Hydrogen Economy Now 8

Hydrogen Hydrogen Everywhere Not a drop to harm Mohideen Ibramsha 1968 Alumni of Thiagarajar College of Engineering, Madurai, TN, India 1974 intellectual son of PhD guide Prof. V.Rajaraman & Mrs. Dharma Rajaramn, CS, EE, IIT, Kanpur, UP, India 1991 First HOD of CSE, CEC [now BSAU] Chennai, TN, India Associate Professor (Retd), Computer Science, Framingham, MA, USA Consultant R&D, M A M College of Engineering, Trichy, TN, India Advisor, HyDIGIT Pte Ltd, Singapore Email: ibramsha7@yahoo.com

This article was posted elsewhere on Tuesday, June 26, 2018 - 04:57 pm. It is re-posted here without modifying the contents. Introduction: Mankind is moving towards the Hydrogen economy. To avoid further pumping of CO2 into the atmosphere renewable sources of energy are preferred. The attempts by two companies to store the renewable energy are analyzed here. Electrochaea GMBH is located in Munich, Germany. Hydrogenious Technologies, GMBH is located in Erlangen, Germany. Electrochaea concept: This Company uses stranded power and CO2 to produce CH4 and store the energy in CH4 as mentioned at http://www.electrochaea.com/technology/ . The biocatalyst used is methanogenic archaea that is tolerant to Oxygen. Excess power generated by wind power stations and solar power stations are stranded power. Instead of storing the CH4 locally this company aims to inject the CH4 to the existing CH4 grid taking advantage of the world wide storage facilities of CH4. Even though stranded power could be solar or wind energy, the solar plants could be easily controlled to avoid generating excess power. It is difficult to control wind mills to avoid generating excess power. We feel P2G, the concept of Power To Gas implemented by this company would be useful to convert the excess wind power to gas.. Hydrogenious Technologies concept: Stranded gas could be used. A Catalytic Methane Decomposition (CMD technique could be used to extract the Hydrogen from CH4 with the carbon getting deposited. The liberated Hydrogen could be stored in a Liquid Organic Hydrogen Carrier (LOHC) which could be treated like petrol and stored for long periods without any loss of energy. The theory behind the above statements regarding Hydrogenious Technologies is found in a paper the abstract of which is available at https://onlinelibrary.wiley.com/doi/abs/10.1002/cssc.201600435 . From a preprint version of the paper we discuss the technology. We know about liquid Hydrogen used as a rocket fuel indicating that the highest energy density of Hydrogen is as a liquid. Stefan Durr and his co-authors of the above paper have possibly used an iron based catalyst for their experiments. As the catalysis proceeds the Carbon from the decomposed Methane deposits on the catalyst and leads to eventual deactivation of the catalyst. It is proposed that the deactivated catalyst be sold to steel industries. The decomposition was not complete and thus Methane and hydrogen were present in the output of decomposition. They used a LOHC to capture the Hydrogen from the mixture. This aspect of LOHC capturing Hydrogen is the basis of the company’s successful industry. From http://www.hydrogenious.net/en/products/ we find that the unloaded LOHC is dibenzyltoluene with greater than 99% purity and the loaded LOHC is perhydro-dibenzyltoluene with more than 95% hydrogenation. Loading the LOHC at 16 liters per hour produces 9 KWh of heat per hour. Unloading the LOHC at a rate of 8 liters per hour consumes 4.5 KWh of heat. Thus the loading and unloading combined do not consume any heat energy. Hydrogenious Technologies business activity: Even though Catalytic Methane Decomposition was used in the research published, the company has avoided the cumbersome process in developing its business. We quote: http://www.hydrogenious.net/wp-content/uploads/2016/02/2016_02_01-Hydrogenious_press_release_english-1.pdf === Erlangen 29.01.2016 … Various innovative next-generation technologies are implemented in the first commercial LOHC systems by Hydrogenious Technologies. A Siemens PEM Electrolyzer generates hydrogen using solar power. The hydrogen is then stored in LOHC by means of the Hydrogenious StorageBOX. The liquid can then be stored in ordinary storage tanks without any losses or boil-off effects for extended periods of time. About 57 kg hydrogen can be stored in one cubic meter of the liquid. That equals approximately 1.9 MWh of energy. The ReleaseBOX by Hydrogenious Technologies can release hydrogen from LOHC and supply the gas to a fuel cell. === Hydrogenious Technologies are opening Hydrogen refueling stations in Germany and neighboring European countries. The data regarding the refueling stations are displayed at https://h2.live/ . This web site was accessed on June 26, 2018 and the data for Germany are: 43 are open; 7 are in commissioning and trial operation; 16 are in execution phase; 14 are under approval process; and 11 are in planning. Hydrogen in LOHC: We extract the following information from Table 1 of the publication referred earlier.

No Energy Source Energy Density KWh/Liter

1 Fossil Gasoline 8.6

2 ...... Fossil Diesel ................................... 9.8

3 Fossil Heavy oil 10.7

4 ...... Fossil Natural Gas .......................... 2.4

5 Hydrogen (1 bar) 0.003

6 ...... Compressed Hydrogen Gas (700 bar) .. 1.3

7 Liquefied Hydrogen 2.4

8 ....... Hydrogenated LOHC ...................... 1.87

From the above table we find that the Hydrogenated LOHC carries 77.92% of the energy carried by liquid Hydrogen and thus Hydrogenated LOHC could be considered for rocket fuel as well if appropriate technology for down sizing the ReleaseBOX to fit inside a rocket is done. Electrochaea Business Activity: In contrast to the La Porte, TX demonstration plant of ALLAM Cycle that is yet to produce electricity from CH4, Electrochaea with partners ran the demonstration plant at Avedore, Denmark for eight months until December 22, 2016. We quote: https://energiforskning.dk/sites/energiteknologi.dk/files/slutrapporter/12164_final_report_p2g_biocat.pdf === Pages 12 and 13 of 34 The BioCat P2G system is a commercial-scale 1MW capacity power-to-gas facility connected to both power and gas grids, providing direct grid interconnection from power to gas. The system operated for 8 months during the project, including commissioning. During the project, the system used 42,193 Nm3 biogas, 170 m3 water and 708,215 kWh electricity for system operations and to produce 129,290 Nm3 hydrogen for methanation of ~16,000 Nm3 CO2 from the the biogas and making available ~15,000 Nm3 renewable methane and 85,000kWh heat for use at Avedøre’s facility. The system operated at variable loads and was used intermittently through 3 seasons until December 22, 2016. === Subtracting the 85,000 kWh of heat produced by the methanation process, the plant used 623,215 kWh of energy to produce renewable CH4. The CH4 produced is claimed to be renewable as the CO2 used that would have been released to the atmosphere from waste water treatment plant was stored in the CH4 to be released when the CH4 is used elsewhere. Thus the technology used by Electrochaea is green using renewable electricity for electrolysis of water to produce Hydrogen. Financial aspect of Electrochaea process: We ignore the cost of capital in analyzing the financial aspects of the P2G system. The demonstration plant used 623,215 kWh of energy. From figure 2 in page 15 of 20 of https://energiforskning.dk/sites/energiteknologi.dk/files/slutrapporter/12164_annex_3_p2g_biocat_-_market_analysis_report.pdf we find that the price of electricity used by the demonstration plant varies from a low of 404 DKK/MWh during low demand for electricity in Denmark to a high of 450 DKK/MWh during peak demand in Denmark. We expect the P2G facility to consume power during low demand and thus to have paid 623.215 x DKK 404 = 251,778.86 DKK. The demonstration plant produced 15,000 Nm3 of renewable CH4. From page 15 of https://energiforskning.dk/sites/energiteknologi.dk/files/slutrapporter/12164_annex_3_p2g_biocat_-_market_analysis_report.pdf we find: === HMN is grid operator in the area and HMN informs that the expected grid injection payment is 0.6 DKK/Nm3 biomethane (Rousing, 2014). It corresponds to 50 DKK/MWh upper calorific value. === Thus the gas injection cost is 0.6 x 15,000 DKK = 9,000 DKK. Including the cost of electricity, the total payment by the demonstration plant was 260,778.86 DKK. From the Table 1 in page 15 of 20 of the above PDF, we find that a plant similar to the demonstration plant would have received a subsidy of 342 DKK/MWh during 2014. As the demonstration plant operated in 2016, one component of the subsidy gets reduced by 2 DKK/MWh and thus the subsidy is 340 DKK/MWh. We assume that the bioreactor is not pressurized and thus the Methane produced by the bioreactor is 15,000 Nm3 at atmospheric pressure. The temperature of the bioreactor is 65 C. We find the weight of 15,000 Nm3 Methane produced at 65 C and 1.013 bar. http://cdm.unfccc.int/methodologies/inputsconsmeth/MGM_methane.pdf === What matters for climate change is methane mass (kg or tonne). Normally, volume (m3 ) or flow rate (m3 /h) is measured using some measurement device or instrument, and these volume values are converted to mass (kg or kg/h). An intermediate step usually involves adjusting the measured volume by measured pressures and temperatures to volumes at standard conditions (0 C and 1 atm, equal to 1.013 bar). The resulting volume (called Nm3 ) is then converted to mass using the density at these conditions = 0.716 kg/m3 ). === We know that PV = RT is true and thus P1xV1 = P2 x V2 = RT. One Nm3 of CH4 at 0 C weighs 0.716 Kg. When we increase the temperature from 0 C to 65 C, the volume increases from 1 Nm3 to (273 + 65) / 273 Nm3 = 1.2381 Nm3. Accordingly, we calculate the weight of 15,000 Nm3 of CH4 to be 15,000/1.2381 x 0.716 Kg = 8674.62 Kg. One Kg of CH4 produces 50 MJ and thus 8674.62 Kg of CH4 produces 50 x 8674.62 MJ = 433,730.77 MWseconds = 120.48 MWh. We have used the LHV of CH4 instead of the HHV. It is felt that using HHV would not make the P2G process profitable. Thus we continue with the LHV of CH4. The subsidy is 120.48 x 340 DKK = 40,963.46 DKK. The cost incurred in producing 8,674.62 Kg of CH4 is 260,778.86 – 40,963.46 = 219,815.40 DKK. What about the sale proceeds of this CH4? https://www.statista.com/statistics/418005/natural-gas-prices-for-households-in-denmark/ === This statistic shows the natural gas prices for household end users in Denmark semi-annually from 2010 to 2016. In the first half of 2016, the average natural gas price for households was 7.17 euro cents per kWh. === We have used the gas price paid by the consumer and not the gas price paid to the producer. As the price paid to the producer is invariably less than the consumer price, recalculation is not attempted as the P2G makes loss even now. One DKK is 0.13 Euro and thus the CH4 price in DKK = (7.17/100) / 0.13 = 0.551538 DKK per kWh. It is 551.54 DKK per MWh. The demonstration plant produced 120.48 MWh. Hence the income from selling the CH4 for the demonstration plant is 120.48 x 551.54 DKK = 66449.54 DKK. The cost incurred in producing the CH4 being 219,815.40 DKK, the demonstration plant incurred a loss of 153365.86 DKK. Even with substantial subsidies, the P2G incurs loss. Conclusion: To convert the stranded power to gas is not economically viable. Electrochaea has invented the process to convert Hydrogen and CO2 to CH4. As Hydrogenious Technologies abandoned the stranded gas and evolved a business model we suggest Electrochaea also abandon the P2G and evolve a business model dumping the stranded power. Storing Hydrogen as Hydrogenated LOHC is about 20% as dense as gasoline. In contrast to the numerous climate negative effects of gasoline, Hydrogenated LOHC is safe and is also green. We hope the world would move to storing Hydrogen as Hydrogenated LOHC and thus enjoy Hydrogen Everywhere with no harm whatsoever.

The other articles in this series are: