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Feasibility Study of Hydrogen Production from H 2 S in Black Sea Waters using Green Energy

Feasibility Study of Hydrogen Production from H 2 S in Black Sea Waters using Green Energy K. Petrov 1 , P. Iliev 1 , D. Uzun 1 , A. Popov 1 , D. Ebrasu 2 , S. Z. Baykara 3 , V. Stanciu 2 , I. Stefanescu 2 , M. Gulin 4 and A. Veziroglu 5

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Feasibility Study of Hydrogen Production from H 2 S in Black Sea Waters using Green Energy

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  1. Feasibility Study ofHydrogen Production from H2S in Black Sea Waters using Green Energy K. Petrov1, P. Iliev1, D. Uzun1,A. Popov1, D. Ebrasu2, S. Z. Baykara3, V. Stanciu2, I. Stefanescu2, M. Gulin4 and A. Veziroglu5 1 Institute of Electrochemistry and Energy Systems of Bulgarian Academy of Sciences, Sofia, Bulgaria 2National Institute for Cryogenics and Isotopic Technologies, Rm. Valcea, Romania 3Chemical Engineering Department, Yildiz Technical University, Davutpasa Campus, Topkapı, Istanbul, Turkey 4A.O. Kovalevsky Institute of Biology of the Southern Seas, Oceanology Centre, NationalAcademy of Science of Ukraine (OC-IBSS)- Sevastopol, Ukraine 5International Association for Hydrogen Energy, Miami, USA

  2. Introduction • Black Sea is an elliptical basin with an area of 423.000 km2. More than 100 million people live around its coast. • Black Sea is unique because 90% of the sea water is anaerobic. • H2S is produced by sulphur reducing bacteria at an approximate rate of 10 000 tons per day. • It keeps reducing the life in the Black Sea. • Oxygen–hydrogen sulphide interface is established at about 70 -140 m below the surface. • Proposal supported by: Agency of the Black Sea Economic Cooperation (BSEC) and International Center for Hydrogen Energy Technologies (UNIDO-ICHET), Istanbul

  3. Map of the Black Sea

  4. Concentration of H2S and O2 in Black Sea water from different authors

  5. Main Idea • The main idea is to exploit the potential of Hydrogen sulphide (H2S) in the Black Sea waters for production of hydrogen, sulphides (sulphur) and sweet water using green energy sources like sun and wind. • The originality of the project is based on the thermodynamical possibility to produce hydrogen from H2S with much less energy than from water (H2O). The thermodynamical potential for splitting water to Hydrogen and Oxygen is E=1.23 V, compared with E=0.17 V for H2S. • Additionally to Hydrogen, electrolysis of H2S is producing polysulphides, which is another valuable commercial product.

  6. Flowchart of the process in consideration

  7. Application of the Absorption/Electrolyzer Unit for cleaning of industrial waste waters and gases

  8. Application of the Absorption/Electrolyzer Unit on the shore of the Black Sea

  9. Objectives • Environmental evaluation of the proposed technology • Technical evaluation of different processes for H2S conversion: Transportation of H2S containing water from the depth of the Black Sea; Extraction of H2S from sea waters by absorbents; Electrochemical production of hydrogen and polysulphides. • Economical feasibility

  10. Environmental evaluation of the proposed technology • Natural water conditions as well as the endemic biological communities are extraordinary and must be protected. • Unique spatial structure of the Black Sea basin can be sensitive to disturbances. Contamination of the uppermost, photosynthetic layer of the Black Sea by its deep waters can produce an effect of anthropogenic upwelling and strong intensification of already observable eutrophication. • Suggested technologies intend to move big volumes of deep Black Sea water.Outlet of technologically discharged deep-sea waters into the superficial layer of the Black Sea is definitely impossible. • Vertical fluctuations of the oxic/anoxic interface of the Black Sea can reach down to 165-meter depth. Hence, environmentally appropriated technology for back discharge of waters after absorption of H2S should be carried out to the depths which are not less than 200 m.

  11. Technical evaluation of processes included in technological scheme • Preliminary technical considerations: Demonstrational pilot installation processing 200 m3/hr Sea water have been considered: FR = Q = 200 m3/hr = 0.06 l/sec Concentration of H2S: C H2S = 8 mg/l. Length of the pipeline (LP) - closest to the shore depth of 1000 m: LP = 15 kM The depth of pumping (DP) of Sea water: DP = 1000 m Depth of Return: DR=200 m.

  12. Hv 50 m 60 m 200 m 1000 m Transportation of H2S containing water from the depth of the Black Sea Scheme of pumping water from the bottom of the Sea. ∆h=1000 m

  13. Transportation of H2S containing water from the depth of the Black Sea • The pump has optimum flow rate of Q = 216 m3/hr and uses power of 54.1 kWhr. The necessary pipe diameter (calculated from the hydraulic losses) is Φ = 400 mm • The above considerations show that we need a pump situated on the shore of the Sea with power around 60 kW and 15 km long pipeline with diameter d=400 mm. Such pumps are offered in the market by companies like “Grundfos”, KSB, “Ploger”, etc. Different types of pipelines are offered too; REHAU, [http://fenix-garant.hit.bg/], etc.

  14. NaOH Sea water NaOH + HS- H2S Adsorption/Desorption Installation Adsorption of H2S from Sea water: Q=200m3/h; CH2S= 8mg/l; which makes 1.6 kg H2S Active carbon AD3 produced in “Buzau”, Romania: Adsorption capacity: aH2S = 0.0021 g H2S/g AD3 Relative weight of AD3 is RW= 400g/l Amount of AD3 = 760 kg ≈ 800 kg; 800 kg at RW=400g/l is equal to 2 m3. We chose 2.5m3 of carbon for reserve. Columns dimensions: diameter Ф=900mm and height H=1800; volume = 1.1m3 or 3.3m3 Desorption of H2S from carbon with NaOH Second group of three columns: about 200l NaOH, CNaOH =10g/l.

  15. H2S Adsorption/Desorption Installation Energy and mass balance of adsorption – desorption and electrolyte preparation unit The Sea water goes through adsorption columns driven by the pumps. Pumping of 200 l of NaOH solution for desorption is negligible; 200 l of 10g/l NaOH solution will adsorb 1600g of H2S and necessary NaCl. For electrolyte with concentrations of 80g H2S/l; 80g NaOH/l and 50g NaCl/l we need 20 l/hr (20 l by 80g H2S/l is equal to 1600g of H2S). Evaporation of 180 l of water ≈ 200 l; 400 cal/g for water; in kWhr for 200 l of water is equal to approximately 100 kWhr. The adsorption columns and evaporator are common chemical apparatuses and they are offered by many companies [EMIS, LLC, Sofia Bulgaria, F. Geckovski]

  16. Electrolysis Cell parameters of flow-type electrolyzer: long term test of 500 hrs at following conditions: NaOH=2M; NaSH=8M; T=80oC; cathode from Raney- nickel; anode is La0.79Sr0.20Mn403; Nafion membrane; Ecell=1.0 V at i=300 mA.cm-2; cathodic efficiency ≈ 100 %; polysulfide chain length - S6S- . There are not commercial H2S electrolyzers on the market. Similar to them are PEM water electrolyzers as a construction and price. The energy required for 1600g H2S/hr ≈ 2.5 kWhr. The produced Hydrogen ≈ 100 g/hr, or 1000 l H2/hr and poly-sulfides ≈ 1500 g/hr.

  17. Economic Feasibility The economical feasibility is an approximation of what is offered on the market. [polymer pipe differ between 30 Euro/m (FENIX) up to 80 Euro/m (REHAU)] All prices are in Euro Equipment: • 1.Transportation of Sea water: 1 300 000 Pump, Q = 200 m3/hr; P = 60 kW – 25 000; plus installment ≈ 50 000 Polymer pipe with Ф 400 мм – 80 Euro/m; For 15 000m – 1 200 000 Installment - 50 000. • 2. Electrolyzer: 2.5 kW ≈ 25 000 • 3. Adsorption – desorption unit: 21 000 Adsorption columns - Ф900 мм; Н1800 мм; V=1.1 м3, 6 by 3000 ≈ 20 000 Active carbon: 2 tons by 300 – 600. • 4. Evaporator – 10 000 • 5. Tanks for hydrogen and poly-sulfides – around 10 000 • Total: 1 400 000 Euro

  18. Economic Feasibility (2) Energy: 130 Euro • 1.Transportation of Sea water: 80 kWhr • 2. Electrolysis: 2.5 kWhr • 3. Evaporator: 100 kWhr Total: 182.5 ≈ 200 kWhr; For 8 000 hr per year: ≈ 1.6 mWhr (price of 1 mWhr is 80 Euro) Total price of equipment and energy ≈ 1 400 000 Euro Conclusions The biggest share of the cost belongs to the pipeline. Probably we should contact the specialists from gas pipeline companies in order to find a cheaper (real) solution. If we assume that the installation will work 50 years the expenses per year will be approximately ≈ 28 000 Euro per year.

  19. Economic Feasibility (3) Products of the installation Hydrogen ≈ 100 g/hr, or 1000 l H2/hr and poly-sulfides are about 1500 g/hr. For 8000 working hours per year the installation will produce: 8 000 m3 of Hydrogen and 12.0 tons of polysulfides Price of sulfur – 500 $/ton (350 Euro/ton) for 12.0 tons – 4200 Euro Price of Hydrogen – 0.20 Euro/m3, market price; 3.0 Euro/m3, proposed EU price for renewable energy sources, or 8 000 m3 x 3.0 Euro = 24 000 Euro Total: 24 000 +4 200 ≈ 28 000 Euro

  20. Conclusions The preliminary feasibility study of the proposed technology shows that the process of producing Hydrogen and poly-sulfides from Black Sea water is close to reach economic feasibility at supported by EU price of Hydrogen. The biggest price share belongs to the pipeline. We shall contact the specialists from gas pipeline companies in order to find a cheaper solution. The proposed technology seems to be very applicable to industrial H2S containing waters as well as some natural sources close to the ground.

  21. Cap Kazantip – South-Easth Crimea

  22. Electrolyzer [CH2CH2S5] n Me2S5 + ClCH2.CH2Cl S Scheme of sulfur and poly-sulfides use for thio-vinil-cloride production

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