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Combined Exergy Analysis and Energy Integration for Design
Optimization of Nitrogen Fertilizer Plants
Conference Paper · July 2017
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Daniel Flórez-Orrego Shivom Sharma
École Polytechnique Fédérale de Lausanne École Polytechnique Fédérale de Lausanne
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Thermal and Environmental
Engineering Laboratory
30th International Conference on Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy
Systems, ECOS 2017, San Diego, CA, July 2nd – 6th, 2017
Combined Exergy Analysis and Energy Integration for Design
Optimization of Nitrogen Fertilizer Plants
Daniel Flórez-Orrego, Shivom Sharma, Silvio de Oliveira Junior and Francois Marechal
Swiss Government Excellence Scholarship for Foreign Scholars and Artists (ESKAS)
Prof. Dr. Francois Maréchal Prof. Dr. Silvio de Oliveira Jr.
École Polytechnique Fédéral de Lausanne Polytechnic School, University of São Paulo
RELEVANCE
• Demand for fertilizers has surpassed Brazilian production capacity → vulnerability to variations in prices in the
international markets and natural gas prices.
• SNF technology has undergone radical developments. But the minimum theoretical consumption ~20GJ/tNH3
<<<< 28-31 GJ/tNH3 BAT .
• Higher overall energy efficiency increase of 5% for the short/midterm (10-20 years) and 20% (30-40 years) for the
long term (European Roadmap for Process Intensification).
• Systematic methods allows an holistic point of comparison of the First law and Second law analysis.
1.18 tair/tNH3
160 kWh/tNH3 PROCESS FLOWSHEET
1000 tNH3/day
790°C
1.56 twater/tNH3 35 bar
Capital cost: US$ 100/tNH3
0.46 tNG/tNH3
4720 MJ/tNH3
Operation cost (NG):
U$ 300-400/tNH3
Energy Consumption:
1.2 tCO2/tNH3 28-31 GJ/tonNH3
Efficiency: 66%
237 kWh/tNH3 Process water: 28 m3/h
450°C Steam: 4.49 tHPsteam/tNH3
200 bar
0.08 tCO2/tNH3
Resources
Furnace
Refrigeration
Cooling tower
Steam Network
Gas Turbine (?)
Heat pump (?)
Reference energy and material costs
OPTIMAL UTILITY INTEGRATION
Minimum Operating Cost
Natural Gas Cost Electricity Cost CO2 Cost Water Cost
Most appropriate operation parameters and sizes of the utility systems
CARBON CAPTURE: CHEMICAL AND PHYSICAL SOLVENTS
Chemical Solvents:
Tertiary and secondary amines mixture reduces the reboiler heat duty (30%wt. MEA: 3.8 MJ/kgCO2)
Recirculation rate 11.9 m3/tNH3 Condenser duty 3706 MJ/tNH3
17.2 m3/tNH3 4535 MJ/tNH3 CO2 captured
1.2 tCO2/tNH3
Pump power 13.27 kWh/tNH3
18.57 kWh/tNH3
Reboiler duty
Rich amine CO2 loading 0.51 kmolCO2 /kmol DEA 5%wt. DEA + 45%wt. MDEA: 3.17 MJ/kgCO2
17.7% CO2 mol 0.45 kmolCO2 /kmol DEA 35%wt. DEA: 3.69 MJ/kgCO2
6550 kmol/h
CARBON CAPTURE: CHEMICAL AND PHYSICAL SOLVENTS
Physical Solvent:
DEPG (Selexol) eliminates desorber over-head condensation and reboiler duty requirements
CO2 stream cooling
Recirculation rate 2.598 m3/tNH3
222 MJ/tNH3
Pump power 66.7 kWh/tNH3
CO2 captured
1.2 tCO2/tNH3
17.7% CO2 mol
6550 kmol/h
Absence of regenerator
DEPG requires higher solvent circulation rates at high temperatures (to avoid additional refrigeration)
Reevaluate the integration strategies and limitations present in the chemical absortion
REACTOR PROFILE INTEGRATION
- Exothermic Reactors:
- Endothermic Reactors:
COMPOSITE
Secondary HT Primary AND
Reformer Reformer Duty GRAND COMPOSITE CURVES
Heat Rec.
Reactants
Preheating Steam Network?
Reduced
Heat pump? Desorber DEA+MDEA -based
Duty DEA -based
Secondary
Reformer
Avoid auxiliary Primary
boilers Preheating? Reformer
(below pinch)
Steam Network?
Process
MP Steam
DEPG -based
PROCESS INTEGRATION
Minimum Energy Requirements
PROCESS INTEGRATION
Auto-Thermal O2-rich Reformer
- Saturator: (Reduce Stack emissions)
Transfer steam generation duty to saturator (30%),
evaporation can be carried out at the partial
pressure of the water in the mixture. Lower
temperature energy source allowed, avoid boiler Self-Sufficient zone
Prereformer
plateau. Concept • Gas Heated Reformer (GHR)
• Gas Heated Pre-Reformer
- Prereformer: Standalone
Boiler Only
In the prereformer an endothermic reforming
reaction at lower temperatures is carried out in Saturator
order to reduce the high temperature reformer duty Only
Reduce inlet actual reactor temperature to better approach the
lower theoretical equilibrium ones
DEA-based plant
PROCESS INTEGRATION
INTEGRATED CURVES
Operating mode 1. Grid MODE
Heat Pump
Activated
Electricity grid
No air preheating
U$1.9/tNH3 Heat Pump Inv. Cost No steam superheating
PROCESS INTEGRATION
INTEGRATED CURVES
Operating mode 2. Auto MODE
Heat Pump
Deactivated
Optimize MP
Steam use
No electricity grid (auto CHP)
- Cogeneration efficiency and costs ratio CNG/CEE Air preheating for DEPG-based
Steam superheating
PROCESS INTEGRATION
INTEGRATED CURVES
Operating mode 3. MIXED
Conventional Steam
HT Utility
Pressure Levels
Integration?
Heat Pump
deactivated
Mixed
Electricity Grid + Steam Superheating
Air Preheating for DEPG-based
PROCESS INTEGRATION
Operating Cost vs. Operating mode
Mode 1: Electricity grid, No air preheating, No steam
superheating
Mode 2: No electricity grid (auto CHP), Air preheating for
DEPG-based, Steam superheating
Mode 3: Mixed, Electricity Grid + Steam Superheating, Air
Preheating for DEPG-based
The operating cost is reduced when operating in a mixed mode by using physical absorption systems.
Lowest OP cost: Mixed < Auto < Grid
PROCESS INTEGRATION
Natural Gas Consumption:
- Almost const. NG consumption operating modes 1 and 2,
regardless the solvent used. Constrain utilization to high
temperature utility (Reformer).
- Marked reduction of natural gas consumption in mixed
operation (mode 3) for physical solvents-based configuration:
Reactants preheating.
BOTH EE and NG consumption
can be reduced by preheating
rect., operating in mixed mode
and partly allowing EE import
Electricity Import:
- EE import remains invariably high in operation mode 1, as NG
consumption remains low.
- As NG import decrease, imported EE in mixed operation
increases (mode 3). However, still lower than for chemical
absorption-based case.
PROCESS INTEGRATION
Typical plant
Autonomous
MEA, DEA solvents
Florez-Orrego et al. (2016)
- Importation of electricity grid (mode 1): Comparable energy efficiencies, highly dependent on the cNG and cEE costs ratio.
- Preheating allows simultaneously reducing the net EE and NG consumption in physical absorption-based process.
PROCESS INTEGRATION
Carnot Composite Curves
Is it the electricity import the most cost-effective option in term of minimum operating cost? And autonomy?
DT Non-profited
Large Driving Force Self-Sufficient zone
Steam (< 100 bar)
Cold stream temperature:
200°C-500°C
Condenser Duty
No Grid
Air Preh (DEPG)
Steam Generation
DEPG absorption-based ammonia plant
Fuel (NG)
Gas Turbine System
Comb. Fuel Heat
Preheat Turbine
Inlet T
Stoichiometry Air
Fuel (NG) Contribution Compr.
Gas Turb.
Work Elec.
Comb.
Stoich. Air Heat Rec.
Preheat
Stack
Compr. Gas Turb.
Work Elec.
Air Heat
Comb. Heat Rec. Preheat Turbine
Air Inlet T
Excess Air
Stack Contribution Compr.
Gas Turb.
Work Elec.
Excess Air Heat Rec.
Increasing the degree of integration of the utility systems and
the process streams above the pinch point Stack
PROCESS INTEGRATION
Gas Turbine System: INTEGRATED CURVES No Grid
Operation Cost: 278.6 U$/tNH3 Operation Cost: 277.6 U$/tNH3
GT net power: 19016 kW GT net power: 15610 kW
Annualized GT cost: 2.56 U$/ tNH3 (9.94 M EUR, Purch.) Annualized GT cost: 2.50 U$/ tNH3 (7.63 M EUR, Purch.)
Stoichiometric Air
contribution
High T
utility
Excess Air
contribution
Self-Sufficient zone
ATR – GHR (?)
Heat Pump Activated
DEA-based plant configuration DEPG-based plant configuration
PROCESS INTEGRATION
Gas Turbine integration No Grid
DEA-based plant configuration DEPG-based plant configuration
Natural Gas Consumption: 69543 kW (non-feedstock Natural Gas Consumption: 61835 kW (non-feedstock
exergy only) or equiv. 6192 MJ/tNH3 exergy only) or equiv. 5619 MJ/tNH3
Exergy destroyed: 71372 kW (6354 MJ/tNH3) Exergy destroyed: 68522 kW (6226 MJ/tNH3)
Exergy efficiency: 78.5 % Exergy efficiency: 78.9 %
By integrating a GT system Operating Cost can be reduced up to 15%
Exergy destroyed can be decreased up to 40% and exergy efficiency be increased up to 19%
GT investment cost affordability depends on Econ.&Op. factors Florez-Orrego et al. Energy (2015)
Single Pressure
Ammonia Loop
(150 bar)
Bring down process irreversibilities while reducing the power consumption in
the syngas compression and ammonia refrigeration (14%)
Dual Pressure
Configurations
(83/200bar)
PROCESS INTEGRATION
Ammonia Converter
Reaction temperature
Boiler temperature
Heat recovered by steam
raising
Heat recovered at the
reaction temperature
PROCESS INTEGRATION
furnace temperature
Primary Reformer
Reaction temperature
Gradually increasing the reaction temperature, while minimizing the large driving forces
in the inlet of the reformer.
Heat supplied at the
furnace temperature
Gas heated reformers, adiabatic reformers at lower temperature and
chemically recuperated steam reformers
Heat supplied at the
reaction temperature
CONCLUSIONS
• A systematic methodology based on a MILP mathematical approach allows to determine the most suitable
utility systems that satisfy the minimum energy requirement (MER) with the lower resources
consumptions and cost.
• By proposing the most appropriate operation characteristics of the utility systems, further opportunities for
producing surplus electricity and heat have been identified. This allowed to increase the cogeneration system
efficiency and reduce the whole plant operation cost
• By operating either in a mixed mode or in autonomous mode by integrating a GT cogeneration systems and
physical absorption systems, the process irreversibilities and operation cost can be radically reduced, whereas
the plant efficiency can be increased. The autonomy of modern ammonia production plants also can be still
guaranteed.
• The energy integration profile for the reactive systems is developed in order to reveal the potential
energy saving opportunities that may remain hidden when conventional integration approaches are
performed.
Colombian Department of Science,
Brazilian National Agency of
Technology and Innovation
Petroleum, Natural Gas and Biofuels
THANKS FOR YOUR ATTENTION
Swiss Federal Commission for
Scholarships for Foreign Students
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