommended that attention be focused on stabilising the crude liquid to
ma(e it more amenable to "ider usage in different applications and to study the upgrading
processes as a means of deriving higher value chemicals