Periodic Report Summary - SUPER METHANOL (Reforming of crude glycerine in supercritical water to produce methanol for re-use in biodiesel plants) Project Context and Objectives: Grant agreement number: 212180 Project acronym: SUPER METHANOL Project name: 'Reforming of crude glycerine in supercritical water to produce methanol for re-use in biodiesel plants' Call: Call FP7-ENERGY-2007-1-RTD Activity code: ENERGY.2007.3.3.2: New uses for glycerine in biorefineries Keywords: glycerine, valorisation, biodiesel production, biofuels, methanol Duration: January 2008 to December 2011 (48 months) Total cost: EUR 2 997 449 Commission funding: EUR 2 093 414 Project website: 'http://www.supermethanol.eu' Project partners: 1. BTG Biomass Technology Group BV (The Netherlands) 2. Acciona Servicios Urbanos s.r.l. (Spain) 3. Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences (Russia) 4. Rijksuniversiteit Groningen (The Netherlands) 5. University of Maribor (Slovenia) 6. UHDE High Pressure Technologies (Germany) 7. Sparqle International B.V. (The Netherlands) Justification Biodiesel is produced by transesterification of vegetable oils with methanol. Glycerine is a major byproduct of this process. Due to the rapid increase in biodiesel production capacity in Europe the amount of (crude) glycerine has also increased rapidly. Since 2004 the amount of glycerine produced exceeds the actual consumption and the mismatch is increasing. By lack of viable market outlets for the extra glycerine supply its price has plummeted, and in late 2006 the price was not much higher than its value as fuel. With the flattening of the growth in biodiesel production, glycerine prices have increased significantly again. Nevertheless, leading stakeholders in the European Union (EU) biodiesel sector confirm that there is an urgent need to identify new (crude) glycerine applications. Project objectives The overall objective of the project was to produce methanol from crude glycerine and reuse the methanol in a biodiesel plant. This project aimed to improve the energy balance, the carbon performance, the sustainability and the overall economics of biodiesel production, as well as to reduce the sensitivity of biodiesel plant economics to volatile methanol and glycerine prices. The specific project objectives included: 1. Demonstration of the complete glycerine-to-methanol (GtM) process on laboratory and pilot plant scale. The specific targets were to achieve glycerine conversions higher than 90 % and to produce a syngas with hydrogen to carbon monoxide ratio (H2/CO) higher than 1, less than 20 vol. % carbon dioxide (CO2) and less than 10 vol. % (CH4+C2+). The overall target was a yield of 50 wt % methanol from glycerine, corresponding to more than 70 % energy efficiency. 2. Preparation of a detailed design for a full-scale methanol production facility integrated in a commercial biodiesel production plant and to establish production costs for the glycerine derived methanol. The target was to produce methanol at a price below EUR 250 per tonne. Background The work in this project expanded on expertise of the project partners on the reforming of biomass in supercritical water, among others in research projects financially supported by Dutch, European and Japanese research programmes. For example, in a previous EU funded project, 'Superhydrogen' a large number of biomass types were tested for their suitability as feedstock for the reforming process. Glycerine was identified as the ideal feedstock for this technology. In a subsequent study the project coordinator BTG explored the technical and economic potential to substitute fossil fuel based methanol with 'renewable' methanol, produced through supercritical reforming of crude glycerine. The Dutch study, completed in December 2006, showed the GtM process to be promising. Through GtM more than 50 % of the required methanol could be produced, while some combustible gases were returned to the biodiesel production plant. Water was required as a feed, while the ash in the crude glycerine was the main byproduct together with CO2. Research issues To demonstrate the complete GtM process the three core processes of this chain would first be analysed, developed and demonstrated at laboratory scale. The three core issues were: 1. the reforming of glycerine in supercritical water (RSW) 2. the conditioning of the raw synthesis gas and 3. the methanol synthesis process. The main research issues included, as an example, the following: 1. The raw synthesis gas composition depended on a number of parameters. A dedicated study on the reforming of crude glycerine would therefore be carried out, focussing on longer term effects (especially build up of contaminants) and recycling of tail water. 2. The raw synthesis gas was rich in CO2. Experiments, supported by thermodynamic calculations, would be carried out to reduce the CO2 concentration, within the RSW process itself or in subsequent conditioning steps. Experiments would be directed to reduce the hydrocarbons in the raw synthesis gas, possibly by use of catalysts. The second project phase was gone underway during the reporting period and the core processes were integrated into a small pilot plant, consisting of a near 1 litre/hr unit, fully integrated with syngas upgrading and methanol synthesis. An experimental programme was underway in this set-up to generate data for a blueprint for a 1 t/hr full-scale demonstration unit that would be integrated with an existing Acciona biodiesel plant. The detailed design would be based on the results from experiments and modelling and would include the integration with the biodiesel plant, legislation and safety aspects, etc. A cost estimate, for investment, operation and maintenance costs, and a calculation of the production costs for glycerine derived methanol would be part of the design. The construction of the demo unit was outside the scope of this project. Project Results: Work performed since the beginning of the project In the first work package (WP1) a laboratory scale test rig was constructed at BTG to study the reforming of glycerine. The rig was integrated with a methanol synthesis set-up. Together with RUG, a testing plan was finalised and sufficient data were generated to help understand the main mechanisms behind reforming in supercritical water. Such data were used for further developing the demo plant design. Acciona supplied batches of crude glycerine for testing. A test rig was constructed and initially tested at Maribor for the further reforming of methane. BIC produced and tested a range of steam reforming catalysts as well as catalysts for the upgrading of the RSW gas. Sparqle formulated possible concepts for reforming technical grade glycerol, for separating salt from this feedstock, and for the recycle of tail water and CO2. In addition, a set-up was built to investigate and optimise the in-situ removal of the ash in glycerine in a dedicated desalination unit by BTG, BIC and Maribor. In WP2 BIC developed, prepared, tested and delivered catalysts for methane steam reforming, methane dry reforming and reverse water gas shift reaction. Maribor, RUG and BTG constructed test rigs for experimental testing of commercial and BIC catalysts. Methanol synthesis experiments were carried out successfully. A patent application was planed to be filed in due course. In WP3 Maribor, BTG and RUG jointly developed process models. Different types of models were explored, ranging from models validating the RSW (Maribor), analysis and modelling of methanol synthesis (RUG) and an integral model of the complete GtM approach (BTG). RUG developed an adiabatic reactor model to describe methanol synthesis in a packed bed reactor. The model would be used to optimise reactor performance. WP4 covered pilot plant design, setting up and experimental testing. BTG constructed a laboratory scale pilot plant combined RSW and methanol synthesis reactor and reconstructed a larger pilot plant for this purpose. First initial mass and energy balances were made based on the use of RME glycerine. UHPT summarised the known and unknown design conditions for the overall GtM concept. For WP5 exploratory research was conducted. Acciona provided technical specs of its biodiesel plant in Caparroso, Navarra region, Spain. BTG and Acciona drafted a market study covering current glycerine uses, research and development (R&D) on glycerine valorisation and relevant market actors. The market study would be expanded and updated throughout the project. WP6 covered project management, dissemination and exploitation. By the end of the reporting period six meetings were held; two in 2008, 2009 and 2010 respectively. Acciona prepared a dissemination and awareness plan and an exploitation plan for use by the project consortium. Both documents would be updated throughout the project. Potential Impact: Expected results The main outputs of the project included: 1. Tested ab rigs for three unit operations, namely supercritical biomass reforming, raw synthesis gas upgrading and methanol synthesis 2. An integrated GtM pilot plant for 100 to 1000 g/hr glycerine input 3. Process models for the three unit operations and the integrated GtM chain validated with the results of pilot scale and real scale experiments 4. Knowledge of the economic viability of decentralised GtM production versus large scale centralised fossil fuel based methanol production 5. A detailed design of a full scale GtM plant to be installed at an existing biodiesel plant 6. Contribution to future bio-based economies 7. An international workshop on new applications and uses of glycerine. Expected impact Strategic impacts of the project included: 1. Development of an innovative technology for the conversion of glycerine into a raw material for renewable transport fuel production 2. Optimal integration of this innovative technology with current and future medium-scale biodiesel plants 3. Maximisation of the renewable energy output from biodiesel production plants Project management BTG Biomass Technology Group BV P.O. Box 835, 7500 AV Enschede, Netherlands Telephone number: +31-534-86 1186 Web address: 'http://www.btgworld.com' Project Manager: John Vos,' vos@btgworld.com' Technical Coordinator: Robbie Venderbosch, 'venderbosch@btwgorld.com' This cooperative research project is financially supported by the Seventh Framework Programme of the European Commission (Grant agreement number 212180). This document reflects only the project consortium's views. The European Community is not liable for any use that may be made of the information contained herein. List of Websites: 'http://www.supermethanol.eu'. Related documents Periodic Report - SUPER METHANOL (Reforming of crude glycerine in supercritical water to produce methanol for re-use in biodiesel plants)
