Liquid organic hydrogen carriers (LOHC) - Concept ...
Transcript of Liquid organic hydrogen carriers (LOHC) - Concept ...
Liquid organic hydrogencarriers (LOHC) - Conceptevaluation and techno-economicsMarkus Hurskainen & Janne Kärki VTT Technical Research Centre of Finland Ltd
Seminar on the Finnish needs and research highlights on hydrogen - focus on liquid LOHC “batteries” and hydrogen legislation
Innopoli 1, Espoo, October 7th 2018
Contact: [email protected]
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Contents
Main characteristics of the LOHC concept
Case study: Logistics of by-product hydrogen
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LOHC concept characteristicsStrengths
Distribution and storage compatible with existing infrastructure
Safety No storage loss: suitable to long-term storage High storage density compared to compressed gas Releases almost pure hydrogen stream with no
major by-products
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Dehydrogenation(endothermic, low p, high T)
Hydrogenation(exothermic, high p, lower T)
Hydrogen
Hydrogen
Heat
Heat
Compoundcarrying H2
H2 is released using heat
H2 is binded which releases heat
Compoundable to bind H2
LOHC concept characteristicsWeaknesses
Releasing hydrogen requires a lot of medium temp (300-350°C) heat• ~30% of the hydrogen would have to be burned
But binding of hydrogen releases the sameamount of heat although at lower temperature(~150°C) Utilisation is important
Dehydrogenation is carried out at only slightly elevated pressures (1-5 bar) High compression demand e.g. for mobility
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27%
27%
100%
Percentages are for dibenzyltoluene (DBT) corresponding to reaction enthalpy of ±65 kJ/mol H2
Applications for the LOHC concept?
LOHC concept is essentially a means to enable efficient transport and/or storage of hydrogen
What creates the need to transport hydrogen? Hydrogen formed as an unavoidable by-product OR Centralized production elsewhere more feasible
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Applications for the LOHC concept? Applications which require hydrogen as a raw material / a
reactant were seen more favourable compared to conversion to electricity • There is no market for long-term energy storage yet and there is not
enough shorter term variance in electricity prices either• Almost pure H2 is released as opposed to some other H2 carriers
(e.g. NH3, SNG)
In future, electricity storage (especially in off-grid solutions) or use in transport sector will become relevant
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Case 1 – Logistics of by-product hydrogen
Rationale (1/2)
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Due to extensive pulp industry, high amounts of electrolytic by-product hydrogen is generated in Finland (~23 000 t/a, ~770 GWh, ~100 MW)
Due to the lack of cost-effective transport means, part of the hydrogen is just vented and part is usedin low-value applications (energy) while at the same time hydrogen is generated using fossil raw materials elsewhere
LOHC could enable feasible transport of by-product H2 to substitute fossil-based H2
Figure courtesy of Kemira
Dehydrogenation(endothermic, low p, high T)
Hydrogenation(exothermic, high p, low T)
Hydrogen
Hydrogen
Heat
Heat
Compoundcarrying H2
H2 is released using heat
H2 is binded which releases heat
Compoundable to bind H2
27%
27%
100%
100%
Rationale (2/2)
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One marked advantage is the possibility to utilise the heat released in hydrogenation in NaOH/chlorate plant to avoid the burning of hydrogen for energyHeat is required e.g. for• Concentration of NaOH solution• Drying, dissolving and precipitation of chlorate• District heating
Percentages are for dibenzyltoluene (DBT) corresponding to reaction enthalpy of ±65 kJ/mol H2
Case 1 description Purpose was to compare LOHC (dibenzyltoluene) delivery chain to
1) the current logistic option (200 bar steel bottle containers) and 2) an advanced 350 bar composite cylinder containers
…in point-to-point delivery from a chlor-alkali/chlorate plant to industrial customers
Two different hydrogen demands (2.5 & 10 MW H2 = 1800 & 7200 kgH2/day) and three transport distances (50, 150, 300 km one-way)
Comparison to on-site water electrolysis20.11.2018 VTT – beyond the obvious 10
Hydrogen supply chains
Purified by-product H2
Heat is utilized at the NaOH/chlorate plant
decreasing the need to burn hydrogen for energy purposes
Compr
Part of the hydrogen is burned to release the hydrogen from
LOHC
LOHC H2 consumer2.5 or 10 MWH2,LHV
demand
Dehydro-genation
Hydro-genation
1)
On-site electrolysis3)
NaClO3NaOH
GH2
2) a) 200 bar steel
b) 350 bar composite
• Three different transport distances: 50, 150 and 300 km (one-way)• Delivery as liquid hydrogen was excluded as the scale of by-product H2 is too low
H2 source
Price of hydrogen or purification were not
considered
LOHC concept assumptions Dibenzyltoluene based (H0-DBT/H18-DBT)
• H2 storage density 6.2 wt%• 100% degree of (de)hydrogenation• Reaction enthalpy ±65 kJ/molH2
• 50 bar hydrogenation• Degradation 0.1% per cycle• DBT price 4 €/kg
For LOHC reactors, there is very high uncertainty regarding CAPEX weused two estimations to give us a range
Fixed O&M 4% of CAPEXReus et al. Applied Energy 200 (2017), pp. 290–302Eypasch et al. Applied Energy 185 (2017), pp. 320–330
Trucking related assumptions
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Truck LOHC tankertrailer (36 000 l)
GH2 trailer (2x 200 bar steel bottle ISO20 containers)
Advanced GH2trailer (ISO40 HC
350 bar composite)
Investment cost 180 k€ 140 k€ [1] 530 k€ [1] 420 k€ [1]
Depreciation period 1.5 Mkm / 8 years 15 years 15 years 15 yearsO&M 0.1 €/km 4% of CAPEX 2% of CAPEX 2% of CAPEXNet H2 payload 2000 kg 400 kg 900 kgUnloading & loading (LOHC)Drop-off & pick-up (GH2)
2 h (total for a trip) [2]
2 h (total for a trip) [2]
2 h (total for a trip) [2]
Diesel consumption 45 l / 100 kmDiesel price (VAT0%) 1.05 €/lAvg. speed (excl. unloading & loading)
65–72–77 km/h (50–150–300 km)
Driver employment cost (incl. indirect costs) 45 k€/a
Truck availability 80%[1] Quotations from suppliers & VTT estimation for rolling platforms[2] Teichmann et al. 2012
~40 t loads,24/7 delivery
ResultsTotal delivery costs
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With low CAPEX estimation, LOHCand composite GH2 equallycompetitive for 50-150 km while300 km favours LOHC
With high CAPEX estimation,composite GH2 is the most feasible
LOHC delivery cost do not increasemarkedly with transport distance
On-site H2 generation costs arehigher, leaving margin to pay for thehydrogen raw material to the H2producer but are highly dependenton the electricity price
Max value of purifiedhydrogen
Electricity @ 50 €/MWh
60 €/MWh
40 €/MWh
On-site electrolysis
ResultsCost breakdowns - 2.5 MW H2 (1800 kg/day) & 150 km
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Trucking
Processing*
In the LOHC deliverychain the costs are mainly related to
hydrogen processingwhile for GH2 chains
trucking costs dominate
*compression, hydrogenation, dehydrogenation, site costs
2.5 MW & 150 km
ResultsNumber of trucks and trailers – 2.5 MW H2 (1800 kg/day*)
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50 km 150 km 300 km
LOHC
200 bar steel
350 bar compo-site
For LOHC ~2600 kg/day as ~30% needs to be burned to release hydrogen
ResultsNumber of trucks and trailers - 10 MW H2 (7200 kg/day*)
17
50 km 150 km 300 km
LOHC
200 bar steel
350 bar compo-site
For LOHC ~10300 kg/day as ~30% needs to be burned to release hydrogen
Conclusions
LOHC seems to be a viable option for transporting by-product hydrogen from chlorate/chlor-alkali plants when the distances are >100 km if the reactor CAPEX are at the lower-end of the literature estimates
• In cases where there would be medium temp waste-heat available at the hydrogen consuming site, LOHC economics would improve markedly
• LOHC could also enable storing more hydrogen at relatively minor additional cost delivery schedule could be more flexible and it would be possible to
prepare for the maintenance and unscheduled breaks
Although the amount of by-product H2 is finite, its transportation could be the low-hanging fruit for the LOHC concept to enter the market 20.11.2018 VTT – beyond the obvious 18
Thanks!
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Literature Eypasch, M., Schimpe, M., Kanwar, A., Hartmann, T., Herzog, S., Frank, T. & Hamacher, T. (2017). Model-
based techno-economic evaluation of an electricity storage system based on Liquid Organic Hydrogen Carriers, Applied Energy 185, pp. 320–330.
FCHJU. (2017). Early business cases for H2 in energy storage and more broadly power to H2 applications, Final Report, Fuel cells and hydrogen joint undertaking, P2H-BC/4NT/0550274/000/03.
NREL. (2010). Hydrogen Delivery Component Model - Version 2.2, National Renewable Energy Laboratory Reus, M., Grube, T., Robinius, M., Preuster, P., Wasserscheid, P. & Stolten, D. (2017). Seasonal storage
and alternative carriers - A flexible hydrogen supply chain model, Applied Energy 200 (2017), pp. 290–302. Teichmann, D., Arlt, W. & Wasserscheid, P. (2012). Liquid Organic Hydrogen Carriers as an efficient vector
for the transport and storage of renewable energy, International Journal of Hydrogen Energy, Volume 37, Issue 23, pp. 18118–18132.
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