Fully Integrated Simulation of a Cement Plant with a Carbon Capture Ca-looping Process Dursun Can Ozcan, Hyungwoong Ahn, Stefano Brandani Institute for Materials and Processes School of Engineering University of Edinburgh 2012/20/08 1
Carbon Capture for Cement Industry CO 2 Emission from Cement Industry Cement is a key construction material (3.78 billion tons in 2012). Large industrial source of CO 2 emission (5% of worldwide emission). Around 50% of the total emission accounts for calcination of limestone in raw material. Energy efficiency improvements are limited, essential to deploy a carbon capture technology to reduce CO 2 emission up to 90%. Technical Options for Carbon Capture Oxy-combustion Technical uncertainty in operating cement kiln under the condition of oxy-combustion Post-combustion amine process Stripper steam should be generated with an external boiler. new boiler, FGD, SCR Post-combustion Ca-looping process The absorbent is one of the cement raw materials purge CaO can be used for cement manufacture The operating condition of a carbonator can be found in cement plant. 2
Chemical Reactions Reaction H (kj) For 1kg of CaCO 3 (Calcite) CaO + CO 2 (g) +1782 CaCO 3 AS4H (pyrophyllite) α-al 2 O 3 + 4SiO 2 (quartz) + H 2 O(g) +224 AS4H AS2H2 (kaolinite) α-al 2 O 3 + 2SiO 2 (quartz) + 2H 2 O(g) +538 AS2H2 2FeO OH (goethite) α-fe 2 O 3 + H 2 O(g) +254 FeO OH 2CaO + SiO 2 (quartz) ß-C2S -734 C2S 3CaO + SiO 2 (quartz) C3S -495 C3S 3CaO + α-al 2 O 3 C3A -27 C3A 6CaO + 2 α-al 2 O 3 + α-fe 2 O 3 C6A2F -157 C6A2F 4CaO + α-al 2 O 3 + α-fe 2 O 3 C4AF -105 C4AF o The enthalpy of formation of 1kg of a Portland cement clinker is around +1757 kj/kg. Ref. Cement Chemistry, H F W Taylor, 2 nd ed. 1997. 3
Phase Change in Cement Plant Preheaters out Pre-Calciner Kiln Pre-heaters 30% sulphur reacts with oxygen Partial CaCO 3 calcination Partial clay minerals decomposition Pre-calciner CaCO 3 calcination (>90%) and clay mineral decomposition completed. Partial conversion of CaO to C 2 S. Ref. Cement Chemistry, H F W Taylor, 2 nd ed. 1997. Kiln C 2 S to C 3 S conversion. C 3 A and C 4 AF formed. Aluminate and Ferrite melting. 4
Mass and Energy Balances Mass Balance Mass in kg/s Mass out kg/s Raw meal 52.41 Clinker 31.45 Air 99.71 Flue gas Fuel From fuel drying 4.53 Wet coal to pre-calciner 2.25 From raw mill 75.57 Wet pet-coke to kiln 1.18 Excess Air 44.00 Total in 155.55 Total out 155.55 Energy Balance o 1.67 kg/s of raw meal is required to produce 1 kg/s of clinker. othe required thermal energy for unit clinker production is 3.18 MJ/kg clinker. Enthalpy in [GJ/h] Enthalpy out [GJ/h] Sensible Heat Heat by combustion Sensible Heat Raw Meal 1.82 Clinker 5.09 Air 3.23 Flue gas Fuel From fuel drying 4.63 Wet coal to pre-calciner 0.12 218.78 From raw Mill 74.13 Wet pet-coke to kiln 0.05 141.06 Excess Air 46.30 Heat lost by radiation and convection 53.29 Heat of Reaction Overall heat of reaction 181.62 (1.60 MJ/kg) Total in 365.06 Total out 365.06
Clinker Composition Bogue Mineral Alite (C 3 S) Belite (C 2 S) Tricalcium Aluminate (C 3 A) Tetracalcium Aluminate (C 4 AF) Free CaO CaO SO3 Ash Total calculation [wt %] 60.6 17.5 11.0 8.6 0.0 2.3 0.0 100.0 Simulation [wt%] 60.4 17.2 10.9 8.2 0.0 2.5 0.8 100.0 The simulated clinker compositions are in a good agreement with those estimated by Bogue equation.
Selection of an Optimal Feed Stream for Ca-looping Process To Atmosphere To Atmosphere Bag Filter Collected Dust Bag Filter Coal Pet Coke Fuel Drying Bag Filter To Atmosphere Primary Air Secondary Air Raw Meal Raw Mill 1 st Preheater 2 nd Preheater 3 rd Preheater 4 th Preheater Pre-Calciner Kiln Cooler Clinker Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Cooling Air Tertiary Air The flue gas temperature and CO 2 mole fraction varies over the process The optimal flue gas stream for the capture process should be selected taking the operating condition of a selected capture unit, ease of heat integration, and CO 2 partial pressure into account. 7
Process Integration in Retrofit Case 40 Raw mill 1 st Preheater 2 nd Preheater 3 rd Preheater 4 th Preheater Precalciner Kiln CO 2 concentration (mole%) 30 20 10 0 The CO 2 concentration at the endof-pipe stream is ~22 vol% The flue gas at the 3 rd preheater exit has a higher CO 2 concentration (~35 vol%) Temperature [C] 1600 1400 1200 1000 800 600 400 200 0 Raw Mill 1 st Preheater 2 nd Preheater 3 rd Preheater 4 th Preheater Pre-Calciner Kiln Cooler Gas Flow Solid Flow Flue gas needs to be heated up to Flue gas temperature is around 650 C 650 C. Relatively low CO 2 no preheating is required. concentration. 8
Process Integration in Retrofit Case 1) The flue gas from 3 rd Preheater is diverted to Ca-looping process for carbon capture. 2) CO 2 depleted flue gas from carbonator is routed to the 2 nd Preheater for the raw material preheating. 3) Part of excess air from the cooler is used for additional raw material heating. 4) Purge from the carbon capture calciner is sent to the kiln. Excess Air Gas Flow Solid Flow ASU Steam Cycle CO2 Compression C Heat stream Qcarbonator Oxygen Make-up To Atmosphere CaCO3 Pet Coke Bag Filter Collected Dust To Atmosphere Bag Filter Carbonator CaCO3 CaO Blower Calciner Purge Coal Pet Coke Fuel Drying Primary Air Bag Filter Raw Meal Raw Mill 1 st Preheater 2 nd Preheater 3 rd Preheater 4 th Preheater Precalciner Kiln Secondary Air Cooler Excess Air Clinke Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Air In-leak Tertiary Air Cooling Air 9
Ca-Looping Process Compressed CO 2 CO 2 Compression gas flow solid flow CO 2-rich flue gas Make-up (CaCO 3) Q 1 Q 2 CO 2 degraded flue gas Carbonator Fuel Calciner O 2 Heat extraction (Q 3) Flue gas from power plant Blower Air Separation Unit N 2 Q 4 Purge to cement plant (CaO, CaSO 4, ash) Calciner needs to operate at 930 o C for 100% calcination while carbonator operates at 650 o C. CaO loses its capacity over the cycles theoretical capture rate is determined by two flowrate ratios: F R /F CO2 and F 0 /F CO2. The operation conditions inside carbonator and calciner are also favourable to the SO 2 capture (effects of sulfidation on the maximum carbonation degree). 10
Carbonator Model Two mathematical models for carbonator have been compared in the study; The simple model (all active fraction of CaO reacts with CO 2 ) The rigorous model 1 : * CFB model operates in the fast fluidization regime * Particle distribution part has been applied from K-L model; lower dense region and upper lean region * The CO 2 concentration at the exit has been estimated from the gaseous material balance by considering the first order kinetic law of carbonation degree. The effect of sulfidation was considering by adjusting the k and X r constants corresponding to sulfidation level of Piaseck limestone 2 (valid up to1% sulfidation) 1 Romano, M.C. Modelling the carbonator of a Ca-looping process for CO 2 capture from power plant flue gas. Chem. Eng. Sci. 2012, 69 (1), 257-269. 2 Grasa, G.S.; Alonso, M.; Abanades, J.C. Sulfidation of CaO particles in a carbonation/calcination loop to capture CO 2. Ind. Eng. Chem. Res. 2008, 47, 1630-1635. 11
Carbonator Model 6 F R /F CO 2 5 4 3 lower limit upper limit F 0 /F CO 2 Sulfidation levels (%) 0.2 0.22 0.25 0.25 0.3 0.28 0.4 0.33 0.6 0.42 0.8 0.50 1.2 0.62 1.6 0.70 3.5 0.90 5.8 1.00 Rigorous model (w/ S) Rigorous model (w/o S) Simple model 2 1 0 1 2 3 4 5 6 F 0 /F CO 2 To keep sulfidation rate maximum at 1%, the S content of fuel has been adjusted. (5.3% 3.6%) 12
Carbonator Model o All the mathematical models for the carbonator have been solved in Matlab, and the carbonator unit was incorporated into the Unisim process simulation (Unisim Matlab Unisim) Unisim User Unit Operation for Carbonator Simulation The interface of the model in Unisim 13
Simulation Retrofit Case Simulation Basis Target: 90% CO 2 recovery in the carbonator and 95+% CO 2 purity. The total clinker production rate is kept constant. ASU : 95% O 2 purity. CO 2 product is compressed up to 150 bar. 14
Results 10 Thermal energy consumption per unit clinker [GJ th /ton] 9 8 7 6 5 4 3 2 1 0 Total energy input (Fuel + ASU+Blower) Total fuel input Fuel input to calciner Fuel input to pre-calciner and kiln 0 1 2 3 4 5 6 F 0 /F CO 2 The thermal requirement for the pre-calciner and kiln decrease reduction in calcite fed to raw mill, and calcite is completely calcined in the calciner. The heat requirement for the calciner shows a minimum. The energy requirement for ASU and blower has decreasing trend less gas flow into the carbonator. 15
Power per unit clinker [MWh/ton] 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Gross power generation Total power consumption CO₂ compressor power Cement plant power ASU+Blower power 0 1 2 3 4 5 6 F 0 /F CO 2 The gross power generation efficiency is estimated as 46 %. It is predicted that the power generated in steam cycle can exceed the power demand in the cement plant integrated with a Ca-looping process up to 2.9 F 0 /F CO2. 16
CO 2 recovery (avoided) [%] 100 98 96 94 92 90 88 0 1 2 3 4 5 6 12 Carbon Dioxide Recovery At oxy-calciner Energy Consumption without Heat Recovery 10 At oxy-calciner Energy Consumption with Heat Recovery At oxy-calciner 8 6 4 2 0 Incremental energy consumption per CO 2 avoided [GJ/ton CO 2 ] F 0 /F CO 2 The percentage of CO 2 avoided is between 92 99 %. Oxy-calciner only no carbonator and all calcites are calcined in the calciner. The incremental energy consumption for 5.8 case is 5.3 GJ/ton CO 2 while that value can be estimated as 4.6 GJ/ton CO 2 for integrated MEA process. With heat recovery, the resulting energy consumption decreases to 2.3 GJ/ton CO 2 for 5.8 case.
Conclusions A way of capturing CO 2 from cement plants by integrating it with a Ca-looping process has been investigated. The clinker composition is in a good agreement with the Bogue equation. The gas stream leaving the 3 rd preheater was selected to be a feed suitable for Ca-looping capture unit since o it does not have to be preheated o it has a higher CO 2 partial pressure and lower total volumetric flow rate o a simpler design of steam cycle for heat recovery is possible Low sulphur fuel is required to minimize CaO circulation. 18
Conclusions Given the 90% carbon capture in the carbonator, the CO 2 avoided in overall process ranges from 92% to 99% depending on the F 0 /F CO2 ratio. The fuel consumption of 2.3 to 3.0 GJ/ton CO 2 avoided which depends on the F 0 /F CO2 ratio with a heat recovery system is estimated. The estimation of heat recovery can be made more accurate by a follow-up study on a detailed steam cycle. 19