IBP1845_12 LIGNOCELLULOSIC MATERIALS AS FEEDSTOCK FOR PETROCHEMICAL: ANALYSIS OF TECHNOLOGICAL PROGRESS ROUTES FOR GASIFICATION AND PYROLYSIS Juliana

C. Cruz, Estevo Freire2, Jos Vitor Bomtempo3

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
Lignocellulosic materials, a biomass renewable feedstock, can be considered a potential alternative for fossil raw materials in the petrochemical industry. Biomass gasification and pyrolysis are technologies under development capable of transforming complex molecules into fuels and chemicals. The number of scientific articles about those technologies is an indicator that they are not well established. This work evaluates and analyzes technological progress for gasification and pyrolysis though scientific articles published by universities, research centers and companies. The objective is to find out institutions that deal with these technologies economically feasible and that one which will be in the market in the near future. This was done by searching scientific articles published between 1979 and 2011 from Web of ScienceSM database and by stating the type of publishing institution. Results showed universities responsible for 62% of biomass gasification and 63% for biomass pyrolysis publications. The analysis of different institutions type cooperation through time indicates that universities and research centers cooperation increased specially compared to research centers/companies and universities/companies cooperation considering both pyrolysis and gasification. Academy and company higher interaction would probably contribute to a shorter term breakthrough of those technologies. This work also evidences that Europe is responsible for most cooperation between different types of institutions.

1. Introduction
Environmental and economic circumstances have resulted in changes on chemical processes concept regarding fossil resources. Lignocellulosic feedstock has been rated as an alternative for oil as a potential substitute for some branches in petrochemical industry. Many scientific studies are focused on the possibility to convert renewable raw materials into transportation fuel, power and chemicals. In this context, several technologies based on thermochemical conversion are developed to enable an alternative for oil in attempt to reduce its dependence. However, the available literature on the subject shows a wide variety of different systems, raw materials, biomass conversion technologies, which are mostly possible only in laboratory scale. These facts indicate that these technologies in innovation process are currently in a fluid phase. Researches continue to seek an environmentally friendly source as well as competitive with the current products on the market. In order to understand the process dynamics and estimate the line to feasible technologies, which is important for researchers and investors, this paper aims to explore the evolution of scientific and technological growth though scientific articles production. The objective is use bibliometric techniques to identify the structure of current research on biomass conversion though gasification and pyrolysis.

______________________________ Master, Bioprocess Engineer Universidade Federal do Rio de Janeiro 2 Ph.D., Chemical Engineer Universidade Federal do Rio de Janeiro 3 Ph.D., Chemical Engineer Universidade Federal do Rio de Janeiro

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2. Biomass Thermochemical Conversion

According to the National Renewable Energy Laboratory, biomass is any plant-derived organic matter, such as herbaceous and woody energy crops, agricultural food and feed crops, agricultural crop wastes and residues, wood wastes and residues, aquatic plants, and other waste materials including some municipal wastes. Plants are, thus, classified as biomass and as lignocellulosic materials, being lignin, hemicellulose and cellulose main components. The heterogeneous and chemically complex renewable resource can be chemically transformed into different products depending on the process. Some of those transformations are economically possible in bench scale, some of them are only concepts, and few are viable in pilot and industrial scale (Venderbosch and Prins, 2011). Techniques for biomass thermochemical conversion rely on old techniques used for different sources. While gasification chemical reactions has an external agent know as gasification medium, pyrolysis process is a process with no oxidizing agent or a limited supply in order to EVITAR gasification to an appreciable extent (Basu, 2010). The two different thermochemical techniques promote biomass conversion into primary products and thereafter further converted by varying degrees to final products (Balat et al.).

2.1 Biomass Gasification The process of biomass gasification involves several elementary reactions. The reaction of solid or liquid materials, such as biomass, coal, oil with gases (air, oxygen and/or steam) results in a gas mixture, known as syngas. The gas produced contains CO, CO2, H2O, H2, N2, CH4, and other gaseous hydrocarbons in different proportions depending on the process conditions and biomass used (Bain and Broen, 2011; Huber et al., 2006). The process begins with a thermal decomposition of lignocellulosic material, then a partial oxidation of the fuel realized by air, steam or oxygen (Bain and Broen, 2011). Although gasification processes for coal as feedstock may achieve successful production, biomass gasification has technical problems particularly concerning to biomass heterogeneity in terms of molecules and water content. This problem results in a difficult comminution, decreasing the heat transfer process to the particles (Basu, 2010). This and others issues make research important for the technology improvement.

2.2 Pyrolysis Pyrolysis process involves a breakdown of large complex molecules into several smaller ones. Different process conditions produce different proportions of liquid, solid and gas as primary products. The types of pyrolysis process are: torrefaction, or mild pyrolysis, slow pyrolysis, and fast pyrolysis. Differences are mainly temperature and residence time. The main issue in pyrolysis process is the composition of the bio-oil, the primary product. The variability of the molecules on the biomass feedstock results in a multicomponent mixture comprised of different size molecules derived from cellulose, hemicellulose ad lignin processing. The consequence of a complex mixture of compounds is a bio-oil with physical propriety significantly different from that of petroleum-derived oils. Viscosity, corrosiveness, combustion behavior, and volatility are some of the proprieties that make bio-oil difficult to handle and limit its application (Czernik and Bridgwater, 2004).

3. Innovation indicators
Research activity, for long time, had been performed and developed exclusively based on empiricism. Experience was the only guide to search for questions and impressions at the time and it also used for driving the economy and industry. After this initial point technology has increasingly become dependent on science. Also, the progress of equipment and techniques operated machines allowed greater reproducibility in the field of research. This mutual relationship of human development can be known as the symbiosis of science and technology (Macedo and Barbosa, 2000). Nowadays it is possible use scientific research over the years as a means for measuring innovation. Since technological measure is important in economic research (Sahal, 1985) knowing trends related to a particular technology may be crucial on decision making. Thus, the use of scientific papers and its guidance along the years is a frequently used indicator to indicate possible technological developments. In the present study it was verified the trends of technological transformation of lignocellulosic biomass by pyrolysis and gasification processes. The following topics explain the concepts of these search parameters. 2

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4. Methods
The use of innovation indicators aims identification of technology progress. Bibliometric analysis is used to measure and understand technological advances, providing indicators of research, development, and innovation. Therefore, it was selected scientific articles published from 1979 to 2011 on biomass conversion by pyrolysis and gasification methods, separately. In order to select the publications, it was used the database Web of ScienceSM, part of Institute for Scientific Information, ISI, Web of KnowledgeSM. This database was chosen because it compares the actual web data base WoS with cover journals with higher impact factors (Lpez-Illescasa et al., 2008). Thompsons of Science website elucidates that the Science Citation Index Expanded over 6,650 of the world's leading scientific and technical journals across 150 disciplines (Science Citation Index Expanded, 2012). Using the tool of Advanced Search some tests were done to define the key words for publications selection. In order to select only publications which had the pyrolysis and gasification as the main subject it was used the field title. After testing the key words, gasification OR syngas AND biomass OR lignocellulosic were defined to sample the publications on gasification of biomass and pyrolysis OR bio-oil OR bio-oil OR pyrolysis oil AND biomass OR lignocellulosic were used to select publications on pyrolysis of biomass. It was considered also only articles and reviews, selected on the websites option restrict result. According to Bar-Ilan (2008) publishing in languages other than English has low visibility. To eliminate articles and reviews of limited reading those not published in scientific journals found in Journal Citation Reports (JCR), also produced by ISI Web of KnowledgeSM, and publication otherwise in English were discarded. The publications considered in this study were from 1979 to 2011. The total of scientific articles and reviews were 772 for gasification and 635 for pyrolysis.

5. Results and Discussions

Results obtained from the research on Web of ScienceSM database related to publication of scientific paper about gasification and pyrolysis of biomass are presented below. Table 1 shows the number of publications from universities, research centre and companies without other institution type cooperation. Universities account for over 60% of all scientific publications related to this work during the period between 1979 and 2011, followed by research centres (15% for gasification and 16% for pyrolysis) and companies (3% for gasification and 1% for pyrolysis). It should be expected universities with the highest percentage as scientific papers are the main publication form. Companies represent the lowest participation on this type of research which is also predictable as companies utilize patents to protect the intellectual work at the same time the study becomes public. Table 1: Percentage distribution of institution type publishing about biomass gasification and pyrolysis. Institution type University Research Centre Company Biomass gasification (%) 62 15 3 Biomass pyrolysis (%) 63 16 1

Results also show cooperation between universities, research centers, and companies is relevant for both technologies analyzed on this work. Figure 1 and Figure 2 represents institution type cooperation evolution over time. The analysis was done considering all publications obtained from 1979 to 2011. However not all years are observed on the figures since those years with zero cooperation was not plotted. This facilitates visualization and does not harm the analysis since no model is tested for the cooperation evolution. The total number of publication cooperation is 153 for gasification and 120 for pyrolysis.

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Figure 1. Cooperation between different types of institution that published scientific articles on biomass gasification (a) and biomass pyrolysis (b) from 1979 to 2011 ( ) University and research centre; ( ) university and company; ( ) 2011. niversity research centre and company; ( ) university, research centre and company. Graphics show increasing collaboration of different type of institution related to gasification and pyrolysis of biomass, especially for universities and research centres. In the other hand, universities interaction with companies is very low compared with the first one. As mentioned before, companies have a tendency to publish technological information thought patents, so their actual participation for developing of those technologies may not be well , represented here. However, cooperation between academy with industrial producers is probably well represented in this work. It is clear that this relation with companies, which are candid candidates to produce long term breaking through technologies, could be more significant. The cooperation between them would able companies to overcome possible knowledge deficit as universities would focus work on industrial interest. The combination of researc center and research companies is also important for the same reason. It is important to notice that the collaboration results are a reflection of the increasing in scientific publications about the technologies. The authors intent is mainly to compare the differ differences between different cooperation groups in the same time range. Figure 2 shows regions/countries where collaboration with other type of institution is more evident. Region/country considered is of the first author and this criterion was chosen as an option for publications having authors with different countries filiations.

(a)

(b)

Figure 2. Cooperation between different types of institution that published scientific articles on biomass gasification (a) and biomass pyrolysis (b) from 1979 to 2011 related with publication country. Vertical axis is in terms of percentage of total number of publications: 153 for (a) and 120 for (b). ( ) University and research centre; ( ) university and company; ( ) research centre and company. Europe is responsible for most of publications in collaboration for both thermochemical technologies. For ble pyrolysis universities and research center collaboration is similar to universities and companies number of publications results. Cooperation between university and companies is apparently similar to university and research center ity collaboration for Japanese publications on biomass gasification and China also seems to have both groups publications number comparable. 4

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6. Conclusions
Converting technologies from renewable source is not yet feasible. However research is done aiming improvements in the process to achieve competitive products to market. This work presented institution types collaboration and their countries filiations as an aspects in bibliometric analysis to prospect further possibilities on gasification and pyrolysis processes of biomass conversion. Conclusions resting on the analysis are: i. Universities contribute for most of scientific publication on gasification and pyrolysis of biomass with more than 60% in each studied technology. Research centers and companies appears with an average of 15% for research centers and 2% for companies. These are number of publications with no cooperation from other institution type. Cooperation involving universities and research centers are significant. They represent 11% of the total in biomass gasification scientific publication 13% of the total in pyrolysis. Number of scientific publications done by companies over the years show an increase of enterprises interest on converting renewable sources. European publications on biomass gasification and pyrolysis technologies have collaborations between institutions of different nature more than the other areas showed on this work.

ii.

iii.

7. Acknowledgements
The authors would like to thank the Brazilian Institute of Oil, Gas and Biofuels (Instituto Brasileiro de Petrleo, Gs e Biocombustveis - IBP) for financial support.

8. References
BAIN, R. L., BROEN, K. Gasification. In: Thermochemical processing of biomass: conversion into fuels, chemicals, and power p. 47-77, John Wiley Publisher, 2011. BALAT, M., BALAT, M., KIRTAY E., BALAT, H. Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1: pyrolysis systems. Energy Conversion and Management, v. 50, p. 3147-3157, 2009. BAR-ILAN, J. Informetrics at the beginning of the 21st centuryA review. Journal of Informetrics, v. 2, p. 1-52, 2008. BASU, P. Biomass Gasification and Pyrolysis: Practical Design and Theory. Academic Press Publisher, 2010. CZERNIK, S., BRIDGWATER, A. V. Overview of applications of biomass fast pyrolysis oil. Energy and Fuels, v. 18, p. 590-598, 2004 HUBER, G., IBORRA, S., CORMA, A. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering, Chemical Reviews, v. 106, p. 4044-4098, 2006. LPEZ-ILLESCASA, MOYA-ANEGN, F., MOED, H. F. Coverage and citation impact of oncological journals in the Web of Science and Scopus. Journal of Informetrics, v. 2, p. 304-316, 2008. MACEDO, M. F. G., BARBOSA, A. L. F. Patentes, pesquisa & desenvolvimento: um manual de propriedade intelectual, Fiocruz Publisher, 2000. NATIONAL RENEWABLE ENERGY LABORATORY, Glossary of Biomass Terms, available on http://www.nrel.gov/biomass/glossary.html. Accessed April 2012. SAHAL, D. Foundations of Technometrics. Technogical Forecasting and Social Change, v. 27, p. l37, 1985.

Science Citation Index Expanded, available on /thomsonreuters.com/products_services/science/ science_products/a-z/science_citation_index_expanded/#tab2, Accessed March 2012.
VENDERBOSCH, R., PRINS, W. Fast pyrolysis. In: Thermochemical processing of biomass: conversion into fuels, chemicals and power, p. 124-156, John Wiley Publisher, 2011.