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Seminario 20 April - Carnegie Mellon...
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20th April 2011 20th April 2011 Mariano Martín Assistant professor University of Salamanca (Spain) (Spain) Advisor Prof. Ignacio E. Grossmann 1
Transcript of Seminario 20 April - Carnegie Mellon...
20th April 201120th April 2011
Mariano Martín Assistant professor
University of Salamanca(Spain)(Spain)
AdvisorProf. Ignacio E. Grossmann
1
Overview
IntroductionEnergy in the worldBiofuels: Raw materials and Processes
Approach to process synthesisMethod
i e Bioethanol from corn (1st generation)i.e. Bioethanol from corn (1st generation)Results
Swichgrass as raw materialBioethanol from switchgrass (2nd generation)
Via hydrolysisVia gasification
Hydrogen from switchgrassFT diesel from switchgrassFT diesel from switchgrass
BiodieselFrom algae
2
From cooking oil
Conclusions
Introduction
Energy in the world: Contribution of renewables[1]
3[1] BP annual report 2010
Introduction
Energy in the world: Contribution of renewables
4[1] BP annual report 2010
Introduction
Energy in the world: Contribution of renewables
Only biomass provides a short term source of fuels for the transportation sector
5
Introduction
Current ethanol from sugar cane or corn and biodiesel from vegetable oils compete with the food market.
Governmental policies support the production of lignocellulosic based biofuels and the reuse of wastes and new sources (algae)
6
Introduction
Governmental policies support the production of 2nd generation of biofuels based on thehigh yields from crop to fuel
50005020Ethanol Biodiesel
There is a need foroptimized productionprocesses of bioethanol, biodiesel and other fuels
3000
4000ns per acre
biodiesel and other fuelsfrom lignocellulosicmaterials and wastes
0
1000
2000
401213
585 483
1150
59506
110 140 170
Gallo
0
7
Introduction
We use mathematicalprogramming techniques toaccomplish the synthesis ofthe production of:
bioethanol, FT‐diesel andhydrogen, from Switchgrass,
biodiesel from cooking oilor algae oil.
8
Introduction
The main concerns in biofuel industry are
energyand water consumption [2,3,4].
[2] Grossmann, I.E., Martin, M. (2010) Chinese J. Chem. Eng, 18 (6) 914‐922[3] Ahmetovic, E.; Martín, M.; Grossmann, I.E. (2010) Ind. Eng. Chem Res. 49 (17) 7972‐ 7982[4] Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2010) I&ECR doi: 10.1021/ie101175p
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Introduction
The main concern in biofuels industry is the energy efficiency of the biofuel.
C th l d d t t b d d th th itCorn ethanol was deemed to consume more energy to be produced than the one itcould generate, [2]
Energy consumption optimization is quite straightforward due to the high cost of energy
10
gy
[2] Grossmann, I.E., Martin, M. (2010) Chinese J. Chem. Eng, 18 (6) 914‐922
Introduction
Water consumption has become a major concern in process industry due to theincrease in the demand as a result of the growth of population and developmentaround the world [5,6]
Two‐thirds of the world population will face water stress by year 2025
IrrigationProcess
11[5] Elcock, D. (2008) Baseline and Projected Water Demand Data for Energy and competing Water Use Sectors, ANL/EVS/TM/08‐8 [6] Chiu, Yi‐Wen, Walseth, B., Suh, S. (2009) Environ. Sci. Technol., 43 (8), pp 2688–2692
Introduction
Water consumption in corn ethanol plants [7]:From 3 to 15 gal water/gal ethanolTh b t ibl l 2 85 l t / l th lThe best possible value 2.85 gal water/gal ethanol Mean industrial value 3.4 gal water/gal ethanol
If we use lignocellulosic raw materials [7]If we use lignocellulosic raw materials [7] 6 to 9.8 galwater/gal ethanol for switchgrass1.94‐2 galwater/gal ethanol for hybrid poplar
Biodiesel production requires [8]1 to 3 galwater/gal biodiesel
The low price of water makes it difficult to take into account in a cost function
12[7] Wu et al (2009) Argone national lab[8] Pate et al 2007 Report SAND 2007‐1349C
Method
We propose a two stage method [2] for the optimization of both:
1.‐Energy optimization: Superstructure and parameter optimizationincluding economic evaluation to select the flowsheet out of a large numberof alternatives and the main operating conditions
2.‐Water optimization:We design the optimal water network [3,4].2. Water optimization:We design the optimal water network [3,4].
[2] Grossmann, I.E., Martin, M. (2010) Chinese J. Chem. Eng, 18 (6) 914‐922[3] Ahmetovic, E.; Martín, M.; Grossmann, I.E. (2010) Ind. Eng. Chem Res. 49 (17) 7972‐ 7982[4] Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2010) I&ECR doi: 10.1021/ie101175p
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Method
Corn based ethanol
1. Energy OptimizationStructural(Multieffect columns)HEN
14[9] Karuppiah et al 2008 AIChE J. 54, 1499‐1525
Method
15[9] Karuppiah et al 2008 AIChE J. 54, 1499‐1525
Method
16[9] Karuppiah et al 2008 AIChE J. 54, 1499‐1525
Method
a‐ Superstrucure opt.b‐Supers + HENb‐Supers. + HENc‐ Supers. + HEN + Mult. d‐ Supers. + HEN + Mult (opt. reflux ratio)
17[9] Karuppiah et al 2008 AIChE J. 54, 1499‐1525
Results
Water network
Freshwater
Process Unit
Demand Unit
Sources
Treatment Unit Discharge
18[3] Ahmetovic, E.; Martín, M.; Grossmann, I.E. (2010) Ind. Eng. Chem Res. 49 (17) 7972‐ 7982
Results
Water network
Treatment Units
Organics removal Salt removalSolids removal
19[4] Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2010) Ind. Eng. Chem Res DOI: doi: 10.1021/ie101175p
Results
Industrial Averagea‐ Superstrucure opt.b‐Supers. + HENc Supers + HEN + Mult3 5
4
4.5
EtOH)
Industrial Goal
c‐ Supers. + HEN + Mult. d‐ Supers. + HEN + Mult (opt. reflux ratio)
2
2.5
3
3.5
tion(gal W
ater/gal
Industrial Goal
0
0.5
1
1.5
Water
consum
pt
0
a b c d
Fresh Water Discharge
20[3] Ahmetovic, E.; Martín, M.; Grossmann, I.E. (2010) Ind. Eng. Chem Res. 49 (17) 7972‐ 7982
Results
Switchgrass as raw materialg
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Results
Hydrolysis and Fermentation
Ethanol from hydrolysis of Switchgrass
AFEX
Dil t id
Rectification
Dilute acid
Adsorption
Molecular sieves
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Pervaporation
[12] Martín, M., Grossmann, I.E. Energy optimization of lignocellulosic bioethanol production via Hydrolysis submitted AICHE
Results
Only thermal energy
Ethanol from hydrolysis of Switchgrass
23[12] Martín, M., Grossmann, I.E. Energy optimization of lignocellulosic bioethanol production via Hydrolysis submitted AICHE
Energy consumption Energy cons. Burning ligning Cooling
Results
Ethanol from hydrolysis of Switchgrass
24[12] Martín, M., Grossmann, I.E. Energy optimization of lignocellulosic bioethanol production via Hydrolysis submitted AICHE
Results
Optimal flowsheet for the production of ethanol from hydrolysis of Switchgrass
25$0.8/gal, $161MM
[12] Martín, M., Grossmann, I.E. Energy optimization of lignocellulosic bioethanol production via Hydrolysis submitted AICHE
Results
Ethanol via gasification of SwitchgrassGasification Reforming Clean up CO/H2 Adj.
Sour gases removal
Fermentation
Catalysis
26[10] Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Results
Superstructure Problem
Low P. Indirect Gasifier High P. Direct Gasifier
Partial Steam Partialid ti
Steam reformingoxidation reforming oxidation reforming
Catalysis Fermentation Catalysis Fermentation Catalysis Fermentation Catalysis Fermentation Subproblem
(A) (B) (C) (D) (E) (F) (G) (H)
Decomposition of GDP in 8 subproblems Decision levels: Gasifier
Reforming modeReforming modeReaction of Syn Gas
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Optimization of : Syngas composition adjustmentSour gases removalEthanol purification removal
Results
Optimal flowsheet for the production of ethanol via gasification of Switchgrass
H2
Major saving due to income from excess of H2
28$0.41/gal, $335MM
[10] Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
j g
Results
G ifi
Water network
Ethanol via gasification of Switchgrass
Gasifier
Washing Solids removal
Freshwater
Wastewater Organics removal
29[4] Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2011) Ind. Eng. Chem Res DOI: doi: 10.1021/ie101175p
Results
Energy consumption: Bioethanol
30[10] Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Results
Water consumption: Bioethanol
31[4] Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2011) Ind. Eng. Chem Res DOI: doi: 10.1021/ie101175p
Results
H d f S it hHydrogen from Switchgrass
GasificationReforming
Partial oxidation
Indirect
Partial oxidation
Steam reforming
Not only bioethanol can
Direct
Steam reforming
be produced
32[11] Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
Results
H d f S it h
Reduced order model for WGSR
Hydrogen from Switchgrass
20.0044·T HX8,Reactor1 0.0924 ·H OtoCOCO _ shift _ conv ;
46815
Example at 155C
2 246815H OtoCO
T HX8,Reactor1
33[11] Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
Choi et al 2003. J. Power Sources 124, 432–439
Results
H d f S it hHydrogen from Switchgrass
34[11] Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
Results
Optimal flowsheet for the production of hydrogen from Switchgrass
$0.68/kg, $148MM
35[11] Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
Results
FT Diesel via gasification of Switchgrass
Gasification Reforming Clean upGasification Reforming Clean up
36[13] Martín, M., Grossmann, I.E. Process optimization of FT‐ Diesel production from biomass. To be submitted
Results
HidrocrackingFT‐Reactor
FT Diesel via gasification of Switchgrass
0.8
0.9
1Selectivity Diesel
Selectivity Gasoline
Conversion
Hidrocracking
0.4
0.5
0.6
0.7
ectiv
ity/C
onve
rsio
n
0
0.1
0.2
0.3Sel
e
340 350 360 370 380 390 4000
Temperature (C)
2
0.2332* 0.633 * 1 0.0039* T _ Synthesis 273 533 co
H co
yy y
1 2(1 ) ·iiw i
Bezergianni et al. (2009) Bioresour. Technol. 100, 3036–3042
37[13] Martín, M., Grossmann, I.E. Process optimization of FT‐ Diesel production from biomass. To be submitted
(1 )iw i
Song et al (2004) Korean J. Chem., 21, 308‐317.
Results
FT Diesel via gasification of Switchgrass
38[13] Martín, M., Grossmann, I.E. Process optimization of FT‐ Diesel production from biomass. To be submitted
Results
Optimal flowsheet for the production of FT Diesel via gasification of Switchgrass
$0.72/gal, $212MM
39[13] Martín, M., Grossmann, I.E. Process optimization of FT‐ Diesel production from biomass. To be submitted
Results
Biodiesel production
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Results
Superstructure flowsheet for the production of biodiesel
41[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Results
Production of biodiesel from algae
Traditional recovery of algae
Extraction
New design
42[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Results
Optimal flowsheet for the production of oil from algae
$0.17/kg$92MM
43[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Results
Production of biodiesel
1.‐Structural decisions to make. Process technologies
2.‐Reactor operating conditions to optimize bioDiesel production
3.‐Recycle of excess of methanol
Simultaneous optimization and heat integration of the process
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Simultaneous optimization and heat integration of the process
[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Results
Production of biodiesel
2
yield (79.444523 1.59614107*T 'HX24', 'Reactor5' 3.12722176*ratio _ met 1.14234895*Cat
0.01193003* T 'HX24', 'Reactor5' 0.75330856* T 'HX24', 'Reactor5' *Cat
0.40574243* T 'HX24', 'Reactor5' *ratio _ met 0
2
2
.175788313*Cat 6.56010529*Cat *ratio _ met
0.02509877*ratio _ met );
Catarci & Kerpen (1999) Trans. ASAE, 42 (5), 1203‐1210 Kulkarni & Dalai (2006). Ind. Eng. Chem. Res. 2006, 45, 2901‐2913
45
( ) g , ,
[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Results
Production of biodiesel
$0.70/gal$17MM
$0.47/gal$102MM
46[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
Summary of Results
[10] Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544[11] Martín, M., Grossmann, I.E. Comp. Chem. Eng. doi:10.1016/j.compchemeng.2011.03.002[12] Martín, M., Grossmann, I.E. Energy optimization of lignocellulosic bioethanol production via Hydrolysis submitted AICHE[13] Martín, M., Grossmann, I.E. Process optimization of FT‐ Diesel production from biomass. To be submitted[14] Martín, M., Grossmann, I.E. Process optimization of biodiesel production from cooking oil and Algae. To be submitted
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Conclusions
‐‐Biomass and waste are promising raw material for biofuels.
‐‐The range of biofuels is broad: hydrogen, bioethanol, biodiesel, green gasoline and diesel, biomethanol….
‐‐Mathematical programming techniques offer a powerful tool to synthesize bioprocesses to make them economically attractive and environmentally friendly.
‐‐It is feasible to produce second generation of biofuels but p gfurther development is required in purification and reaction technologies to increase water recycle and reuse and increase the yield of the processesthe yield of the processes.
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Acknowledgements
Prof. Grossmann Muchas gracias Dr. Ricardo LimaD R k K i hDr. Ramkumar KaruppiahDr. Víctor ZavalaDr? Sebastián TerrazasDr? Juan RuizDr? Juan RuizRosanna FrancoRodrigo López‐NegreteLin Lin YangLin Lin YangVijay GuptaRavi KarmathSumit MitraMarjtin Van ElzakkerMarcelo EscobarProf. Elvis AhmetovicProf. KravanjaLidija CucekMabel 49
University of Salamanca
from 1218
Where is the frog?
50
Just a hint.
For the rest, you have to vist Salamanca
