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Low temperature hydrogen production from second generation biomass

Final Report Summary - HYTIME (Low temperature hydrogen production from second generation biomass)

Executive Summary:
To support the sustainability of the future hydrogen economy, hydrogen has to come from renewable resources. Therefore hydrogen should be produced from water using ‘green’ electricity from solar or wind energy or from biomass.
In HyTIME, 6 industries, 2 universities and 1 research organisation have worked together to develop a process for production of hydrogen, at low temperature, from biomass resources having a high moisture content. This process is based on fermentation with natural micro-organisms and is an alternative to gasification of biomass. HyTIME leans heavily on the technology of anaerobic digestion but is special in having hydrogen as its product. In anaerobic digestion hydrogen is an intermediate product which is immediately consumed by hydrogen eating bacteria which make methane. In HyTIME the processes in anaerobic digestion are separated to make first a hydrogen fermentation which is then followed by methane production in separate anaerobic digester. Hydrogen is harvested and purified to make a product whereas the methane in the biogas is used to cover the heat demand of the process.
HyTIME has started with the successful mobilization of sugars from verge grass and wheat straw using mechanical and chemical pretreatment, followed by enzymatic hydrolysis. Hydrogen and subsequent methane production from wheat straw hydrolysates were successfully tested in simple stirred tank reactors. Although the hydrogen concentration in the raw gas was high (44% v/v), productivity and yield were fairly low. Hydrogen production from verge grass hydrolysate was tested in a dedicated high cell density reactor. Here hydrogen productivity and yield were high but the hydrogen concentration in the raw gas was lower (19%) due to dilution with nitrogen which is used as stripping gas in the dedicated reactor. Methane production using the effluent from the hydrogen reactor was successful. The volume of the dedicated hydrogen reactor was scaled up to 225L but as a result of contamination causing a decrease in yield, hydrogen productivity halted at 109 g hydrogen/day. For online monitoring and control of the fermentation special devices to measure performance indicators were developed and installed together with sensors for pH, pressure flow rate etc. Automation and visualization was realized to facilitate the management of the fermentation by means of a smart phone.
In order to enable efficient hydrogen upgrading, several membrane contactors were tested for removal of carbon dioxide from the fermenter off gas and the proof of principle was delivered by connecting 2 modules to the hydrogen reactor. At the same time, applicability and cost effects of conventional gas upgrading methods (VSA and PSA) were modelled and simulated for the recovery of hydrogen from the raw gas at low volumetric concentration, pressure and temperature.
For system integration all technological data over the entire process chain were collected to form the backbone of the simulation model for the techno-economic assessment at commercial scale. Optimization options for the process were identified. The foreseen methane production in the anaerobic digester would be sufficient to cover the heat demand of optimized process. Among the assessed process routes the chemical pretreatment of verge grass with lime seems to be the most favorable route concerning economics. In general, major cost contributions to hydrogen production costs resulted from biomass pretreatment. Besides lowering enzyme and chemical costs an increase of sugar yields and avoidance of sugar losses would improve the techno-economic results.

Project Context and Objectives:
H2 production by fermentation is a natural process which is part of the well-known anaerobic digestion (AD) which gives biogas as its end-product. In general, biogas contains circa 60 % methane and 40 % CO2 depending on the type of biomass which has been used as feedstock. Anaerobic digestion has been developed in the past to replace aerobic water treatment where aeration is an undesired cost factor. Currently, AD has become fashionable because of the production of methane which can add to the “green” energy supply. Anaerobic digestion is the result of collaboration of several micro-organisms, which either produce organic acids, H2 and CO2 in the acetogenic phase or consume organic acids, H2 and CO2 to produce methane in the methanogenic phase. In AD, biomass is completely converted with methane and CO2 as products.
The core issue of HyTIME is to separate the 2 phases which together form the AD process. HyTIME starts with a fermentation by specialist, natural bacteria which are selected because their efficient H2 production. Hydrogen and CO2 are the gaseous products from this fermentation whereas the organic acids remain dissolved in the fermentation liquid. Hydrogen is separated from CO2 by a novel process for gas upgrading. The liquid fraction with the organic acids, mainly acetic acid, is sent to a second vessel for AD. In this second step, biogas with methane and CO2 is the gaseous end-product. In HyTIME, biomass is converted to pure H2 and methane and CO2.

The proof of principle of H2 production from biomass has been delivered in previous RTD projects. These projects have been aimed at achieving a H2 yield which approaches the theoretical maximum and at preventing the growth of methane producing bacteria. The unique approach of employing thermophilic H2 producing bacteria rapidly growing at temperatures of above 70 °C has shown its success.
HyTIME builds on this knowledge and is geared towards increasing the productivity whilst maintaining the high yield in H2 fermentation.
The technique of H2 fermentation is quite similar to the established AD. However, the employment of thermophilic bacteria at larger scale is a new challenge since these bacteria have not been extensively investigated. Since HyTIME is based on the separation of H2 fermentation from methane production, the optimisation of the H2 production is extremely important to make up for the additional investments needed to maintain 2 separate vessels plus auxiliary equipment. As a result, all activities to enable an efficient H2 production system are integrated in the strategy of HyTIME.
HyTIME starts with the supply of suitable feedstock which is followed by the optimisation of the H2 fermentation in specially designed bioreactors. The rapid recovery of H2, at ambient pressure, 70 °C and low concentration requires new approaches in gas upgrading techniques and analysers. The integration of all these components, including the last step with using methane from AD for internal heat and power, will bring HyTIME to beyond the state-of-the-art of current fermentative H2 production.
Project objectives
The main objective of HyTIME is to produce H2 from second generation biomass with a production rate of 1-10 kg/H2.day.
Sub-objectives: 1) Efficient mobilisation of fermentable feedstock from second generation biomass
2) Increased productivity of H2 fermentation
3) Construction of dedicated bioreactors
4) Efficient gas purification at low pressure and temperature
5) Construction of online measurement and control devices
6) Process modelling and simulation studies
7) Techno-economic evaluation of a 400 kg H2/day plant

Project Results:
Biomass supply and fractionation
Verge grass and wheat straw have been selected as 2nd generation biomass. In the Netherlands, straw is available at 700-84 and verge grass at 240-500 ktonne dry matter /year at a cost between € 0- 100/ tonne dry matter. Fractionation resulted in 11 to 28 g sugars/L hydrolysate and was lowest in verge grass hydrolysate. Thermal and electrical demand of steam explosion, chemical impregnation and enzymatic hydrolysis and combinations hereof ranged from 0.43 to 3.6 kWh/kg dry biomass with the highest value using steam explosion. The suitability the fractionation procedures for H2 fermentation was validated. H2 productivity with the bacteria growing at 70° C (Caldicellulosiruptor saccharolyticus) was almost 4 times higher as compared to bacteria growing at ambient temperature.
Thermophilic fermentation
Caldicellulosiruptor spp. were selected for their high H2 yield. Element composition of molasses and nutrient requirements and sensitivity towards CO2 of the bacteria were determined, showing that i) supplementing molasses would be superfluous but ii) stripping a culture with CO2 would impair growth.
With the prototype labscale reactor, volume 5.7L a productivity of 4.6 g H2/day was achieved with 16 % H2 in the off gas and with pure glucose and xylose as substrate, and 6.0 g H2/day with 19 % H2 with verge grass hydrolysate. The yield of H2 was > 80 % and the mass balance was circa 100%.
With a bigger reactor, volume 58L, a productivity of 23.4 g H2/day was achieved with 17% H2 in the off gas and with pure sucrose as substrate; H2 yield was 88%. When the feed was switched to molasses and non-sterile conditions, the productivity dropped to 8.1 g H2/day with 7% H2 in the off gas and a yield of 25%. This poor behaviour could be counteracted by increasing the organic loading rate to a final productivity of 18.3 g H2/day with 12% H2 in the off gas and a yield of 22%.
The volume of the final reactor was 225L. This reactor was also run under non-sterile conditions and as a result the initial culture of Caldicellulosiruptor spp was rapidly outcompeted. The highest productivity observed was 109 g H2/day with 8% H2 in the off gas and a yield of 30%.
Methane was never observed and all mass balances were as expected with significant quantities of lactate, ethanol and butyrate besides acetate in the contaminated cultures.
Gas upgrading
The application of membrane contactors (MC) was investigated because of their low energy demand and high yield. With an off gas with 20 % H2, 10 % CO2 and 70 % N2, purification of H2 to 98% required 9.5 and 28.8 kWh/ kg H2 for MC or PSA, respectively. H2 yield was 89% (MC) as compared to 40% (PSA). Due to the cost of MC modules, only proof of principle was delivered by removing some CO2 from off gas from the 225L reactor. Several dedicated devices have been developed for monitoring and controlling the fermentation by measuring H2, CO2, O2 , CH4 and H2S. A distributed open source control/visualisation system following IEC 61512 and using MQTT protocol, was connected and successfully tested for operating the 225L reactor.
System integration
The integration in HyTIME started with testing biogas production using effluents of H2 fermentations in simple BioMethane Potential (BMP) systems. All effluents showed satisfying BMP for making HyTIME self-sufficient based on minimum heat demand. Simulation models were developed for techno-economic evaluation at 400 kg H2/d scale. Integration reduced HyTIME’s heat demand by up to 67% and 77% with optimized heat exchanger area and utility demand, respectively. As the cost factor for the hydrolytic enzymes amounted to circa 60-75% of the operating costs, alternatives as onsite production have been investigated. The effect of process parameters, i.e. 75% yield in gas upgrading to purity 1.8 and reduction of enzymes costs to 30%, was simulated. For all routes H2 yield was assumed to be 70%.

Potential Impact:
Potential impacts and use
In the EU, 118-138 million tons of bio-waste (waste from crops, garden waste, food and kitchen waste and waste from food processing plants) are produced on a yearly basis. This bio-waste is usually used for composting but is getting more and more attention to be used for anaerobic digestion. This is because of the production of methane in biogas which can be used as an energy carrier. The theoretical production of methane could amount to 2 million ton. With the same bio-waste availability, 0.34 million ton hydrogen could be produced, theoretically, with the technology developed in HyTIME where the co-product biogas is used for the power and heat demand of the process. If only half of the theoretical amount of hydrogen is recovered, an overall production of 20 PJoule/year is the result. This will increase because of the 10% increase in bio-waste production foreseen in the EU and because the technology can grow from its infancy to full maturity after 10 years following the start of HyTIME. The impact for the EU is twofold: a significant contribution to the ‘triple 20% by 2020’ objective with green hydrogen and a contribution to improved bio-waste management.
As HyTIME’s technology is comparable to anaerobic digestion, a first introduction of small scale units close to the origin of the biomass production as e.g. food processing industries, is envisaged. In this way, hydrogen could be used to cover the power demand of the industry or used as fuel in material handling vehicles. At the same time, HyTIME’s technology could be installed at communal or regional sites to replace either waste water purification or composting of domestic waste. These developments will need to be supported by further developments in pretreatment and hydrolysis protocols.
Main dissemination activities
All HyTIME partners have intensely contributed to the dissemination of HyTIME. Amongst the 13 general activities are interviews, available in hard copy and online, in the Dutch Financial Daily, in Petrochem (magazine for managers in the oil and chemical industry) and Research*EU Results Magazine and in national or regional papers or magazines. Numerous contacts have been made with representatives of Ministries or other governmental organisations. These representatives have come from HyTIME-partner countries but also from countries like Morocco, Russia, Greece, India and Japan. HyTIME has also been presented at >10 workshops organised for workers in the field but also for local entrepreneurs and policy makers. The international conferences, ACHEMA, PRES, WHEC, Hypothesis XI are the major ones where HyTIME has been presented with 23 oral and 4 poster presentations. Six papers have been published in peer-reviewed journals and 2 papers have been submitted. Over 25 students have worked on HyTIME issues throughout the project to acquire their degrees (2 PhD and 7 Master theses). Three training courses for external training have been developed. HyTIME has been promoted world-wide as an example of R&D in the EU in Canada, Japan, Malaysia, Korea, Taiwan and the HyTIME strategy was also discussed at 3 meetings of the Hydrogen Implementation Agreement of the IEA.
Exploitation of results
A dual sensor system was developed with both an electrochemical and a thermal conductivity sensor for the measurement of hydrogen in gas mixtures with CO2, CH4, O2 and CO. Industrial sectors are: Power to gas applications; production of pyrolysis gas; production of biogas with a high hydrogen content. The thermal conductivity sensor is sold as an option for the Awite gas analysis systems series 10. Communication and Visualisation software modules were developed for storage of data and display of history on common computers and mobile devices. It is fully based on open source and Industry 4.0 protocols and will be integrated into future automation systems of Awite. It is planned to make an add-on software “awiCharts” which uses the described components.

List of Websites:
Project website
www.hy-time.eu
Coordinator contact details
Pieternel Claassen
Stichting Dienst Landbouwkundig Onderzoek-Food & Biobased Research
Bornse Weilanden 9
6708 WG Wageningen, the Netherlands
Pieternel.claassen@wur.nl
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final1-beneficiary-list.pdf