Simulation of Electrolyte Processes: Status and Challenges
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1 Simulation of Electrolyte Processes: Status and Challenges Paul M Mathias and Chau-Chyun Chen Aspen Technology, Inc. 12 March 2002 AIChE Spring 2002 Meeting AIChE 2002 Spring Meeting.
2 Summary Opportunities/needs for electrolyte simulations Special complexities of electrolyte simulations Successes and status Future challenges AIChE 2002 Spring Meeting 2
3 Electrolyte applications are widespread in chemical technology Wastewater treatment Seawater desalination Gas scrubbing Normal and extractive crystallization Salt-effect enhanced extraction and distillation Hydrometallurgical processes Salt-added bioseparations.. AIChE 2002 Spring Meeting 3
4 Use of process simulation is standard practice, even for electrolyte processes Study process alternatives Assess feasibility and preliminary economics Interpret pilot-plant data Process design and optimization Pollution control Plant trouble-shooting Plant retrofit AIChE 2002 Spring Meeting 4
5 Finance / Planning/R&D Conceptual Design Process Engineering Detailed Engineering Construction / Start-up Operations / Asset Mgt,PSURYH&DSLWDO (IILFLHQF\ Reliable and consistent economic evaluation and project scheduling Synthesis for systematic exploration of design alternatives Modeling to accurately predict process performance AIChE 2002 Spring Meeting 5
6 Finance / Planning/R&D Conceptual Design Process Engineering,PSURYH Detailed (QJLQHHULQJ Engineering 4XDOLW\ (IILFLHQF\ Construction / Start-up Operations / Asset Mgt Concurrent engineering for error free and efficient workflow Consistent properties, models and economics throughout the life cycle Downstream integration with detail design (e.g. Intergraph) Fast evaluation of optimized alternatives AIChE 2002 Spring Meeting 6
7 Finance / Planning/R&D Conceptual Design Process Engineering Detailed Engineering Construction / Start-up Operations / Asset Mgt Consistent Models and Physical Properties for Accurate evaluation and prediction of plant performance Ability to solve large scale complex optimization problems On-line process monitoring and optimization,qfuhdvh 2SHUDWLRQDO 3URGXFWLYLW\ AIChE 2002 Spring Meeting 7
8 Special challenges of electrolyte processes Many extra species form due to ionization and complexation (e.g., aqueous FeCl 3 has 14 different species.) Solution nonideality is complex because of ionic forces and numerous species. Chemical and physical equilibrium must be solved simultaneously, causing problems for user interfaces and flash algorithms Kinetics and mass transfer often need to be included to develop an accurate model AIChE 2002 Spring Meeting 8
9 Successes and Status Aqueous FeCl 3 Sour water (aqueous CO 2 /H 2 S/NH 3 ) Scrubbing of CO 2 /Cl 2 with caustic Nitric acid AIChE 2002 Spring Meeting 9
10 FeCl 3 Aqueous Chemistry FECL3 l FECL2+ + CL- FE2OH2+4 l 2 FEIII OH- FECL2+ l FECL+2 + CL- FECL4- l FECL3 + CL- FECL+2 l FEIII+3 + CL- FEOH2+ l FEOH+2 + OH- FEIIIOH3 l FEOH2+ + OH- FEIIOH4- l FEIIIOH3 + OH- FEOH+2 l FEIII+3 + OH- H2O l H+ + OH- HCL l H+ + CL- Salt FECL3W6 l FEIII CL- + 6 H2O Salt FECL3-S l FEIII CL- Salt FEOH3-S l FEIII OH- Salt FECL3W25 l FEIII CL H2O Salt FECL3W2 l FEIII CL- + 2 H2O AIChE 2002 Spring Meeting
11 of 1 Mole FeCl 3 in Moles Water at 25qC and 1 atm Comp Moles Comp Moles H2O FECL HCL 2.634e-09 FEIII FEIIIOH e-09 FEOH e-06 FECL OH e-13 FE2OH e-07 FECL FECL e-06 FEIIOH e-16 FEOH H CL Fe complexes with OH to form FEOH+2, which shifts the water dissociation to form H+ ions. ph = 2.22 AIChE 2002 Spring Meeting
12 FeCl 3 Aqueous Chemistry FECL3 l FECL2+ + CL- FE2OH2+4 l 2 FEIII OH- FECL2+ l FECL+2 + CL- FECL4- l FECL3 + CL- FECL+2 l FEIII+3 + CL- FEOH2+ l FEOH+2 + OH- FEIIIOH3 l FEOH2+ + OH- FEIIOH4- l FEIIIOH3 + OH- FEOH+2 l FEIII+3 + OH- H2O l H+ + OH- HCL l H+ + CL- Salt FECL3W6 l FEIII CL- + 6 H2O Salt FECL3-S l FEIII CL- Salt FEOH3-S l FEIII OH- Salt FECL3W25 l FEIII CL H2O Salt FECL3W2 l FEIII CL- + 2 H2O AIChE 2002 Spring Meeting
13 ph of Aqueous FeCl 3 Solution at 25ºC ph E-08 1.E-06 1.E-04 1.E-02 1.E+00 Molality of FeCl 3 AIChE 2002 Spring Meeting
14 Sour Water System 7HPSHUDWXUH &DQG & /LTXLG&RPSRVLWLRQ 1+ PRODO ZW &2 PRODO ZW + 6 PRODO ZW + 2 EDODQFH AIChE 2002 Spring Meeting 14
15 Sour Water System - Model Vs. Data NH 3, CO 2, H 2 S Treated as Molecular Species Calculated Partial Pressures (mmhg) NH3 CO2 H2S Calc=Exp Experimental Partial Pressures (mmhg) AIChE 2002 Spring Meeting
16 Sour Water System - Model Vs. Data Electrolyte Speciation Included Calculated Partial Pressure (mmhg) NH3 CO2 H2S Calc=Exp Experimental Partial Pressure (mmhg) AIChE 2002 Spring Meeting
17 Electrolyte Reactions in Sour Water System H 2 O H + + OH - NH 3 (aq) + H 2 O NH 4+ + OH - CO 2 (aq) + H 2 O H + + HCO - 3 HCO - 3 H + + CO 2-3 NH 2 CO 2- + H 2 O NH 3 (aq) + HCO - 3 H 2 S(aq) H + + HS - HS - H + + S 2- AIChE 2002 Spring Meeting
18 Scrubbing of Cl 2 /CO 2 Gas with Caustic Caustic 1,200 kg/hr H 2 O 100+ kg/hr NaOH Gas 2.3 kmol/hr H 2 O 0.1+ kmol/hr CO kmol/hr Cl kmol/hr N 2 25 C 1 atm Scrubbed Gas Liquid Study scrubbing capacity as a function of CO 2 level and NaOH in caustic feed AIChE 2002 Spring Meeting
19 Aqueous Chemistry in Caustic Scrubbing of Cl 2 /CO 2 Salt Dissociation HCL H+ + CL- HCLO H+ + CLO- CO2 + H2O H+ + HCO3- H2O H+ + OH- HCO3- H+ + CO3-2 CL2 + H2O H+ + CL- + HCLO NACO3- NA+ + CO3-2 NAHCO3 NA+ + HCO3- NAHCO3-S NA+ + HCO3- NAOH OH- + NA+ AIChE 2002 Spring Meeting
20 Chlorine Mole Fraction in Exit Gas Cl2 Mole Fraction in Exit Gas E-05 1E-06 1E-07 1E-08 1E-09 1E-10 The numbers in the legend refer to the CO 2 flow in kgmole/hr High CO 2 Low CO NaOH:Cl 2 Mole Ratio AIChE 2002 Spring Meeting 20
21 0.009 Precipitation of NaHCO 3 Precip of NaHCO3 (NaHCO3/NaOH) The numbers in the legend refer to the CO 2 flow in kgmole/hr High CO 2 Low CO NaOH:Cl 2 Mole Ratio AIChE 2002 Spring Meeting 21
22 Challenges of Nitric Acid Modeling Performance is flow rate and pressure sensitive Multiple reactions occur in most equipment, including pipes, gas coolers, heat exchangers and condensers Special physical properties are needed for nitric acid VLE and heat of mixing calculations Absorption tower has rate-limited and equilibrium vapor and liquid reactions, rate-limited mass transfer, and cooling coils on most trays Many recycle streams for heat and power integration AIChE 2002 Spring Meeting
23 Electrolyte NRTL and Chemistry High Accuracy for thermodynamic properties: ƒ Vapor-liquid equilibrium ƒ Enthalpy ('H mix, C p ) ƒ Density H O+HNO 2 3 H O+ 3 + NO 3 AIChE 2002 Spring Meeting
24 Excess Enthalpy of Mixing of Nitric Acid- Water Mixtures at 25 C Excess Enthalpy (Cal/g) Weight% HNO 3 AIChE 2002 Spring Meeting 24
25 Heat Capacity (Cal/gm.K) Heat Capacity of Nitric Acid-Water Mixtures at 25 C Weight% HNO 3 AIChE 2002 Spring Meeting 25
26 Txy Diagram of Nitric Acid - Water at 760 Torr Temperature ( C) Full line is calculated dew point Dashed line is calculated bubble point Points are experimental data Liquid or Vapor Mole Fraction of HNO 3 AIChE 2002 Spring Meeting 26
27 Kinetics and Mass Transfer for Absorber Three gas-phase reactions: 1. 2NO + O 2 mo 2NO 2 -- Kinetic 2. 2NO mo 2 N 2 O N 2 O 4 + 2H 2 O mo 4HNO 3 + 2NO -- N 2 O 4 (g) o N 2 O 4 (l) Implemented in user subroutines NOABS Reaction 3 rate correlated as a function of: Temperature N 2 O 4 partial pressure Tray dimensions (e.g., column diameter) Liquid-phase HNO 3 concentration AIChE 2002 Spring Meeting 27
28 Input Variables for NOABS Integer variable: 1 sieve tray; 2 bubble-cap tray Real Variable 1 Description Column diameter (m) Suggested value From equipment 2 3 Bubble-cap slot or sieve-hole submergence (m) Factor for NO 2 formation From equipment 1 4 Factor for N 2 O 4 absorption rate 1 AIChE 2002 Spring Meeting 28
29 Tuning of Absorber Model Cooling-water flow assumed proportional to number of heaters UA: U 250 Btu/hr.ft 2. F, A from equipment measurement Vapor hold-ups from plant measurement Cooling water temperature from plant data Factor for NO 2 formation to match profile Factor for N 2 O 4 absorption to match profile Procedure gives accurate NO, NO 2 in tail gas, acid strength and temperature of tailgas compared to plant data AIChE 2002 Spring Meeting 29
30 Acid-Strength Profile in Absorber 80% 70% Acid Strength 60% 50% 40% 30% 20% 10% Plant Simulation 0% Tray AIChE 2002 Spring Meeting 30
31 Temperature Profile in Absorber Tray Temp ( F) Plant Simulation Tray AIChE 2002 Spring Meeting 31
32 Future Challenges Hands-on expertise and education Predictive methods for nonideality Mixed-solvent electrolytes Systems containing small molecules, polymers and electrolytes Ionic surfactants and micelle formation Reliable flash calculations, particularly for liquid-liquid systems New applications such as corrosion AIChE 2002 Spring Meeting 32
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