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Development of bio-oil dewatering and fractionation processes and testing of upgraded bio-oil as engine fuel and feedstock for the production of lubricants

Periodic Report Summary 1 - GREEN-OIL (Development of bio-oil dewatering and fractionation processes and testing of upgraded bio-oil as engine fuel and feedstock for the production of lubricants)

Project Context and Objectives:
The consortium of European SMEs behind the GREEN OIL project wished to address a major market opportunity through the development of new technology to upgrade bio-oil for utilization in transportation (engine fuels) and for the production of lubricants.
GREEN OIL deals with a global problem for the bio-oil producing industry, namely the need for efficient and cheaper processes for upgrading bio-oil to enable production and sale of bio-fuels without public subsidies on the market.
OFT, an SME in the GREEN-OIL consortium, holds a promising innovative process, based on microwave enhanced catalytic depolymerisation for the production of 2nd generation bio-fuels from feedstock materials like straw or organic waste. The main fuel product is bio-oil, which is not bio-diesel, but rather bio-crude oil comparable to pyrolysis oil in some parameters, but with superior characteristics, e.g. with regard to heat value, yield and fewer heavy compounds in the oil. Currently, the OFT process generates bio-oil with high water content (28-33%) in the form of a very stable emulsion. The only immediate fuel application of this product is to substitute coal in power plants. The sales price of the product is correspondingly low, thus rendering the current OFT technology unfeasible for commercialization without public subsidies.
The development of a dewatering process based on innovative ceramic membranes technology should reduce the water content below 2% and enable bio-oil utilization for heat and power generation in industrial plants. Moreover, novel bio-oil fractionation and conversion process schemes should expand bio-oil market opportunities into engine fuel for transportation usage. Furthermore, the heavy fractions may be used as feedstock for producing valuable goods, like bio-lubricants.
The GREEN OIL partnership is formed around a core of three SME partners:
• Organic Fuel Technology A/S (OFT), from Denmark, provides the original idea and coordinated the project. OFT has advanced in the development of an innovative and very promising process for bio-oil production, but the development of the dewatering and fractionation processes targeted in GREEN OIL is essential to the economic viability of the OFT bio-oil producing plants in the near future. With the integration of the novel upgrading processes into its process layout, in the near future OFT expects to be able to hold a leading position in the supply of small/medium sized bio-fuel producing units, first to the European and US markets, then expanding globally.
• Process Integration Limited (PIL), from UK, owns and provides leading-edge process integration technology that has been applied worldwide in the oil, gas, petrochemical and chemical industries. This way, PIL helps its clients to increase the technical and economic efficiency of industrial processes. Through the participation in GREEN OIL the company expected to gain access to a suite of novel process integration technologies focused on the market for renewable energy. Therefore, PIL expected to break into this attractive market as a software and consultancy services provider in design and operation.
• Zimmermann GmbH (ZIM), from Germany, has extensive experience in separation process engineering and industrial plant planning and construction throughout Europe and other parts of the world. In particular, ZIM has longstanding expertise in engineering and construction of compact units based on membrane technology for several applications. Through the leading position in the development of the dewatering process for OFT bio-oil during GREEN OIL, ZIM expected to widen its industrial expertise and business operations towards water-in-oil separation for approaching the highly attractive bio-fuels market.
The SME partners identified the following four RTD providers as highly qualified partners for the GREEN OIL project:
• DHI Water & Environment (DHI), from Denmark, responsible for developing the bio-oil dewatering process; the team at DHI has key qualifications in separation processes, namely water-oil separation based on membrane technology, as well as industrial unit operations.
• Centre of Process Integration at the University of Manchester (UNIMAN), responsible for developing the refining and fractionation technologies; UNIMAN is a pioneer Centre of Excellence in Process Integration with major contributions in reaction, separation, and energy recovery systems.
• Biomass Research Group, Department of Energy Technology, Aalborg University (AAU), responsible for testing the refined bio-oil in several types of engines; AAU has key competencies in combustion physics (including fluid mechanics, heat transfer, reacting multiphase flows, combustion modeling) and bio-oil (including production, optimization of process parameters on bio-oil yield and quality, and end-use of liquefaction bio-oil).
• Institute of Heavy Organic Synthesis “Blachownia” (ICSO), from Poland, in charge of modifying and testing the heavy fractions of OFT bio-oil as raw-material for obtaining lube formulations. ICSO has large experience in utilization of oils, like rapeseed oil, for the production of high-standard lubricant agents to be used e.g. by the food, forestry and paper industry.
The consortium has established the following scientific and technological goals for the project:

• Objective 1: To develop a dewatering process that reduces the bio-oil water content to below 2%. The development will focus on compact, cost- and energy-efficient technologies.
• Objective 2: To develop a cost-effective and compact fractionation and conversion process for the production of transportation fuels from the OFT bio-oil.
• Objective 3: To test the performance of refined OFT bio-oil in engines.
• Objective 4: To test the production of lubricating agents using the heavier fractions of the OFT bio-oil as raw-material.

Project Results:
Bio-oil samples produced at the OFT batch type test facility were characterized by ICSO, and found to be of inadequate quality for further processing, particularly due to water content above 50 %. A task force comprising all project partners was established to analyze the problems. The task force recommended a continuous mode operating pilot plant for production of appropriate bio-oil samples. OFT established such plant during a project suspension period, and produced several preliminary bio-oil samples during the plant start-up. Characterization of the samples at DHI proved the quality to be appropriate, in particular water content below 30 %. But problems in the pilot plant start-up introduced a delay of a magnitude forcing the consortium to request termination of the project half way through the planned period.
DHI performed a literature study on bio-oil from pyrolysis, revealing that water is often present in the form of emulsions and identifying methods for characterization and breaking of such emulsions. Characterization of the bio-oil samples verified presence of the expected emulsions. Demulsification was tested using several methods, comprising heating, pH adjustment, ethanol addition, salting out, microwaves and ultrasonic treatment. All methods showed some effect in the preliminary tests, but none were able to reduce to water content below the target of 2 %. Optimization was however not performed due to the lack of appropriate bio-oil samples.
The concept of a technology for dewatering the bio-oil to the target was developed by ZIM, DHI and OFT. The concept comprises three steps; 1) condensing the bio-oil vapor in a two-step condensation, 2) separate a bio-oil rich product by spontaneous phase separation of the condensate and 3) further dewatering the bio-oil product by an optimized method developed by DHI.
A membrane-based method for collecting the bio-oil residues from the combined water products was designed by ZIM, and ready to be tested in the OFT pilot plant by implementation of a standard ZIM test facility.
A thorough literature study on pyrolysis oil properties was performed by UNIMAN, proving OFT bio-oil properties determined in the ICSO testing to be in line with other pyrolysis oil products, i.e. not suitable for conventional fossil fuel fractionation processes. Further literature studies by UNIMAN and PIL identified a number of non-conventional applicable methods for fractionation of the bio-oil product, including hydrodeoxygenation, catalytic cracking and steam reforming. A route for hydrodeoxygenation was identified as the most promising, and the general frame for modeling such scheme was established. Modeling was however not initiated due to lack of bio-oil data.
AAU established a test bench for studying atomization of the refined OFT bio-oil as first step of using it as engine fuel. The test bench was not put in operation due to lack of bio-oil samples. But a model of ignition of the atomized bio-oil was derived, and tested using literature data and simplified systems. The model was verified on the simplified systems, and is ready for verification on bio-oil as soon as suitable data exists.

Potential Impact:
The current OFT process can produce bio-oil with high water content (28–33%) in the form of a very stable emulsion, whose possible application is to substitute coal in power plants. The sale price of this product is low, thus rendering the current OFT technology unfeasible for commercialization. The development of a proper dewatering process during GREEN OIL was expected to upgrade the bio-oil into a marketable product, specifically for use in small and medium size decentralised district heating/CHP (Combined Heat and Power) plants. Furthermore, and most importantly, the development of fractionation/refining processes during GREEN OIL was expected to be of key importance to OFT, given that this would take the company from marketing a process for the production of bio-oil to be used for heat and power generation – sold at the price of 0.35 €/L – to a process that generates higher added-value bio-oil for the transport sector selling at 0.8-0.9 €/L. If OFT plants can deliver a final product at the price of 0.85 €/L or even more then the company’s market potential will be very large. For instance, the business case for OFT customers (end-users) in European Nordic Countries is attractive, with the investment of €6M in an OFT commercial plant for conversion of straw into fuel being returned in less than 4 years; the business case will be much stronger in some cases, where e.g. the feedstock is received at 50% lower cost, which could be the case for corn and rice producers in the US. Furthermore, the heavier fractions from the bio-oil might be modified into valuable products, such as bio-lubricants – as investigated in GREEN OIL – creating an additional income to the OFT clients.
Hence, the successful achievement of the GREEN OIL objectives was expected to significantly strengthen the competitiveness and economy of the three SMEs in the consortium. OFT, as the initiator of the project and holder of the background technology, expected the highest benefit, with an estimated turnover for OFT in the 5-year period post-project in the order of €158M. In general, PIL expected benefit from the development of expertise and advanced technological tools that will allow the company to enter the renewable energy and biofuels market sectors, strengthening its position as a world leading technology provider for integrated chemical process and energy system design and operation. Moreover, PIL expected a specific gain from GREEN-OIL in the form of an added turnover in the 5-years post-project of €16M, through technology licensing, technical support, training and consultancy services for OFT plants. Finally, the supply of dewatering units for OFT plants was expected to generate an additional turnover for ZIM in the 5-years post-project in the order of €17M. The participation in GREEN OIL should also have expanded ZIM’s client base towards the biofuels market.
The GREEN OIL project addressed several objectives of European policies, particularly environmental and energy strategies. The 2nd generation bio-oil product envisaged would be very well suited for replacing fossil fuels, preventing, on an annual basis, the emission of almost 20 thousand tonnes of CO2 per full scale plant (producing 1000 L bio-oil per hour) in operation. The bio-oil can be produced and used locally, complying with good environmental practices and sustainable energy policies.
The project would promote EU objectives on biofuels and energy policy, as set in the Renewable Energy Directive to an incorporation rate of 10% of energy from renewable sources in transports by 2020.
The GREEN-OIL project has a number of additional positive effects with respect to sustainability and the protection of environment as well as key EU environmental legislation. First, the project was expected to contribute to recycling of fertilizing minerals, in particular phosphorus, to the fields. The residual solid material from the OFT process has a good potential use as fertilizer, as the mineral contents (nitrogen, potassium and phosphorus) are available without further treatment. Second, the GREEN OIL project would have contribute to the objectives of the EU Landfill Directive by promoting the recovery of energy from biomass residues and other organic wastes thus reducing the amount of waste materials channeled to landfills. Finally, GREEN OIL targeted the development of a process for recuperating the water fraction from the bio-oil without the use of chemicals. The dewatering process was expected to generate a clean water stream suitable for direct disposal or for utilization as process water without requiring further treatments.
Finally, EU’s external energy dependence is projected to increase from a level of 54% in 2008 to 65 % in 2030 in a business-as-usual scenario. Specifically, the reliance on imports of gas is expected to increase from 57% to 84% by 2030 and from 82% to 93% for crude oil. As such, increasing security of supply is an important goal and is being put forward by the European Council as a major motivation for taking steps toward an integrated climate and energy policy for Europe. Diversification of internal sources of supply and creating a different fuel mix is one important key to increasing security of supply. This project was expected to contribute significantly to this by releasing a large energy potential from biomass residues and organic waste. Finally, there was an expected direct employment effect of GREEN OIL as, for each plant in operation, 1-2 jobs would have been created for collecting and handling the biomass feedstock. These jobs would be located in rural areas, appealing to less-skilled workers and thus remain within the EU.

List of Websites:
http://green-oil.dk/