Workshop on Measurements and Standards for Biofuels:
Enabling a Transition from Petroleum as a Vehicular Energy Source

Rio de Janeiro, Brazil

September 14-15, 2006

Background:

Following up on the agreements reached at the First US-Brazil Commercial Dialogue between Secretary Gutierrez and Minister Furlan held in Brazil on June 6, 2006, and the US-Brazil Ministerial Joint Commission Meeting held in Washington DC on July 21, 2006, the two sides agreed to explore cooperation in Measurements and Standards for Biofuels.

As a first step, a workshop on “Measurements and Standards for Biofuels: Enabling a Transition from Petroleum as a Vehicular Energy Source”, organized by NIST and INMETRO (National Institute of Metrology, Standardization and Industrial Quality of Brazil), was held on September 14-15, 2006, in Rio de Janeiro. The participants represented government and private sector organizations from Brazil and the US. 

Goal of Workshop:

The goal of this workshop was to explore mutual interests in collaboration on measurement and documentary standards, along with the underpinning metrology to support the movement of biofuels as international commodities. This goal is clearly aligned with the missions of both National Metrology Institutes (NMI).  NIST is the NMI for the United States and its mission is to promote U.S. innovation and industrial competitiveness by advancing measurement science, standards, and technology in ways that enhance economic security and improve our quality of life.  INMETRO is the NMI for Brazil, whose mission is to improve the quality of life of the ordinary citizen as well as to improve the competitiveness of the economy through metrology and quality.

Setting the Tone - Welcome and Context:

The meeting was hosted by INMETRO’s President Prof. Joao Jornada, and Prof. Humberto Siqueira Brandi, Director for Scientific and Industrial Metrology.  Both welcomed the US delegation to Brazil. Prof. Jornada provided context for workshop from the Brazilian perspective stating that Brazil has a 25- year experience with sugarcane-based ethanol and has developed the technology for flex fuel cars that can run on gasoline, ethanol, or any combination of the two.  This Brazilian-developed technology enables Brazil to transition completely to renewable transportation energy. Flex fuel cars were introduced in Brazil in 2003 and they currently represent 70% of new passenger car sales. He stressed that any standards developed for ethanol as a commodity should be “universal” or international, and proposed that the US and Brazil work on reference materials and standards collaboratively to help ensure that regulations and normative standards are homogenous throughout the world. 

Dr. Hratch Semerjian, Chief Scientist of NIST, led the delegation and thanked Brazil and INMETRO for their hospitability. He acknowledged and commended Brazil for its long-term success in the utilization of sugarcane-based ethanol as fuel. He spoke briefly of US Advanced Energy Initiative (AEI) introduced by the US Administration in Feb 2006 that is aimed at the reduction of US dependence on fossil fuels, by increasing investment in the development of alternative energy sources. The lead agencies of the AEI are the US Departments of Energy and Agriculture. Over a period of five years, it proposes an additional investment of $10B in R&D that relates to the development of cleaner and more reliable alternate energy sources, including an increase in R&D funding to “change the way we fuel our vehicles”. In the transportation area three goals were identified: develop advanced battery technologies; foster the technologies to make cellulosic ethanol; enable large number of hydrogen fuel cells by 2020. Dr. Semerjian mentioned that the energy challenges in the US impact areas of security, economic growth, as well as climate change. As the US develops new strategies for the development of alternate fuels it is clear that analytical methods that fall into the category of systems biology, and imaging technologies including computational modeling and data infrastructure will be critical components of the necessary tool box for science-based decision making. http://www.whitehouse.gov/stateoftheunion/2006/energy/energy_booklet.pdf

Dr. Semerjian closed by mentioning President Bush’s US American Competitiveness Initiative (ACI) which doubles investment over 10 years in NIST, the National Science Foundation in the US, and the US Department of Energy.  The ACI commits federal investment in cutting edge research, and in the tools of science. http://www.whitehouse.gov/stateoftheunion/2006/aci/aci06-booklet.pdf

OPENING SESSION:

Presentation 1: Prof. Joao Jornada, President, INMETRO
"INMETRO’s Strategies for Biofuels"

Prof. Joao Jornada opened the technical session with a review of INMETRO’s capabilities and responsibilities.  INMETRO is a regulatory agency, responsible for scientific and industrial metrology, legal metrology, assessment, national accreditation and Brazil’s body for technical collaboration. It is also the TBT/WTO enquiry point. Its strategies as Brazil’s NMI include building a strong science and technology base, producing and certifying relevant CRMs, provide a network for its industry that include secondary laboratory producers, disseminating knowledge, and establishing strong international partnerships and mutual recognition, to support Brazilian Government policies. INMETRO values partnerships with academia and industry within Brazil as well as international partnerships. In biofuels, there are three research areas which are interconnected: machines and equipment (corrosion and materials studies); energetic or calorific content of ethanol (as a commodity); and environmental and human impact. The linkages among these are illustrated in the diagram. 

INMETRO has convened two relevant panels: alcohol fuel (Oct 2003), Biodiesel (Nov 2005), and has planned a panel on S&T strategies for Biofuels (Oct 2006). These panels engaged the S&T community and the government, and identified metrological needs for the continued development of biofuels as a commodity and agreed on the need for standardization. INMETRO has recently released an Ethanol fuel Certified Reference Material, the first (and only) ethanol fuel standard in the world. Parameters certified include: water content, acidity, pH, conductivity, density, copper content, and alcohol content. INMETRO has both developed new methods and used existing methods such as ASTM D8423 and ABNT (Brazilian Association for Technical Standards Organization) NBR 10891. INMETRO researchers have also been studying the effects of biodiesel fuels on engine parts. Under controlled temperatures and for periods up to 6000 h, engine parts are exposed the biodiesel fuel to detect surface changes in the material. In addition a Motors and Fuels Laboratory has been designed to evaluate emissions, power output, energy consumption and wear of biodiesel engines over time.

SESSION ONE: BARRIER TO TRANSITION TO BIOFUELS

Presentation 2: Dr. Willie E. May, Director, Chemical Science and Technology Laboratory, NIST
"NIST Role and Capabilities for Supporting Expanded Use of Biofuels"  

Dr. Willie May of NIST presented a review of the NIST role and capabilities for supporting the expanded use of biofuels in the US. The political context is provided in both the Advanced Energy Initiative and the American Competitiveness Initiative.  The desire to move from a fossil-fuel based economy has environmental, social and security related implications. Dr. May stressed that the measurements and standards required for the development of biofuels, and even more critically with its distribution and trade, is consistent with the mission of NIST as well as its congressionally mandated weights and measures responsibility. NIST has long provided the measurement infrastructure required for the production, distribution and commerce regarding fossil fuel energy in the US. For example, the metering of gasoline at the pump is directly traceable to primary flow and volume standards at NIST. NIST is utilizing its experience and expertise in the fossil fuels economy to address challenges arising from the hydrogen economy and can extend this to biofuels.

NIST research and measurement service activities serve a broad customer base from manufacturing to pharmaceuticals and from microelectronics to construction. To serve this broad customer base, NIST has a premier program in measurement science and standards, and its laboratories are organized along discipline lines, similar to a university. Its research laboratories are located in Gaithersburg, MD (580 acre site with 29 laboratory buildings) and Boulder, CO (205 acre site with 9 laboratory buildings).  NIST Gaithersburg Campus has some unique research facilities including Advanced Measurement Laboratory with stringent control of temperature, vibration, humidity and cleanliness, along with state-of-the-art nanofabrication capabilities. In addition, the NIST Center for Neutron Research is a user facility and offers advanced thermal and cold neutron measurement capabilities and is the only US facility for the studies of biological dynamics, in which both temporal and spatial information are obtained. NIST partnerships with industry, academia and other government agencies have been an integral part of the NIST culture since its founding in 1901.

One of the formal ways NIST conducts collaborative research is through three joint institutes mentioned here because of their current or expanded programs in the area of bioscience and bio-metrology.

1.     Center for Advanced Research in Biotechnology: with the University of Maryland (structural biology with plans for expansion into plant and insect transformation).

2.     JILA:  with the University of Colorado (plans to expand its program in bioscience).

3.     Hollings Marine Laboratory: with National Oceanic and Atmospheric Administration, South Carolina Department of Natural Resources, University of Charleston, the Medical University of South Carolina (studies linkages between environmental conditions and marine and human health).

Presentation 3: Dr. Curtis P. Williams, Director, Georgia Department of Agriculture, State Oil Laboratory
"ASTM International Standards for Biofuels "

Dr. Williams represented ASTM Committee D02 on Petroleum Products and Lubricants, and presented an overview of ASTM, as well as details concerning his committee’s activities. He began by stating that ASTM International is an independent, not-for-profit organization that provides a global forum for the development of voluntary, consensus standards, but does not provide certification or accreditation.

More than 60 nations utilize ASTM standards in their regulations, and he remarked that there are active participants from Brazil on many ASTM committees. He described the ASTM standardization concept as a decentralized public and private partnership that provides an open forum for technical discussions in the standards arena, thus enabling the private sector to more easily comply with regulations. The technical committees determine the scope of standards development in their particular area of responsibility, and standards under development are available for public review on the ASTM webpage. In general, ASTM’s standards are voluntary, unless they are cited in a regulation or called out in a contract. Standards are reviewed at least every five years, and revisions reflect changes in technology. Standards development is the chief task of ASTM’s committees and subcommittees, and members have the opportunity to influence a standard by both participation and voting.

Technical Committee (TC) D02 includes over 1,500 members from 52 countries and develops test methods and specifications for liquid transportation fuels (typically petroleum based) but more recently has expanded to include ethanol blends and biodiesel fuels. TC D02 has many technical subcommittees: 12 product subcommittees (specifications and performance testing); 14 properties subcommittees (test methods and measurements); and 5 coordinating subcommittees. Ethanol standards are included in the scope of the subcommittee on Gasoline and Oxygenated fuels and has 260 members from more than 20 countries with active participation from PetroBras.  Biodiesel specifications and standards are included in scope of the subcommittee on diesel fuel. This subcommittee has 290 members from 17 countries, with active participation from PetroBras. The subcommittee on Biomass Conversion includes test methods for converting cellulose feedstock to fuels using enzymes, yeasts and pyrolysis. For example, the test method for Performance Evaluation of Fuel and Ethanol Manufacturing Facilities is applicable to starch and sugar, and their combination, in both batch and continuous feed manufacturing.

Presentation 4: Dr. Jose Felix Silva Junior, Copersucar
"Market Specification and Methods for Ethanol Analysis"

Dr. Silva is a technical expert from Copersucar, a Brazilian industrial producer of ethanol for about thirty years. His talk was entitled “Market Specification and Methods for Ethanol Analysis. He began by putting the ethanol market in Brazil in perspective. He noted that around 1982 the first ethanol-run cars were produced in Brazil, and along with it, a steady increase in the production of sugarcane and sugar. A similar increase is noted along with the introduction of Flex-Fuel cars in 2003. Copersucar anticipates both the domestic demand for ethanol as a fuel, as well as its export to double in the next five years. He emphasized the complexity of implementating a quality system, and the necessity of providing an economically viable product to the end-user. Analytical measurements must be made in order to ensure product reliabililty between producer and supplier; however, specifications and methods are variable and confusing, there are no uncertainty statements, units are not uniform, and repeatability and reproducibilty are unknown. Quality assurance is required from the sugar factory, to factory tanks, to port tanks, ships in the port of origin and in the ports of destination.

Domestically, Brazilian standards for ethanol are used, and proficiency testing of sugar factory laboratories is coordinated by Copersucar.  Within this program, a consensus reference standard for ethanol has been produced, along with a certificate of analysis. However once the ethanol leaves the factory tanks, other laboratories are involved in testing and the quality assurance process begins to break down. The lack of harmonization of specifications and standards throughout the world hampers the introduction of ethanol as a global commodity. For ethanol to be a viable commodity, science-based decision points are critical. This will require the development of relevant, internationally-accepted specifications as well as simple, reliable and internationally-accepted methods and standards.

SESSION TWO: CURRENT EXPERIENCES WITH BIOFUELS

Presentation 5: Dr. Robert Goldberg, Senior Research Scientist, Biochemical Science Division, NIST
"Thermodynamic Data and Measurements for Biofuels"

Dr. Goldberg’s talk was entitled “Thermodynamic Data and Measurements for Biofuels. He began by defining biomass and how it might be used for energy production. According to the US Dept. of Energy, biomass is a fully renewable resource, that is its use for biomass-derived fuels, power, chemicals, materials or other products essentially generates no net green house gas. Its production and use is generally domestic, so it has substantial environmental, economic, and security benefits. Biomass is making key contributions today, and has surpassed hydro-electric power as the largest source of renewable energy in the US. Biomass-derived ethanol and biodiesel are of growing importance providing the only renewable alternative liquid fuel for transportation. Biofuels represent only one part of biomanufacturing from a glucose feedstock. Other valuable commodities range from indigo to aspartame, and from nylon to liquid crystal polymers -  being produced from glucose through the chorismate pathway using recombinant bacteria. However, in order to design manufacturing processes, essential scientific data are required on structural and molecular biology, thermodynamics, and kinetics.

NIST has produced a series of review articles that cover the scientific literature on the thermodyamics of enzyme-catalyzed reactions to include: oxidoreducatases, transferases, isomerases, lyases, hydrolases, and ligases. This has been published in the Journal of Physical and Chemical Reference Data, but is also avalaible on the Web at: http://xpdb.nist.gov/enzyme_thermodynamics.

Dr. Goldberg closed with suggestions of how NIST expertise might be applied to biofuel research: molecular and structural biology for catalyst research; analytical chemistry for needed SRMs; thermodynamic and kinetic reference data; data and models to understand mechanisms; calorimetry and calorimetric standards for sale of biofuels based on energy content instead of volume.

Presentations 6 and 7: Two presentations were given by Tecbio.
"Lipofuels: Biodiesel and Biokerosene"
"Technical Aspects of Biodiesel Production"

The first talk was given by Expedito Parente, President of Tecbio, and entitled “Lipofuels: biodiesel and biokerosene”. He opened with some strategic considerations regarding petroleum; that is, it is a finite energy resource while the energy demand world-wide is increasing. One solution to this supply/demand issue is an increased production of fuels from biomass. There are several lessons to be learned from the Brazilian bioethanol program including: the development of industrial processes; the increase in agricultural productivity; and the exploitation of by-products. Lipofuels are those biofuels obtained from vegetable and animal oils as methyl or ethyl esthers. Lipofuels offer a significant advantage as a bio-based fuel since there is potential to provide food for human consumption (protein portion), as well as energy to power machines (lipid portion).  A biokerosene that has been patented in Brazil is made from babassu oil (nuts have 62% oil), and was first used as an aviation fuel. Its desirable properties include lubricity and detergency, thus improving engine performance. In 2001, TECBIO was founded and is considered the cornerstone of the biodiesel industry in Brazil.

Dr. Expedito Jose de Sa Parente, Jr, Technical Director of Tecbio, gave a second presentation entitled “Technical Aspects of Biodiesel Production. He described biodiesel as a renewable fuel of fatty acid methyl (or ethyl) esters, produced by a transesterification reaction between vegetable oil or animal fats and methanol (or ethanol). Biodiesel production has become a priority in Brazil.  In December 2004, ANP 42/04 was released that articulated biodiesel specifications and authorization of its use. Federal laws also encourage the development and use of biodiesel including tax incentives.

In the commercialization of biodiesel fuels, a variety of raw materials have been evaluated for such features as yield per hectare and oil content. Other considerations include: cost and price, feasibility of use, nature of impurities and composition of fatty acid (number of carbons, number of double bonds, presence of chemical groups, etc.). The technical aspects of the industrial process currently used include: raw materials pre-treatment and catalyst preparation, transesterification, separations, purification and byproduct recovery. Operational aspects include: process control, maintenance, dynamics and flexibility of the process. Dr Parente also described the lack of uniformity and international-acceptance of standards and specifications. These issues are further complicated by the desire for multi-feedstock biodiesel production.

Presentation 8: Prof. Paulo Suarez, Laboratory of Materials and Fuels, Institute of Chemistry, University of Brasilia.
"Alternative Fuels from the Thermo-catalytic Cracking of Triglycerides"

Prof. Suarez described the use of thermocatalytic cracking of triglycerides for the production of alternative fuels. In the 1920’s to 1940’s, high temperature cracking was used in China to make motor oil from tung oil. Professor Suarez studied other oils including soy, palm and castor, along with tallow beef and soap-stock as potential feedstocks for fuel production using thermal cracking. Based on cetane number using ASTM method D613, he demonstrated that all but one of the raw materials studied met the Brazilian specification for diesel fuel. Castor oil was shown to be the least effective fuel, and did not meet specification, presumably due to its chemical structure. Further studies demonstrated that the cracking process could be improved using metal oxide catalysts containing aluminum. The thermocatalytic process developed by Prof. Suarez’s research team has been patented jointly by UnB and industrial partners, and pilot plants have been constructed in Brazil, such as the one seen in the photo (Embrapa is the Brazilian Agricultural Research Corporation). The UnB research team also works with PetroBras, and its patented process uses biomass (soybean) to make hydrogen. Prof. Suarez concluded by stating that it is possible to produce “diesel-like” fuels from triglycerides with properties that match the petro-diesel specification, and that thermocatalytic cracking enhances the high temperature cracking process. However, he warned, further studies are needed to understand how oxygenated compounds impact engine wear.

SESSION THREE:

Presentation 9: Mr. Luciano Almeida, Secretary of Industry and Commerce, Brazil

Luciano Almeida’s presentation provided a broad perspective on the ethanol market in Brazil. He opened with a video introduction showing the revitalization of the agricultural community as it moved to a sugar-based energy economy. His presentation began with the statement that in 1906 in the US, ethanol first became popular as a fuel, when it was mixed with gasoline to run the Model T Ford.  In 1975, during the international petrol crisis, Brazil began using ethanol as an additive to gasoline as a liquid transportation fuel. At the same time there was an incentive program for the development of vehicles that could run on 100% ethanol. Today, the shift is to a flexible fuel vehicle, which was introduced in 2003, with approximately 100,000 automobiles and light vehicles being sold per month by 2006. Brazil is one of the primary producers of sugar cane in the world, and it is an ideal feedstock for ethanol production. The sugar cane industry produces ethanol for fuel, food, and health products, as well as sugar for human consumption. Even the bagasse (pulp or dry refuse left after the juice has been extracted from sugar cane, grapes, or sugar beets) can be used for fuel (burning), cattle feed, or making paper. An interconnected industrial process allows for flexibility in product manufacturing that can be quickly altered based on consumer demand. In addition to the products and services currently provided by the sugar cane industry, research is being directed toward future domestic and global markets including carbon trading, biodiesel and bioplastics. Over the last 45 years, investments by the Brazilian government resulted in the improvement in agricultural processes to produce 65% more sugar cane (in tons) per acre, as well as increases in the overall production of sugar cane by 420%. Brazil is looking to approximately double its export of ethanol as a commodity to 4 billions liters of liquid fuel within the next 5 years, and has identified new areas of land mass for agricultural use (all outside the Amazon rain forest). Almeida stated that in 2005, an impressive 30% of Brazil’s the energy portfolio was from biomass. He then closed by introducing the concept of an “Ethanol Cluster” through the example of ALPA (Arranjo Produtivo Local do Piracicaba) or the Ethanol Cluster of the Piracicaba area.

The cluster seeks to integrate all aspects of the ethanol production chain to include relevant equipment manufacturers, R&D centers, and the ethanol producers. He noted that ALPA also provides products, services, and technology to interested entities both domestic and international. Some of these services include: economic feasibility studies and analysis of local environmental conditions; supply of genetically diverse, healthy sprouts; and technology to fight and control crop plague.  It also offers specialized machinery, “turn key” plants, and process design and consultation.

Presentation 10: from US EPA presented by proxy:

Contact information: Robert Larson, Associate Director, Transportation and Climate Division, US EPA.

The paper noted US Federal activity supporting the shift to renewable fuels in three ways: regulations, voluntary programs, support of research and emissions impact. The proposed renewable fuel regulation was signed September 7, 2006, and the final ruling is expected in early 2007. This regulation would specify the minimum amount of renewable fuels used in the US transportation sector, for example from 4.0 billion gallons/year in 2006 to 6.8 billion gallons/year by 2010. EPA will work to promote the use of E-85 and biodiesel through a voluntary partnership program that would involve automakers, oil refiners, fuels producers, fleet owners, states, etc. This effort is designed to maximize environmental benefits of biofuels, improve energy security, and create a voluntary complement to the regulations. Barriers to the expanded use of E-85 range from lack of public awareness and physical infrastructure, to lack of economic incentive, that is the relative cost of E-85 vs. gasoline. Biodiesel is derived from natural oils, and can be used with petroleum-based diesel fuel in existing engines. Biodiesel has reduced emission, and adds cetane and lubricity. However it is currently not cost-competitive with petroleum diesel, therefore EPA is focusing on “low blends” of biodiesel (B5-B20). The paper concluded that research and analysis is needed to determine emission impacts, life cycle emissions of various renewable fuels, economic impacts (on farmers, refiners, consumers), and energy security benefits.

DISCUSSIONS AND CONCLUSIONS:

Overarching Topic: US-Brazil cooperation on Biofuels standards.

In keeping with the missions of both organizations, it was agreed that NIST and INMETRO should establish a collaborative program on metrology and standards for biofuels.

Focus areas were identified to include: anhydrous ethanol, petroleum-ethanol blends, and biodiesel, others?

Types of Activities/Issues Recommended for Joint Effort:

Review of Specifications for Biofuels as a Commodity

• Small group(s) to be convened to address topic and report back next meeting; the relevance of various measurands/analytes/properties are a very important part of this discussion.

Materials Research, Data and Testing Technology (NIST/INMETRO)

• A small group of experts should be convened to identify relevant materials issues and present findings  at the  next meeting as a potential cooperative research target.

Reference Methods and CRMs (NIST/INMETRO)

• Development and critical evaluation of higher order methods and CRMs to underpin measurements against specifications (NMIs)
• Critical evaluation of field methods to be used to assess conformance with specifications.

Thermophysical Property Data (NIST/INMETRO)

Felix Silva of Copersucar summarized the industry view of the measurement issues.

• Standardize the units and the temperature used in all pertinent specifications.
• Work on the existing methods to see if they are applicable to both denatured and non-denatured ethanol.
• Try to adopt a single method for each desired quantity.  For example, ASTM has three methods for sulfur.
• Look for simple methods that have wide applicability.
• Have an understanding of the repeatability and accuracy of the various methods.
• Evaluate the specifications that are being used by various countries, e.g. in the US, Europe, Japan, etc.

Action Items:

• Form a smaller group to look at all the presentations from this workshop to see what CRMs are needed, and circulate the list to the entire group.
• Plan a second meeting with the US as host - around an existing meeting to minimize travel costs.
• Plan a Brazilian technology day at NIST – with a focus on biofuels.