Advancement of CO2 Compression and Purification Plant in the Integration with the Oxyfuel Technology
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1 Advancement of CO2 Compression and Purification Plant in the Integration with the Oxyfuel Technology R. Ritter, N. Schödel CCT 2009 Conference Dresden, May 2009
2 Table of Contents New Process Developments for NOx and SOx Removal Catalytic DeNOx Alkali-based Scrubbing Unit 2 N. Schödel / 0901 / LE-Presentation_E.ppt
3 Contents New Process Developments for NOx and SOx Removal Catalytic DeNOx Alkali-based Scrubbing Unit 3 N. Schödel / 0901 / LE-Presentation_E.ppt
4 New Process Development for NOx and SOx Removal Background Background The flue gas of oxyfuel power plants with CSS has to be purified before transportation and storage. There are several common technologies for flue gas purification for: DeNOx DeSOx Simultaneous removal The purification steps are cost intensive. Due to this, an optimization is desirable. There is a high operation pressure available in the CO2-stream. new process ideas 4 N. Schödel / 0901 / LE-Presentation_E.ppt
5 New Process Development Selected concepts Simultaneous removal of SOx and NOx possible Elevated Pressure NO+N O 2 Fast SCR +Reduction media N 2 (Linde- Patent) NO Self induced homogeneous Oxidation NO+N O 2 Absorption Alkali based scrubber Reduction N 2 Fertilizer (Linde-Patent) Selected Linde R&D concepts: Catalytic DeNOx and Alkali-based Scrubbin 5 N. Schödel / 0901 / LE-Presentation_E.ppt
6 Contents New Process Developments for NOx and SOx Removal Catalytic DeNOx Alkali-based Scrubbing Unit 6 N. Schödel / 0901 / LE-Presentation_E.ppt
7 Catalytic DeNOx State of the Art Technology State of the art arrangement Boiler SCR Filter FGD CO2 Compression High dust Boiler Filter SCR FGD CO2 Compression Low dust Tail end NH3-DeNOx: vanadium-titanium-oxide catalyst, C, approx. atmospheric pressure 7 N. Schödel / 0901 / LE-Presentation_E.ppt
8 Catalytic DeNOx Linde Concept Pressure Reaction Catalyst bar preferred: 5 50 bar 4NO + 4NH 3 + O 2 4N 2 + 6H 2 O 2NO + 2H 2 N 2 + 2H 2 O vanadium-titanium-oxide or other, e.g. noble metal Temperature C preferred: C 8 N. Schödel / 0901 / LE-Presentation_E.ppt
9 Catalytic DeNOx Proof of Principle Tests Tests performed: reduction medium NH3 or H2 PI TI TI TI pressure up to 25 bar TE-(1-6) TE-(7-12) Te-(13-18) GHSV up to h-1 PI TI PI temperature down to 150 C Wasserdampferzeugung PI 1 Multiportventil Analytik PI 2 Multiportventil Analytik PI 3 Multiportventil Analytik NOx content up to 0,07% Waage Multiportventil Analytik Abgas Abgas Abgas O2 content up to 6% F1 F2 F3 F4 F5 in CO2/N2 matrix (~ 85/10) FIC FIC FIC FIC FIC Stickstoff CO2 Kohlenwasserstoffe O2 Results: Conversion under pressure possible Positive effect of the pressure on the performance Patent application prepared Example NH3-DeNOx: NOx converion [%] barg 10 barg V2O5/TiO2 catalyst 0.04% NOx T 250 C GHSV h-1 9 N. Schödel / 0901 / LE-Presentation_E.ppt
10 Catalytic DeNOx Technology Comparison State of the Art low pressure NH3 as reduction medium V2O5-TiO2-(WO3)catalyst temperature C (heat integrated) highly contaminated stream large stream Salts formation (sulfate/nitrate) possible Linde fast DeNOx Concept high pressure reduction medium e.g. NH3, H2 V2O5-TiO2 or other, e.g. noble metal catalyst (low temperature types possible) temperature C, preferred: C (use of compression heat) relatively pure stream reduced stream (1/3 to CO2 plant, pressure) positive effect on reaction rate due to, e.g., NO2 formation, increased NOx concentration, pressure Depending on reduction media no or limited salt formation (nitrate) possible 10 N. Schödel / 0901 / LE-Presentation_E.ppt
11 Contents New Process Developments for NOx and SOx Removal Catalytic DeNOx Alkali-based Scrubbing Unit 11 N. Schödel / 0901 / LE-Presentation_E.ppt
12 Alkali-based Scrubbing Unit State of the Art Technology flue gas FGD NO Oxidation Gas Scrubber Cleaned flue gas alternative Oxidation media Washing media Product NO Oxidation: NO+H 2 O 2 NO 2 + H 2 O or NO+O3 NO 2 + O 2 Water Scrubber for Nitric Acid Production: 3NO 2 + H 2 O 2HNO 3 + NO Alkaline Scrubber for Fertilizer Production: NO + NO 2 + 2NH 3 + H 2 O 2NH 4 NO 2 Fertilizer is produced in several processes using O 3 or H 2 O 2 for NO oxidation and subsequent alkaline scrubbing. (e.g. Walter-Process) Nitric acid produced from NO rich gas needs a continuous oxidation of the released NO. This increases the amount of oxidation media in the washing media or decreases the NO removal. 2NO 2 + 2NH 3 + H 2 O NH 4 NO 2 + NH 4 NO 3 NH 4 NO 2 + 1/2 O 2 NH 4 NO 3 12 N. Schödel / 0901 / LE-Presentation_E.ppt
13 Alkali-based Scrubbing Unit Linde Concept flue gas FGD Cleaned flue gas Gas Scrubber alternative Regeneration Alkaline washing media Product (Fertilizer) NO and SO 2 Oxidation: NO+1/2O 2 NO 2 SO 2 + NO 2 SO 3 + NO Alkaline Scrubber: SO 2 + 2NH 3 + H 2 O (NH 4 ) 2 SO 3 SO 3 + 2NH 3 + H 2 O (NH 4 ) 2 SO 4 NO + NO 2 + 2NH 3 + H 2 O 2NH 4 NO 2 2NO 2 + 2NH 3 + H 2 O NH 4 NO + NH 2 4 NO 3 Regeneration: NH4NO2 N2 + 2H20 (decomposition > 50 C) Ammonia solution washing media is also able to remove NO 2 remove water-insoluble NO in presence of NO 2 remove SO 2 and SO 3 The resulting nitrites and nitrates can be oxidized to a mixed sulfur/nitrogen fertilizer decomposed to N 2 and H 2 O (Denitrification) 13 N. Schödel / 0901 / LE-Presentation_E.ppt
14 Alkali-based Scrubbing Unit Proof of Principle Tests Test conditions: NOx removal rate depending on washing media NOx removal rate (p/t/t) Nitrate, Nitrite formation depending on NO/NO 2 Nitrite decomposition (regeneration) Simultaneous removal tests Pressure: bar Temperature : C Gas composition: CO 2 70 mol% O 2 1,5-6 mol% NO Vppm SO Vppm N 2 balance Results NOx removal possible Removal improved at higher pressure Simultaneous SOx and NOx removal possible Nitrite selectivity > 90% achievable Patent application prepared 14 N. Schödel / 0901 / LE-Presentation_E.ppt
15 Alkali-based Scrubbing Unit Proof of Principle Tests Example: NOx Removal 10 bar; 3,0 vol% O2; 70 vol% CO NO removal in alkaline washers is two times faster than NO oxidation itself U p p e r NO vppm Mechanism of NO removal is understood Probable Mechanism: [NO] >> [NO 2 ] 2NO + O 2 2NO 2 s e c t i o n tim e in sec. NO+NO 2 +2NH 3 +H 2 O 2NH 4 NO 2 4NO + O 2 + 4NH 3 +2H 2 O 4NH 4 NO 2 Example: Simultaneous SOx and NOx Removal t =0 sec. l o w e r s e c t i o n SO2 in vppm Feed Bottom 0 sec 13 sec 25 sec 39 sec. Sample SO2 conversion 11 bar; 23 C; 3,0 vol% O NO conversion SO2 NO NO in vppm Conversio n 99.5% 85% simultaneous removal feasible 15 N. Schödel / 0901 / LE-Presentation_E.ppt
16 Alkali-based Scrubbing Unit Technology Comparison Washing media Water Oxidation requiremen t 100% NO Oxidation 100% SO2 Oxidation required Product Benefits Disadvantage Acids Only water as washing media Material handling (corrosion) For high NOx removal sufficient residence time in the scrubber is needed Acid mixture in case of simultaneous SOx and NOx removal NH3 in water Only 50% NO 2 in NOx required No SO2 Oxidation required Fertilizer or N 2 No corrosion issue Increased NOx removal rate Lower residence time is needed (smaller process units) Reduction to N 2 possible Ammonia consumption Defined product 16 N. Schödel / 0901 / LE-Presentation_E.ppt
17 Feasibility of Concepts Gate Process Gate 1 Gate 2 Gate 3 Gate 4 Gate 5 Final Gate R&D Idea Prefeasibility Feasibility Lab Scale Pilot Scale Commercial Scale LINDE Phase Gate Criteria for R&D projects: e.g. Technology ownership / patent situation Implementation concept Time schedule / time to market Technical feasibility Process economics 17 N. Schödel / 0901 / LE-Presentation_E.ppt
18 Feasibility of Concepts Economics Comparison to State of the Art Technology Reference Case: 250 MW (electrical) oxyfuel power plant CO2-content: ~75 vol% High dust conventional NH3-DeNOx with 90% NOx conversion Preliminary Cost Estimate Commercial NH 3 -SCR High Dust fast-scr bar Alkaline Wash Unit 10 bar Conversion Up to 90% Up to 90% 80-95% Invest costs total % High Dust NH3-DeNOx Utilities total % High Dust NH3-DeNOx Overall cost (10% depreciation/a) % High Dust NH3-DeNOx N. Schödel / 0901 / LE-Presentation_E.ppt
19 Thanks for your attention.
20 New Process Development Common DeNOx Technology in Gas Processing Units Principles of NO x Reduction Chemistry NO Oxidation +Oxidation media or Radical formation or catalytically via O 2 catalytic Reduction +Reduction media non catalytic Reduction N 2 NO Reduction 2 Absorption e.g.+h 2 O/NH 3 /(NH 4 ) 2 SO 3 selective Nitric acid, Nitrates, Nitrites, Fertilizer not selective N 2 N 2 Walther process, Electron beam process SCR and SNCR units Absorption +Absorption media for NO Reduction +Reduction media N 2 EDTA - process Catalytic Decomposition N 2 20 N. Schödel / 0901 / LE-Presentation_E.ppt
21 New Process Development Common DeSOx Technology in Gas Processing Units DeSOxprocess regenerative wet dry dry Wellman-Lord DESONOX Activated carbon process SOLINOX Sorbent injection process Principle: Sorption Desorption Product: Products are mainly SO 2 rich gas streams or sulfuric acids, not regenerative semi -dry Spray dryer absorption Principle: Chemical Absorption Lime (stone) scrubbing Product: wet Sodium(hydroxide) scrubbing Ammonia scrubbing (Walther) Hydrogen peroxide scrubbing Seawater scrubbing In general, the final product is gypsum. Special applications are producing sulfuric acid, Ammonia sulfates (fertilizer) 21 N. Schödel / 0901 / LE-Presentation_E.ppt
22 New Process Development Simultaneous Removal Technology in Gas Processing Units SOx Sorption / Desorption SOx rich process gas CuO process NOx Reduction N 2 Activated carbon process SOx NOx + Oxidation media Oxidation Oxidation Absorption Fertilizer Walther Simultan - process SOx Absorption Gypsum or Fertilizer EDTA Process NOx Reduction N 2 Simultaneous removal rates of NOx and SOx are generally lower compared to the selective processes Removal rates are depending on SOx/NOx Ratio 22 N. Schödel / 0901 / LE-Presentation_E.ppt
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