EnBW s post-combustion capture pilot plant at Heilbronn

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1 EnBW s post-combustion capture pilot plant at Heilbronn OCTAVIUS project - Results MEA campaign CCS Conference Paris November 2015 Alexander Rieder EnBW T-BTV

2 EnBW s post-combustion pilot plant at Heilbronn Agenda Introduction post-combustion capture pilot plant Heilbronn OCATVIUS MEA pilot plant campaign Investigation of solvent-life time Emission control and reduction with an acid wash section Conclusions 2

3 EnBW s post-combustion pilot plant at Heilbronn Location and connection to the power plant Combined heat and power plant Heilbronn Three units (5, 6 and 7) are in operation Electric output (total) MW el District heating300 MW th Unit 7 FlueGas Cleaning CO 2 -capture plant Commissioned in MW el Fuel: hard coal, sewage sludge co-firing SCR-DeNO x ESP FGD Commissioned in 2011 Slip streamof Nm³/h CO Vol.%, O Vol.% (full-load) Plant design: 330 kg CO 2 /h at 90% capture rate Since 2011 a total of hours of operation achieved 3

4 EnBW s post-combustion pilot plant at Heilbronn Simplified process flow diagram CO 2 -lean fluegas Absorber CO 2 7 Wash Section II ID-fan 6 Wash Section I Stripper NaOH Prescrubber Intercooling Lean cooler Reboiler Flue gas after FGD 1 1 Hight: 5,5 m : 0,6 m Material: PP Hight: 41,2 m : 0,6 m Material: PP / GRP Hight: 30,5 m : 0,6 m Material: SS / 316 Ti

5 EnBW s post-combustion pilot plant at Heilbronn Partitioned material concept For the construction of the pilot plantan alternative material concept has been developed and realized Low temperature section: Pre-scrubber and absorber incl. piping and random packing is made in polypropylene (PP) High temperature section: Stripper incl. piping and random packingis constructed in stainless steel ( / 316 Ti) Random packing Type VFF VSP-25 Random packing Type VFF Twin-Pack

6 The OCTAVIUS project Demonstration activities at Heilbronn Two pilot plant campaigns were performed at Heilbronn MEA campaign (long-term) 30 % wt. Monoethanolamine Benchmark campaign CESAR I campaign (short-term) Mixture of 2-Amino-2-methylpropanol and Piperazine Key aspects of activity within the MEA campaign Investigation of solvent life-time and operability under real power plant conditions Solvent quality: time development of degradation products Reclaiming: Electro-Dialysis Dynamics Emissions and reduction with a double wash system and the use of sulfuric-acid

7 OCTAVIUS Results MEA campaign Hours of operation - operation history Pilot plant operation depending on the power plant Power plant standstill / Christmas break Continuous operation from Monday to Sunday 1421 hours of operation achieved

8 OCTAVIUS -Results MEA campaign Investigation of solvent life-time Many samples were taken for chemical analyses during the long-term campaign Heat-stable-salts (HSS) by IC Primary oxidative degradation products / Organic HSS Formate, Oxalate, Glycolate, Acetate Flue-gas compounds / Inorganic HSS Sulfate, Nitrate, Nitrite, Chloride Degradations products by LC-MS Secondary oxidative degradation products HEF, HEA, BEHOX, HEGly, HEHEAA, HEPO, HEI Thermal degradation products OZD, HEEDA Heavy metals by ICP-OES Iron, Chromium, Nickel

9 OCTAVIUS -Results MEA campaign Solvent life-time: time development of heat-stable-salts Different behavior of inorganic and organic HSS Adding of fresh solvent High sulfate concentration due to a leakage around the acid wash section after 1100 hours Major compounds Formate, Sulfate and Oxalate with a total share of 87 % after 1421 hours

10 OCTAVIUS Results MEA campaign Solvent life-time: degradation products after 1421 h Oxidative degradation products >> thermal degradation products Secondary oxidative degradation products [mg/l] Thermal degradation products [mg/l] => Oxidative degradation clearly dominates under real operating conditions Major compounds HEPO, HEGly and HEEHEA with a total share of 90 % after 1421 hours

11 OCTAVIUS Results MEA campaign Emission control and reduction - Double wash system

12 OCTAVIUS Results MEA campaign NH 3 -Emissions and reduction with sulfuric acid Second wash section in operation with acid Two characteristic time periods of NH 3 emissions Phase 1: from the beginning around 50 mg/m³ NH 3 Phase 2: increasing trend up to 350 mg/m³ NH 3 NH 3 reduction with the use of sulfuric acid is possible

13 OCTAVIUS Results MEA campaign NH 3 -Emissions and iron Adding of fresh solvent High concentrations of heavy metals Iron 935 mg/l Strong dependence of NH 3 emissions and iron content in the solvent Catalytic influence on oxidative degradation

14 OCTAVIUS Results MEA campaign Parameter study acid wash section Ammonia ph value Inlet* Outlet* Separation rate [-] [mg/m³] [mg/m³] [%] 3 58 <1 99, <1 99, , , ,3 Overall target: Keeping neutral water balance of the pilot plant Variation of ph-value from 3 and 7 High separation of NH 3 is possible Separation rate drops down at a ph-value of 7 * Average valueovertestperiod(min 2 hours)

15 EnBW s post-combustion pilot plant at Heilbronn Conclusions MEA campaign In order to investigate the solvent-life time long-term campaigns are essential Oxidative degradation dominates under real power plant operation conditions Major primary degradation products: Formate, Oxalate and NH 3 -Emissions Major secondary degradation products: HEPO, HEGly and HEHEAA => NH 3 -Emissions can be used as an online-indicator for the oxidative degradation High concentrations of heavy metals Indicates corrosion Catalytic influence of Fe on oxidative degradation NH 3 -Emissions can be successfully reduced with the acid wash section => Counter-measurements are necessary for a stable and long-term operation Solvent cleaning and regeneration Emission control and reduction (NH 3 < 5 mg/m³)

16 Thankyouforyour attention! Any questions?

17 Back-up

18 EnBW s post-combustion pilot plant at Heilbronn Impressions and pictures of the capture plant Flue gas duct and ID-fan Absorber and second wash section Pre-scrubber sumpand NaOH storage tank