In-situ catalytic cracking of biomass to high quality bio-energy products

Abstract

Biomass has gained increased attention in the past decade because it does not only provide an effective
option for the provision of bio-energy services from a technical point of view, but also based on bio-
resources that can be utilized on a sustainable basis all around the globe. Biomass can be converted into
bio-energy through several thermo-chemical processes and one of them is by using fast pyrolysis process
to produce bio-oil, bio-char and bio-gas. Current bio-oils produced from fast pyrolysis of biomass are
inherently unstable due to their high oxygen content and acidity which leads to polymerization of reactive
components and subsequent viscosity increase which hinders direct refining. Catalytic processes are
capable of reducing acidity and oxygen content of fast pyrolysis bio-oils under moderate conditions thereby
improving oil stability and allowing direct refining. In-situ catalytic fast pyrolysis (ICFP) is a new promising
technology to convert directly solid biomass in the presence of catalysts to product value-added products in
one step. This process is cheap and has great potential to produce hydrocarbons directly from biomass or
produce higher quality bio-oils with improved stability lending them more amenable for the subsequent
upgrading process.

However, the design of the suitable catalyst to achieve high bio-oil yield and better deoxygenation is still a
potential challenge. This study will develop new heterogeneous catalyzed processes to convert
lignocellulosic or aquatic biomass to high value platform and commodity chemicals. Achieving the aims of
the project requires novel fast pyrolysis reactor and multifunctional catalyst which optimizes the process
and deoxygenation capability. Target formulations could be scaled up and dispersed onto the porous
architectures for study in lab-scale industrial-style reactors. These will priority promising pathways by
working closely with industry to benchmark novel processes against established ones and also develop the
performance measures (e.g. techno economic analysis).

1. Research Background:

Power-generating plants running on fossil fuels have been identified as the main source of greenhouse
gases (GHG), which leads to global warming [1]. Approximately 80% of the world primary energy
consumption is still dependent on fossil fuels [2]; thus, the substitution by renewable energy sources, in
conjunction with other clean energy sources, appears to be the best and necessary alternative [3]. There
are many other sources of renewable energy such as solar, wind, and geothermal, but biomass have been
receiving a lot of attention lately. Biomass has gained increased attention in the past decade because it
does not only provide an effective option for the provision of bio-energy services from a technical point of
view, but also based on bio-resources that can be utilized on a sustainable basis all around the globe [4].
Biomass can be converted into bio-energy through several thermo-chemical processes and one of them is
by using fast pyrolysis process to produce bio-oil, bio-char and bio-gas. A techno-economic analysis of
three conversion platforms (i.e., pyrolysis, gasification, and biochemical) comparing capital and operating
costs for near-term biomass-to-liquid fuels technology scenarios was performed recently [5]. The analysis
showed that the standalone biomass-to-liquid fuel plants are expected to produce fuels with a product value
in the range of $2.00–5.50 per gallon gasoline equivalent, with fast pyrolysis being the lowest and bio-
chemical conversion the highest. Fast pyrolysis shows the highest yield to liquid fuel products and retains
most of the energy from feed stocks in the liquid products. Typical bio-oil from fast pyrolysis of woody
biomass has high oxygen content and a low H/C ratio compared to crude oil (Table 1.1). Some properties
of bio-oil from fast pyrolysis of lignocellulosic biomass significantly limit its direct utilization as transportation
fuel in current systems [6]. Generally, bio-oils are characterized by low vapor pressure, low heating value,
high acidity, high viscosity, and high reactivity [7-9].

Table Error! No text of specified style in document.-1: Typical properties of bio-oil and crude oil [10]

Composition Bio-oil Crude oil

Water (%) 15 – 30 0.1

pH 2.8 – 3.8 -

Density (kg L-1) 1.05 – 2.05 0.86 - 0.94

Viscosity 50 °C (cP) 40 – 100 180

HHV (MJ kg-1) 16 – 19 44

C (wt%) 55 – 65 83.86

H (wt%) 5–7 11 – 14

O (wt%) 28 – 40 <1

Ash (wt%) < 0.2 0.1

H/C 0.9 – 1.5 1.5 – 2.0

O/C 0.3 – 0.5 ~0

Bio-oils show a wide range of boiling temperatures due to their complex compositions. These adverse
characteristics, particularly the instability of bio-oil, are associated with the high oxygen content in the bio-
oil, which is considered to be a primary issue among the differences between bio-oils and hydrocarbon
 fuels [17,21].The low heating value and flame temperature, greater ignition delay, and lower combustion
rate of bio-oil are largely due to the high water content (15–30 wt%), although water could reduce the
viscosity and enhance the fluidity [17, 23]. The low pH of 2–3 of bio-oil is due to the significant amount of
carboxylic acids, mainly formic and acetic acids and leads to its corrosiveness to common construction
materials such as carbon steel and aluminium as well as some sealing materials [17]. The high content of
acidic components also makes the bio-oils extremely unstable. The physicochemical properties of bio-oils
change as a function of time under ordinary storage conditions [24]. The viscosity of bio-oil increases due
to secondary condensation and polymerization of the high concentration of reactive components like
aldehydes, ketones, and phenols [25]. In distillation, 35–50 wt% of the primary bio-oil is left as a residue
due to the polymerization of reactive components and the substantial amounts of non-volatile sugars and
oligomeric phenols. Highly oxygenated bio-oils are immiscible with hydrocarbon fuels.

2. Problem statement:

Bio-oil produced directly from the fast pyrolysis process exhibits rather a low quality compared with
standard petroleum-derived fuels. It is acidic and highly oxygenated due to the highly oxygenated
compounds such as acids, phenols, ketones, aldehydes, and furans. It is necessary and desirable to
improve the quality of bio-oil towards properties similar to hydrocarbons fuel by employing upgrading
techniques. Catalytic fast pyrolysis (CFP) is one of the alternative ways which involves the introduction of
suitable catalyst to directly upgrade the pyrolysis vapors to produce bio-oil with improved quality and
convert different oxygenated groups into desirable commodities such as benzene, xylene, toluene, and
naphthalene.

The previous research available hardly addresses in situ catalytic fast pyrolysis (CFP) by using zeolites to
achieve optimum oil yield and high deoxygenation degree. Current catalytic fast pyrolysis processes show
low oil yield by using in-bed (in situ) mode which influence low degree of deoxygenation. Moreover, the
comparisons of catalytic pyrolysis performance of commercial zeolites with new synthesized zeolites are
not reported in the literature [14, 16-19].The feasibility of using fast pyrolysis techniques for transforming
biomass into potentially useful products, i.e., bio-oil and bio-char through one step is still a challenge. The
fundamental research will also be focussing on bio-oil production through fast pyrolysis techniques that is a
promising and an environmentally friendly disposal method for waste materials (e.g. forest, agricultural
residue or aquatic biomass). The routes to refinery feedstocks to valuable products will be measured
technically and economically.

3. Objectives:
 The potential research project aims to achieve the following goals by overcoming the gaps in existing work
on upgraded bio-oil production via biomass catalytic pyrolysis through implementation of following research
activities:

 To determine the physical, chemical, and fuel characteristics of biomass and products.
 To enhance and develop prototype research apparatus for the investigation of the feasibility of converting
biomass to potentially useful bio-energy products using catalytic pyrolysis techniques.
 Explore the novel catalysts for in-situ catalytic fast biomass pyrolysis (ICFP).
 Synthesis, characterize and evaluate the performance of novel catalyst for in-situ catalytic fast biomass
pyrolysis (ICFP).
 To investigate the influence of the various key process parameters (e.g. process temperature, catalyst) on
the product yield and quality.
 Study the techno-economic measures of the catalytic fast pyrolysis for high quality bio-oil production.

4. Methodology:

The overall research activities is summarised in Figure 1. Furthermore the experimental data is crucial to
support the Process Synthesis and Integration of a Biorefinery. Kinetic data and parametric studies and
optimization will be carried out.

The research approach will cover the following tasks;

1. Feed pre-treatment: Three types of biomass such as soft wood, hard wood/agricultural or
microalgae residues will be characterized.
Feedstock e.g. lignocellulosic biomass or aquatic biomass are abundant and distributed in many global
regions and countries. These residues could be characterized via proximate and ultimate analysis. The
behaviour of biomass during devolatilization will be estimated by thermogravimetric analysis (TGA) and
Fourier-transform analysis (FT-IR).

2. Catalyst Screening:

Hierarchical zeolites catalysts have unique properties in a number of reactions that are similar to those
involved in the fast pyrolysis process. Full evaluation of zeolites (e.g. improvement in the accessibility ratio
of Bronsted acid sites and structure) may provide an opportunity for limiting coke deposition and improving
the low aromatics yield. Non-precious metal deoxygenation cracking catalysts including doped zeolite
material and bi-functional metal (e.g. Fe, Ni, Mo) based catalysts) will also be synthesized and inquired the
thermal conversion process.

Rigorous characterization analysis is planned in this work:

 Characterizati
on Technique Analysis

SEM Pore size will be measured by examining the topography using

SEM.
FTIR Analysis To measure the functional group attachment.
To measure the thermal stability of catalyst, as high temperature
TGA is required for methane decomposition.

To measure the crystallinity of catalyst and to investigate the

XRD Analysis molecular structure.
Catalyst structure uniformity and surface adsorption will be
XPS analysis analyzed using XPS analysis.

3. Catalytic fast pyrolysis of biomass

Catalytic activity will be tested in a Py-GC/MS which is a unique technique that can be used to characterize
the biomass pyrolysis vapors. Effect of catalytic/biomass ratio, temperature variations will be analyzed.
Product gas will be analyzed using an online GC with TCD detector and spent catalyst will be analyzed for
amount of Carbon deposited, morphological changes, and transition changes with XRD, FESEM and FTIR
techniques.

4. Product Characterization and Purification: Quality of the products will be analysed and purified.

5. Process Development: Parametric studies will be carried out to generate data to support the
process simulation work.

Bio-oil Bio-oil testing

for fuel
Catalytic
Thermo- application
chemical Fast Pyrolysis
Biomass Platform
 Bio-char

Figure 1: General Research Plan

6. Flow char of Research Activities (Appendix A)

7. Gantt Chart of Research Activities (Appendix B)

5. Expected outcomes and deliverables:

The potential research project would expect to achieve the following milestones;

 Completion of physical, chemical, and fuel characteristics of biomass.

 Completion of enhancement of prototype research apparatus.
 Completion of Investigate the influence of the various key process parameters on the product yield and
quality.
 Completion on development of catalyst for in situ catalytic pyrolysis process.
 Completion of process synthesis and integration tools for bio-refinery.
 Publications & annual report submission.
6. Reference:

1. R.S. Kempegowda, K-Q. Tran, 2015. CHP-Integrated Fischer-Tropsch Biocrude Production under
Norwegian Conditions: Techno-Economic Analysis. Energy & Fuels 29, 808-822.
2. J. Goldemberg, 2006. The promise of clean energy. Energy Policy 34, 2185–2190.
3. T. Yoshioka, S. Hirata, Y. Matsumura, K. Sakanishi, 2005. Woody biomass resources and conversion in
Japan: the current situation and projections to 2010 and 2050. Biomass & Bioenergy 29, 336–346.
4. S.R. Naqvi, Y. Uemura, S. Yusup, 2014. Catalytic pyrolysis of paddy husk in a drop type pyrolyzer for bio-
oil production: the role of temperature and catalyst. Journal of Analytical and Applied Pyrolysis 106, 57-62.
5. S. Mekhilef, R. Saidur, A. Safari, W. E. S. B. Mustaffa, 2011. Biomass energy in Malaysia: Current state
and prospects. Renewable and Sustainable Energy Reviews 15, 3360-3370.
6. C. Liu, H. Wang, A.M. Karim, J. Sun, Y. Wang, 2014. Catalytic fast pyrolysis of lignocellulosic biomass.
Chemistry Society Reviews 24, 7594-7623.
7. S. Czernik, A.V. Bridgwater, 2004. Overview of Applications of biomass fast pyrolysis. Energy Fuels 18(2),
590-598.
8. D. Mohan, C.U. Pittman, P.H. Steele, 2006. Pyrolysis of wood/biomass for bio-oil: A critical review, Energy
Fuels 20(3), 848-889.
9. G.W. Huber, S. Iborra, A. Corma, 2006. Synthesis of transportation fuels from biomass: Chemistry,
catalysts and Engineering", Chemical Reviews106, 4044-4098.
10. T. Dickerson, J. Soria, 2013. Catalytic fast pyrolysis: A review", Energies 6, 514-538.
 APPENDIX A

FLOW CHART OF RESEARCH ACTIVITIES

Map out the literature understanding for catalytic pyrolysis

Determine the physical, chemical, and fuel characteristics of biomass

Enhancement and development prototype research apparatus

Converting biomass to potentially useful products using catalytic pyrolysis techniques

Investigate the influence of the various key process parameters (e.g. process
temperature, catalyst) on the product yield and quality

Determine the physical, chemical, and fuel characteristics of bio-energy products

Analysis of the collected data including publication

Preparation of a comprehensive annual report

 APPENDIX B

GANTT CHART OF RESEARCH ACTIVITIES

Activities (Months) 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36

Literature review

Determination of the physical, chemical,

●
and fuel characteristics of biomass

Development to enhance the prototype

●
research apparatus

Investigate the influence of the various

●
key process parameters on the product

Development of catalyst for pyrolysis

●
process

Development of process synthesis and

●
integration tools for biorefinery

Determine the physical, chemical, and

●
fuel characteristics of products

Analysis of the collected data including

● ● ●
publications

Report submission ● ● ●

● Milestone