Jose Granjo Set2013

BIOFUEL PRODUCTION
PROCESSES BASED ON
SYSTEMATIC OPTIMIZATION
METHODOLOGIES
September 18th, 2013
Coimbra, Portugal
Jos F.O. Granjo
josegranjo@eq.uc.pt
GEPSI PSE Group, CIEPQPF
Chemical Engineering Department
University of Coimbra, Portugal
Nuno M.C. Oliveira
nuno@eq.uc.pt
INTEGRATED BIOFUEL PRODUCTION PROCESSES BASED ON SYSTEMATIC OPTIMIZATION METHODOLOGIES / JOS F.O. GRANJO / NUNO M.C. OLIVEIRA / UC / SEPTEMBER 2013
Presentation outline
Motivations
Project framework
Some work developed
Modelling & parameter estimation of LLE and VLE systems
Sodium methylate production process. Simulation and analysis
Optimal design of solid-liquid extraction units
End notes
(4/53)
MOTIVATIONS
5/53
Economy based on fossil resources
MOTIVATIONS
RAW MATERI AL S I NT ERMEDI ATES
PRODUCT S/
USES
COMMODI TI ES
SECONDAR Y
COMMODI TI E S
UPSTREAM REFINERY
DEPLOYMENT
&
DISTRIBUTION
Figure 1. Fossil-based refinery concept.
Highly cost-efficient industries since the
upstream to the downstream steps.
Broad number of products and uses.
Well stablished technologies.
Oil & gas combined global market value of
$2.6 trillion of dollars in 2010.
Coal, gas & oil combined annual volume of
77 billion BOE spent in 2012.
Coal market value is $600 billion of dollars
in 2010, more 14.5% than 2007.
6/53 MOTIVATIONS
RAWMATERIALS
Petroleum
Natural gas
Coal
Tar sands bituminous
Oil shales
COMMODITIES
Benzene
Gasoline
Diesel
Xylene
Toluene
Butanes
Ethane/Ethylene
Chlorine
CO / H
2
O
2
/N
2
SO
2
SECONDARYCOMMODITIES
Ethylene benzene
Cyclohexane
Cumene
P-Xylene
Iso-butylene
Butadiene
Ethylene oxide
Propylene
Ethylene Dichloride
Methanol
Ammonia
Sulphuric acid
Styrene
Adipic acid
Caprolactam
Phenol
Acetone
Terephthalic acid
Ethylene glycol
Propylene oxide
Acrylonitrile
Vinyl Chloride
Formaldehyde
MTBE
Acetic acid
Nitric acid
INTERMEDIATES
Polystyrene
Nylon 6,6, polyurethanes
Nylon 6
Phenol-formaldehyde resins, Bisphenol A,
Caprolactam, Dalicylic acid
Methyl methacrylate, Solvents, Bisphenol A,
Pharmaceuticals
Toluene diisocyanate, foam polyurethanes
MTBE
Polybutadiene, neoprene, styrene
butadiene rubber
Polypropylene, polypropylene glycol,
propylene glycol
adiponitrile, acrylamide
Polyvinyl chloride
Urea-formaldehyde resins,
phenol-formaldehyde resins
Oxygenated gasoline additive
Vinyl acetate
Polyvinyl acetate
Polyvinyl alcohol
Polyvinyl butyral
Ammonium nitrate, adipic acid,
fertilizers, explosives
Phosphate fertilizer, ammonium
PRODUCTS/USES
TEXTILS
coatings, foam cushions, upholstery,
drapes, lycra, spandex
SAFE FOOD SUPPLY
Food packaging, preservatives,
fertilizers, pesticides, beverage
bottles, appliances, beverage can
coatings, vitamins
TRANSPORTATION
Fuels, oxygenates, anti-freeze, wiper
belts hoses, bumpers, corrosion
inhibitors
CONSTRUCTION
Paints, resins, siding, insulation,
retardents, adhesives, carpeting
RECREATION
Footgear, protective equipment,
tires, wet suits, tapes- CDs-DVDs,
golf equipment, camping gear,
Rboats
COMMUNICATION
Molded plastics, computer casings,
displays, pens, pencils, inks, dyes,
paper products
HEALTH & HYGIENE
Plastics eyeglasses, cosmetics,
detergents, pharmaceuticals, suntan
lotions, medical- dental products,
disinfectants, aspirin
Figure 2. A product flow-chart from petroleum feedstocks.
7/53 MOTIVATIONS
Figure 3. World total proved reserves of oil (BP, 2013).
Geographic concentration of resources.
10. 000 +
8. 000 - 9. 999
6. 000 - 7. 999
4. 000 - 5. 999
2. 000 - 3. 999
0 - 1.99 9
NO DATA
(mtoe )
PROVED
RESERVES
8/53 MOTIVATIONS
0
50
100
150
200
250
1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012
P
r
i
c
e
i
n
d
e
x
e
s
(
i
n
d
e
x
2
0
0
5
=
1
0
0
)
Year
Non-fuel
Industrial
inputs
Fuel
Food
OPEC production
Asian l crisis
9/11
Iraq war
PDVSA strike
Weaker dollar
Arab
Spring
Subprime
mortgage crisis
Lowspare
production
0
25
50
75
100
125
150
175
200
225
250
1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012
R
/
P

(
y
r
)
Year
Coal
Gas
Oil
Figure 4. Price indexes adjusted to inflation. Data fromBP (2013). Figure 5. Reserves-to-production ratio of coal, gas and oil. Data fromBP (2013).
Geographic concentration of resources.
Energy security and prices instabilities.
Long-term supply shortcomings.
Contributes to global-warming.
CO
2
levels surpassed 400 ppmfor the first time in
3 to 5 million years, a time where climate
was considerably warmer than it is today. (BBC
News, May 10th, 2013).
9/53 MOTIVATIONS
Figure 6. Bio-economy concept.
Bio-economy
BI OMAS S
BI OREFI NERI ES
BI O-ENERGY
PRODUCT, FUEL AND ENERGY MARKETS
BI O-ECONOMY
BI O-PRODUCTS BI O-FUELS
Market valorises bio-products.
Global market value for bio-products
increased from 2001 to 2012 from $20 billion to
$200+ billion of dollars.
Biofuels global market was $83+ billion in
2011 and is forecasted $185 billion of dollars for
2021.
BI OMAS S PRECURSORS
SECONDARY
CHEMI CAL S
I NT ERMEDI AT ES
PRODUCT S
USES
I NTER MEDI AT E
PLAT FORMS
BUI LDI N G
BL OCKS
Develop bio-products mimicking
functionalities of petroleum-based or improved.
Valorise biomass regarded as waste.
Figure 7. Bio-economy concept.
DEPLOYMENT BIOREFINERY
HARVESTING
10/53 MOTIVATIONS
BIOMASS PRECURSORS
Lignocellulosic materials
(e.g. trees, barks, sawdust)
Cereals
(e.g. corn, wheat)
Plant oils and animal fats
(e.g. soybean, beef tallow)
Sugar and molasses
(e.g. sugar cane, beets)
Green plants
(e.g. grasses, algae)
Miscellaneous
organic wastes
Agricultural wastes
(e.g. corn stover)
Carbohydrates
Starch
Hemicellulose
Cellulose
Lignin
Oil, fats
Protein
Bio-based
Syngas
SG
C1
C2
C3
C4
C5
C6
Ar
Direct
Polymers & Gums
Sugars
Glucose
Fructose
Xylose
Arabinose
Lactose
Sucrose
Starch
Hydrogen
Methanol
Mixed alcohols
Higher alcohols
Oxo-synthesis
products
Iso-synthesis
products
Fischer-Tropsch
Liquids
Glycerol
Lactic acid
3-Hydroxyl-
-propionate
Propionic acid
Malonic acid
Serine
Succinic acid
Fumaric acid
Malic acid
Aspartic acid
3-Hydroxy-
-butyrolactone
Acetoin
Threonine
Itaconic acid
Furfural
Levulinic acid
Glutamic acid
Xylonic acid
Xylitol/Arabitol
Citric/Aconitic
acid
5-Hydroxy-
-methyl-furfural
Lysine
Gluconic acid
Glucaric acid
Sorbitol
Gallic acid
Ferulic acid
Ammonia synthesis, hydrogenation products
Methyl esters, formaldehyde, acetic acid, dimethylether,
Linear and branched alcohols, and mixed higher alcohols
Iso-C4 molecules, isobutene and its derivatives
Fermentation products, propylene glycol, malonic, 1,3-PDO,
diacids, propyl alcohol, dialdehyde, epoxides
Acrylates, L-Propylene glycol, Dioxanes, Polyesters, Lactide
Acrylates, Acrylamides, Esters, 1,3-Propanediol,
Malonic acid and others
Reagent, propionol, acrylate
Pharma intermediates
2-amino-1,3-PDO, 2-aminomalonic, (amino-3HP)
THF, 1,4-Butanediol, -butyrolactone, pyrrolidones, esters,
diamines, 3,3-bi onelle, hydroxybutyric acid
Unsaturated succinate derivatives
Hydroxy succinate derivatives, hydroxybutyrolactone
Amino succinate derivatives
Hydroxybutyrates, epoxy--butyrolactone, butenoic acid
Butanediols, butenols
Diols, ketone derivatives, indeterminant
Methyl succinate derivatives, unsaturated esters
Many furan derivatives
-aminolevullinate, 2-Methyl THF, 1,4-diols, esters, succinate
Amino diols, glutaric acid, substituted pyrrolidones
Lactones, esters
EG, PG, glycerol, lactate, hydroxy furans, sugar acids
1,5-pentanediol, itaconic derivatives, pyrrolidones, esters
Numerous furan derivatives, succinate, esters, levullinic acid
Caprolactam, diamino alcohols, 1,5-diaminopentane
Gluconolactones, esters
Dilactones, monolactones, other products
Glycols (EG, PG), glycerol, lactate, isosorbide
Phenolics, food additives
Fuel oxygentates
Reagents-building unit
Antifreeze and deicers
Solvents
Green solvents
Speciality chemicals
intermediate
Chelating agents
Amines
Plasticizers
Polyvinyl acetate
pH control agents
Resins, crosslinkers
Polyvinyl alcohol
Polyacrylates
Polyacrylamides
Polyethers
Polypyrrolidones
Phthalate polyesters
PEIT polymer
Polyhydroxypolyesters
Nylons (polyamides)
Polyhydroxypolyamides
Bisphenol A replacement
Polycarbonates
Polyurethanes
Phenol-formaldehyde resins
Polyhydroxyalkonoates
Polysaccharides
Polyaminoacids
INDUSTRIAL
Corrosion inhibitors, dust control,
boiler water treatment, gas
TRANSPORTATION
Fuels, oxygenates, anti-freeze,
seats, belts hoses, bumpers,
corrosion inhibitors
SAFE FOOD SUPPLY
Food packaging, preservatives,
fertilizers, pesticides, beverage
bottles, appli ances, beverage can
coatings, vitamins
TEXTILS
coatings, foam cushions,
upholstery, drapes, lycra, spandex
ENVIRONMENT
chelators, cleaners and
detergents
COMMUNICATION
Molded plastics, computer
liquid crystal displays, pens,
pencils, inks, dyes, paper products
CONSTRUCTION
Paints, resins, siding, insulation,
cements, coatings, varnishes,
carpeting
RECREATION
Footgear, protective equipment,
& tires, wet suits, tapes-CDs-
DVDs, golf equipment, camping
gear, boats
HEALTH & HYGIENE
Plastics eyeglasses, cosmetics,
detergents, pharmaceuticals,
suntan lotions, medical-dental
products, disinfectants, aspirin
INTERMEDIATE
PLATFORMS
BUILDING
BLOCKS
SECONDARY CHEMICALS INTERMEDIATES PRODUCTS/USES
Figure 8. A products flow-chart concept from biomass.
11/53 MOTIVATIONS
Bio-economy
High spatial distribution of biomass resources and intermittent availability.
Technological hindrances in the conversion of cheap feedstock (e.g. forest and agro
wastes).
Biomass morphology and chemical composition are highly variable.
Intensification of biomass usage increases water demand.
High uncertainty in the prediction of thermodynamic properties.
Identification of the adequate product portfolio for the biorefinery.
Main challenges
PSE tools and know-how are being use to tackle above issues in
biorefinery context.
12/53
* Scope of this work.
*
MOTIVATIONS
Figure 9. Decisions hierarchy in PSE (Grossmann, 2010).
More focus on process synthesis & analysis.
Decision-making with PSE tools
13/53
Figure 10. Academic & Industry perspectives
(adapted from Neves, 2007).
Major concerns in biofuel industry at single-site level are feedstock
costs, equipment cost, and energy and water consumptions.
MOTIVATIONS
Modelling
(complexity)
Simulation
Optimisation
(poor solutions)
Energy
(costs )
Separation
(efficiency )
Reaction
(production )
PSE
Academic view
(difficulties to overcome)
Industrial view
(benefits to accomplish)
(large-scale)
Decision-making with PSE tools
(14/53)
PROJECT
OVERVIEW
15/53
PROJECT OVERVIEW
TRANSPORT
& HARVE STI NG STORAGE SURGE BI N
& SCALE
DESTONI NG DRYI NG
CRACKI NG,
ASPI RATI ON
& DEHULLI NG
HULLS &
MI LL FEED
CONDITI ONI NG FLAKI NG MI LL
SOLVENT
SOLVENT MARC
FLASH
DESOLVEN-
TIZI NG
BAGASSE
EXTRACTI ON
SOLVENT
MAKEUP
YEAST
ENZYMES
SOLVENT
MAKEUP
FLASH
EVAPORATOR
FLASH
YEAST
RECYCLE
GLYCEROL
PROTEI N
CONCENTRATE
BI OETHANOL
WATER
WATER
2
SEEDS
PREPARATI ON
1
COLLECTING
& TRANSPORTI NG
3
SOLVENT
EXTRACTI ON
4
BI OETHANOL
PROCESS
5
BI ODI ESEL
PROCESS
MI SCE LLA
VEG. OI L
SACCHARI FI CATI ON
METHANOL
LL
EXTRACTI ON
REACTI ON
FERMENTATI ON
FLOUR
WORT
FERMENTED
WORT
SEPARATI ON
OI L RECYCLE
BI ODIESEL
SEPARATI ON
SEPARATI ON
WATER
+ GLYCEROL
BI ODI ESEL
+ OI L
FI BERS
SOY BEANS
Biorefinery based on whole-crop biomass
Figure 11. Whole-crop biorefinery
based upon soy bean.
16/53 PROJECT OVERVIEW
Work performed within the project
Modelling & parameter estimation of LLE and VLE systems.
Kinetic studies of transesterification reaction for biodiesel production.
Sodium methylate production process. Simulation and analysis.
Optimal design of industrial solid-liquid extraction units.
(17/53)
MODELLING & PARAMETER
ESTIMATION OF LLE AND VLE
SYSTEMS
18/53 MODELLING & PARAMETER ESTIMATION OF LLE AND VLE SYSTEMS
Study of water ethanol IL LLE ternary systems.
Application to ethanol purification.
Modelling and parameter regression of VLE data for IL-water and IL-
ethanol binary pairs.
Solubilities of ILs in water (ongoing).
Parameter regression for single strong aqueous electrolytes.
Tasks accomplished
19/53
Development of an alternative process to purify ethanol based on L-L extraction.
7 phosphonium-based ionic liquids were tested as potential solvents.
Experimental data of water ethanol IL ternary systems was gathered.
LLE modelling and parameter regression with NRTL model.
LLE predictions with COSMO-RS.
P
+
N
-
S
O
O
F
F
F
S
O
O
F
F
F
O O
-
P
O
-
O
-
N
N N
S
O
O
O
-
[TDTHP]
+
Cl
-
Br
-
[Deca]
-
[Phosph]
-
[CH
3
SO
3
]
-
[N(CN)
2
]
-
[NTf
2
]
-
MODELLING & PARAMETER ESTIMATION OF LLE AND VLE SYSTEMS
* Join collaboration with PATh-CICECO
group, University of Aveiro.
Study of water ethanol IL ternary systems
Figure 12. Molecular structures of all IL studied.
Detailed description of this work in
Neves et al. (2011).
20/53
Figure 13. Local molecular clusters.
Modelling
Necessary condition for liquid-liquid equilibria.
2
1 1
2
1
2
1
2 1
2
2
1
Molecule 1
in centre
Molecule 2
in centre
g
21
g
11
g
12
g
22
NRTL
1, 2, ...,
I II
i i
i N = =
= 1, 2, ...,
I II
i i
I II
i i
i i i
f f
a a
a x i N
=
=
=
NRTL model (Renon, 1968) used to describe non-ideality.
ln
c c
E n n
i i
i i
i i
i
x L g
x
RT M
= =

ln
c
n
j ij j
i
i ij
j
i j j
x G L
L
M M M
t
| |
= +
|
|
\ .
c
n
i k ki ki
k
L x G t =
c
n
i k ki
k
M x G =
ij ij
ij
G e
o t
=
( )
, and 0,
ij ii ij
ij ij
g g g
i j i j
RT RT
t t
A
= = = = =
NRTL parameters regression
3 adjustable parameters per binary pair ( )
, , .
ij ji ij ji
t t o o =
Problem easy to formulate and small, but can be hard to tackle due to its high
non-linearity and non-convex nature.
NLP1
( )
2
2
exp mod
min = ( )
. . ( , ) 0
1 0 1,2,... ; 1,2

0, 1,2,... ; 1,2,... ; 1,2
t c
n n
ijk ijk ijk
z
i j k
ijk t
j
L U
ij ij ij
ijk t c
w w
s t NRTL x
x i n k
x i n j n k
| e t
t
t t t
=
= = =
s s
> = = =
NLP 1 implemented in GAMS and solved with CONOPT, OQNLP and BARON.
Regression problem formulation:
NRTL parameters regression
4th law of thermodynamics: "Anything that can go wrong, will go wrong."
Figure 14. Excess Gibbs energy curve of a
binary mixture system. LLE example.
After regression, stability tests must be done to avoid meaningless parameter values.
0
0 1.0
m G
R T
X
1
X
1
L1
X
1
L2
1
L1
1
L2
0
0 1.0
m G
R T
X
1
X
1
L1
X
1
L3
X
1
L2
F(y)
1
L1
1
L3
1
L2
Figure 15. Excess Gibbs energy curve of a
binary mixture system. 3 phase LLE example.
Stability test problem formulation
Minimization of F(y):
NLP2
( ) ( )
min ( )=
. . (y; ) 0
1 0
0, 1,2,...
c
n
F
i i i
y
i
i
i
i c
F y y y
s t NRTL
y
y i n

t
=
=
> =
Phases are stable if and only if F(y) u

for all space of candidate phase with composition y.
1) Solve NLP1 with OQNLP.
2) Generate a pool of all local solutions found.
3) Test stability solving NLP2 for each experiment.
4) If all stable finish. Else, go to 3) with the 2nd best solution, etc.
Numerical procedure adopted
24/53
Figure 17. Ternary phase diagram[TDTHP][Deca] + EtOH + H2O
at 298 K (mass fraction units).
NRTL parameters for seven water(1) etanol(2) Ionic liquid(3) ternary systems were obtained.
Figure 16. Ternary phase diagram[TDTHP][Phosph] + EtOH + H2O
[TDTHP][Phosph]
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
[TDTHP][Deca]
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Results
A commercial package of COSMO-RS model is used to predict LLE. It uses quantum
calculations coupled with statistical thermodynamic approaches.
25/53
Figure 19. Ternary phase diagram[TDTHP][CH
3
SO
3
] + EtOH + H2O
Figure 18. Ternary phase diagram[TDTHP][Cl] + EtOH + H2O
[TDTHP]Cl
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
[TDTHP][CH
3
SO
3
]
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Parameters
1S
,
S1
,
2S
,
S2
are adjusted while:
12 13 23 12 21
0 3031 0 2 0 3 670 4 55 2 . , . , . , . / , . / T T o o o t t = = = = =
are fixed as suggested by Song and Chen (2009).
Results
26/53
Figure 21. Ternary phase diagram[TDTHP][N(CN)
2
] + EtOH+ H2O
All systems are type I.
Figure 20. Ternary phase diagram[TDTHP][Br] + EtOH+ H2O
[TDTHP]Br
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
[TDTHP][N(CN)
2
] 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Results
27/53
Figure 22. Ternary phase diagram[TDTHP][NTf
2
] + EtOH + H2O
[TDTHP][NTf
2
]
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
EtOH
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
2
O
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
System D S
Maximum EtOH
extraction (%)
[TDTHP]Cl 0.82 6.6 72
[TDTHP]Br 0.68 7.9 78
[TDTHP][NTf
2
] 0.07 22 87
[TDTHP][Phosph] 0.85 5.7 72
[TDTHP][Deca] 0.81 5.3 70
[TDTHP][N(CN)
2
] 0.51 7.8 82
[TDTHP][CH
3
SO
3
] 0.89 6.7 65
[TDTHP][B(CN)
4
] - - 91
a
[TDTHP][C(CN)
3
] - - 80
a
Table 1. Distribution coefficients and ethanol selectivities for each system
at the lowest tie-line, and maximum ethanol concentration obtainable
(mass basis).
a
Predicted by COSMO-RS.
Results
Concentrations of up to 65% wt in ethanol can
be achieved from 2% wt ethanol feed, using a
single LL extraction stage.
28/53
Values of 0 at the optimum varied
between 0.710
-3
and 710
-3
for systems
Br
-
and [N(CN)
2
]
-
, respectively.
Ionic liquid
NRTL binary interaction parameters
13
31
23
32
[TDTHP]Cl 11.14 -2.555 5.230 -3.181
[TDTHP]Br 21.09 6.265 4.688 -2.760
[TDTHP][NTf
2
] 11.36 4.674 4.798 -1.520
[TDTHP][Phosph] 25.25 -1.450 6.064 -3.917
[TDTHP][Deca] 23.82 -1.169 5.487 -3.559
[TDTHP][N(CN)
2
] 14.82 1.313 4.865 -2.873
[TDTHP][CH
3
SO
3
] 11.09 -3. 487 5.998 -3.318
Table 2. NRTL binary interaction parameters for each
system at 298.15 K.
Results
Number of local optima varied
between 5 and 77 for the systems
[NTf
2
]
-
and [Br]
-
, respectively.
F(y) varied between -110
-10
and 0.
Therefore all data points were
considered stable for the best NRTL
parameter set found.
29/53
Pervaporation
Vaporizer
Cooling
LL
extractor
Fermenter
Feed
Water
makeup
Broth
Recycle
Residue Solvent
Purge
IL
makeup
Extract
Hydrated
ethanol
Anhydrous
ethanol
Water
residue
Figure 23. Block diagram for ethanol purification
based on liquid-liquid extraction and pervaporation.
A LL extraction stage coupled to an extractive fermentation.
IL is continuously recycled to the fermentator.
Further ethanol concentration is carried out by pervaporation.
This design applicable in other contexts, where ethanol is to be separated.
Alternative process for bioethanol purification
30/53
Characteristics of electrolyte solutions
Modelling (single strong electrolyte)
Complete or partial speciation of some molecular species.
Possible salt precipitation and salting-out effect.
Possible presence of complexing compounds.
Simultaneous phase and solution equilibrium.
Mean activity coefficient of a salt completely dissolved.
( )
CA C (sol.)
- ln
c a
ca c c a a
o
ca ca
A
RT m
v v
v
v v

+

+
= +
=
( )
( )
1/
1/
where
c a
c a
c a
c a
c a
m m m
v
v v
v
v v

v v v
=
=
= +
eNRTL model (Chen, 1980)
was used to estimate y
_
Single strong electrolyte solutions
31/53
* *, *, *,
ln ln ln ln
PDH Born lc
i i i i
= + +
2 2
*, 2
1 1
ln 10
2
Born
e i
i
s w i
Q z
kT r
c c

| || |
=
| |
\ . \ .
( )
1/2
2 2 1/2 3/2
*, 1/2
1/2
2 2 2 1000
ln ln 1
1
PDH
i i x x
i x
s x
z z I I
A I
M I

(
| | | |
= + +
( | |
+
\ . \ .

1/2
1/2
2
2 1
3 1000
A s e
s
N d Q
A
kT
t
c
| |
| |
=
| |
\ .
\ .
2
1
2
x i i
i
I x z =

, i c a =
Long-range interaction contribution
eNRTL model
Born termcorrection (only in mixed-solvent solutions)
* denotes unsymmetric reference state:
1
w
x =
Detailed model derivation in
Chen and Song (2004).
, i c a =
Figure 24. Molecule and ions clusters.
c
a
a
a
c
c
c
m
a
g
ac
g
mc
g
ma
g
ca
g
cm
g
mm
g
am
eNRTL
Cation in
centre
Anion
in centre
Molecule
in centre
m
m
m
m
m
m
m
m
m
eNRTL accounts contributions of local and electrostatic interactions.
32/53
, ,
,
, ' , '
' , '
, '
'
, ' , '
1
ln
k kc ac kc ac k km km
lc
m cm k k
c a cm
a m
c k kc ac k km k km
k k k
k ka c a ka c a
c a ca c a
k
ca c a
a c
k ka c a k ka c a
k k
X G X G
X G
Y
z X G X G X G
X G
Y X G
X G X G
t t
t
t
t
| |
|
= +
|
|
\ .
| |
|
+
|
|
\ .

' ' , ,
,
m' '
' ,
'
' ' , ,
, ,
,
,
, ,
ln
j jm jm
k km km k kc ac kc ac
j
lc a c mc ac
mm k k
m mm mc ac
m c a
k km k km k km k kc ac k kc ac
k k k k k
k ka ca ka ca
c a Ba ca
k
mc ca
k ka ca k ka ca
k k
X G
X G X G
Y X G
X G
X G X G X G X G X G
X G
Y X G
X G X G
t
t t
t t
t
t
| | | |
| |
= + +
| |
| |
\ . \ .
+

a c
| |
|
|
|
\ .
Short-range interaction contribution

,
ln
lc
m wm mw mw
G t t
= +
,
,
1
ln
lc
c a wc ac cw cw
a
c
Y G
z
t t
= +
,
,ca
1
ln
lc
a c wa aw aw
c
a
Y G
z
t t
= +
*,
ln ln ln
lc lc
i i i

=
, , , , i j k m c a =
eNRTL model
33/53
, ,
,
, ' , '
' , '
, '
'
, ' , '
1
ln
k ka ca ka ca k km km
lc
m am k k
a c am
c m
a k ka ca k km k km
k k k
k kc a c kc a c
a c ac a c
k
ac a c
c a
k kc a c k kc a c
k k
X G X G
X G
Y
z X G X G X G
X G
Y X G
X G X G
t t
t
t
t
| |
|
= +
|
|
\ .
| |
|
+
|
|
\ .

,m cm a ca
a
G Y G =
,m am a ac
a
G Y G =
'
'
c
c
c
c
X
Y
X
=
a'
'
a
a
a
X
Y
X
=
, mc cm a m ca
a
Y o o o = =
, ma am c m ca
c
Y o o o = =
, , , ma ca am ca m m ca
t t t t = +
,ac , , mc cm ca m m ca
t t t t = +
Adjustable parameters:
Molecule molecule
Ion-pair molecule
Ion-pair ion-pair
' ' ' '
, ,
mm m m mm m m
t t o o =
, , , ,
, ,
ca m m ca m ca ca m
t t o o =
, ' ',ca , ' ' ,
, ' ', , ' ' ,
, , , ,
,
ca ca ca ca c a c a ca
ca ca ca ca ca c a c a ca
t t t t
o o o o = =
In practice, values
are fixed to 0.2 or 0.3.
Mixing rules:
eNRTL model
34/53
Case studies
Used to test eNRTL implementation in GAMS .
eNRTL model was regressed to experimental data of mean activity
coefficient from NaCl and KCl aqueous solutions.
eNRTL parameters regression problem formulation:
NLP3
( )
2
exp mod
min = ( )
. . e ( ) 0
1,2,... ; 1,2,...
t
n
k
z
j
L U
ij ij ij c c
s t NRTL
i n j n
| e t
t
t t t

=
s s = =
Parameter o
ca,m
= 0.2.
co
,
m
and
m
,
co
are adjusted.
35/53
Table 3. Results of NRTL parameter regression for NaCl and KCl aqueous
solutions.
Results for case studies NaCl and KCl aqueous solutions
NaCl KCl
z
ca
,
m
z
m
,
ca
z
ca
,
m
z
m
,
ca
GAMS -4.572 8.949 -4.132 8.126
ASPENTECHDB -4.550 8.888 -4.131 8.122
Zemaitis Jr., (1986) -4.549 8.885 -4.107 8.064
Figure 25. Experimental and predicted mean activity
coefficient versus molality for NaCl aqueous solution.
Figure 26. Experimental and predicted mean activity
coefficient versus molality for KCl aqueous solution.
AAD%(y
_
NaCl) ~ 0.007.
AAD%(y
_
KCl) ~ 0.001.
(36/53)
SODIUM METHYLATE
PRODUCTION PROCESS.
SIMULATION AND ANALYSIS
37/53
Sodium methylate production process
Traditional production process (Tse, 1997) simply consists upon mixing of Na(s) with
MeOH.
SODIUM METHYLATE PRODUCTION PROCESS. SIMULATION AND ANALYSIS.
High cost of Na(s) limits the selling price of sodium methylate.
Alternative process based on RD (Guth, 2004) uses more cheap 50% NaOH (aq.) as raw
material.
Both these processes are simulated in Aspen Plus and their preliminar economical potentials
estimated.
Base of production considered for NaOCH
3
is 3000 ton per year (dry basis).
38/53
Figure 27. Process for the production of methanolic
solution of sodiummethoxide frommetallic sodium.
H
2
(g)
Na(s)
D=1.31m
H=2.19m
T ~ 80 C
H-601
R-601
F-601
25% NaOCH
3
in
methanol
CH
3
OH (g)
recycle
Methanol
make-up
3 3 2
0 -1
rx
1
Na+CH OH NaOCH + H
2
( H 200.96 kJ mol , Chandran et al. (2007)) A =

Traditional production process (Tse, 1997)
1508 kg/h
Hydrogen is produced as by product.
Reaction highly exothermic.
1355 kg/h
MeOH
160 kg/h
39/53
Alternative process based on RD (Guth, 2004)
+ -
2 3
+ -
(aq.) (aq.) (aq.)
+
3(MeOH) (MeOH) 3(MeOH)
2H O H O + OH
NaOH Na + OH
NaOCH Na +OCH
Solution reactions
3 3 2
0 1
rx
CH OH+NaOH NaOCH +H O
( H 58.3 kJ mol , Chandran et al. (2007))
A =
Chemical equilibria
14.41, 7012 K (estimation) A B = = ln
x
B
K A
T
= +
Missing parameters of eNRTL model
Hc0E
,
No0CES
,
No0CES
,
Hc0E
were
estimated using methanol activity data in solution with NaOCH
3
of
Freeguard (1965).
40/53

Hc0E
,
No0CES
,
No0CES
,
Hc0E
estimation:
NLP4
( )
2
exp *
, , , ,
min = ( ( ) ( ))x
. . e ( , ) 0

t
n
i MeOH i MeOH i MeOH i MeOH
z
i
L U
ij ij ij
a
s t NRTL x
| t t
t
t t t
+
=
s s

Figure 28. Experimental and predicted metanol
activity versus molality of sodium methylate.
( )
,
% ~0.002.
i MeOH
AAD a
, 3
3,
3, , 3
1.180
2.856
0.2
MeOH NaOCH
NaOCH MeOH
NaOCH MeOH MeOH NaOCH
t
t
o o
=
=
= =
41/53 SODIUM METHYLATE PRODUCTION PROCESS. SIMULATION AND ANALYSIS.
Figure 29. Process for the production of methanolic solution of sodiummethoxide fromsodium hydroxide.
H = 14 m
T ~ 71 C
P = 1 bar
50% wt
NaOH (aq.)
T-602
H = 28 m
T ~ [65;100] C
P = 1 bar
T-601
H
2
O
< 0.1 % wt methanol
30% wt NaOCH
3
in methanol
CH
3
OH
recycle
TK-601
CH
3
OH (g)
Methanol
make-up
H-601
H-602
H-603
R-601
R-602
C-601
42/53
Alternative
Fixed capital Waste treatment
Utilities Raw materials
Tradicional
Fixed capital Waste treatment
Utilities Raw materials
Total Costs : 4.7 Myr
-1
Revenue : 7 Myr
-1
Economical Potential: 2.3 Myr
-1
Total Costs : 6 Myr
-1
Revenue : 6.8 Myr
-1
Economical Potential: 863 kyr
-1
Summary
(43/53)
OPTIMAL DESIGN OF S-L
EXTRACTION UNITS
44/53 OPTIMAL DESIGN OF S-L EXTRACTION UNITS
Figure 31. Rotocel extractor. Figure 30. Crown Model extractor.
Figure 32. DeSmet extractor.
Can extract large mass flows of oil (2000 ton/day).
Counter-current cross flow patterns.
All share the same flowpattern in the extraction
area.
Mathematical model of a DeSmet extractor
Figure 33. DeSmet extraction area scheme.
c
t c
| | c c c c c
+ + +
|
c c c c c
\ .
2 2
2 2
(1 )
= ( )
b
m f p p h
b
C C C C C
V Es K a C C u
z x z x
Bulk phase equation is
t c c
c c
c + c
( )
=
(1 )
p f p p p
v
p p d
C K a C C C
u
E x
Pore phase equation is
Diffusion and mass transfer with
spatial distribution of concentrations in
the extraction section are incorporated.
c t t
t

}
( , , ) ( )
=
k
m
b m s T
X
m
n
b
X
HV C x L dx C Q
dC
d V
Conservation balance in each tray volume
The section dimensions, components
velocities, and porous media porosities
are accounted.
= oil concentration
= flakes bed thickness [m]
= horizontal coordinate [m]
= vertical coordinate [m]
C
H
x
z
46/53
Figure 34. Loading section
scheme.
Figure 35. Particles filling scheme.
OPTIMAL DESIGN OF S-L EXTRACTION UNITS
c c c
| |
+
|
\ .
2
1
= (1 )
1
in
p
p s h b b p
C
Q HL u u
C
Average exit concentration is
determined by the equation:
( )
u
C
t
}
1
0
1
1
= ( , , )
X
u r
C C x L dx
X
c
c
c c
+
+ +
2
2
2
2
1
=
(1 )
1
p
s
in
p
p v
p d p
C
C
C
C
C
E
C
The flow into the loading zone is
determined by the equation:
( )
P
Q
Pore phase concentraction in the loading
zone:
1
1 1
where, 0, ..., ; if 1 and
= ( ( 2) ), ,( ( 1) )
if =2, ,( 1)
s s
s
x X m
x X m X X m X
m m
= =
+ +
Figure 36. Drainage section scheme.
c t t t
t
(
+
(

} }
0
( , , ) ( , , ) ( )
=
L
s
k
m
b m s h f T
X
ms n
b
X
H V C x L dx u C X Z dz C Q
dC
d V
c + + = =
T q D q s h b
Q Q Q Q HL u
t c c c t ( +
}
0
( ) = (1 ) (1 ) ( , , )
L
s v
f b p p d p f
Q Hu E C X Z dz
2 (0, , ) = ( ) = 0, , ; >0
s
C z C z L t t t
from sections =1, ..., ( 1) :
s
m m
1
( , 0, ) = ( ) >0
m
C x C t t t
+
Miscella vertical flowrate:
Average concentration in the last tray:
Volume of oil losses:
Initial & Boundary conditions
( , , ) / =0 =0, , ; >0
f s
C X z x z L t t c c for the drainage zone:
for section m
s
: ( , 0, ) = =( ), ,
in f ms f
C x C x X X X t
( , , ) / = 0 = 0, , ; >0
s f
C x L z x X t t c c
bottomboundary:
(0, , ) = ( ) = 0, , ; >0
p p
in s
C z C z L t t t
0 0
( , , 0) = ( , ) and ( , , 0) = ( , )
p p
C x z C x z C x z C x z
loading zone:
Initial values:
=0, ,
f
x X =0, ,
s
z L
Optimal design of a S-L extraction unit
X
s
/ m X
1
/ m L
s
/ m H / m X
ms
/ m m
s
u / (m/s)
2.0 1.4 2.0 2.4 1.4 6 0.005
M
n
/ (kg/s) Q
q
(dm
3
/s) C
in
he
/ % N
t
/ % u
h
/ (m/s) g
fe
/ % a
p
/ (1/m)
9.3 8.8 0.1 21.3 0.002 0.65 72
ol
/ (kg/m
3
)
he
/ (kg/m
3
)
Mn
/
(kg/m
3
)
s
/ (kg/m
3
) / (Pa s)
b
p
910 680 520 1180 3.2E-4 0.4 0.24
Experimental data fom an industrial DeSmet extractor unit was retrieved
from Veloso (2003).
PDE system was implemented in GAMS in a discretized form.
Model was validated against experimental data at S.S.
Table 4. Extrator parameters.
49/53
, , ,
=
min
s.t S.S. model eqs. (discretized FE)
,
,

V H L u
m
op cap
s d L U
u
L U L U
m m m
L U
Z C C
C C L L L
u u u V V V
H H H
+
> s s
s s s s
s s
Optimal design of a S-L extraction unit
NLP for operating and capital cost minimization.
Capital costs ( C
cap
) L H
Operating costs ( C
op
) Q
T
and power for pumps.
CONOPT solver was used.
NLP5
50/53
Figure 37. Steady state bulk concentration in De Smet extractor. Figure 37. Average concentration in De Smet extractor.
Total costs
Results
Parameter Reference Optimal
Vm/ (m/h) 36 37.54
H /m 2.0 1.946
L / m 10.8 6.943
u / (m/h) 72 54
Z / (/day ) 319.421 224.150
Oil conc. miscella
30% 20%
Table 5. Numerical results summary.
(51/53)
END NOTES
52/53
Some Future Work
END NOTES
Process simulation of the whole soy bean-based biorefinery.
Performsensibility analysis of the whole process.
Identify key variables and bottlenecks.
(53/53)
Thank you
for your
attention!
Fundao para a Cincia e Tecnologia
Ministrio da Cincia, Tecnologia e Ensino Superior
Ph.D grant SFRH/BD/64338/2009
Acknowledgements:
Nuno M.C. Oliveira
Joo A.P. Coutinho
Belmiro P.D. Duarte

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BIOFUEL PRODUCTION

Phases are stable if and only if F(y) u

Short-range interaction contribution

Sodium methylate production process

SODIUM METHYLATE PRODUCTION PROCESS. SIMULATION AND ANALYSIS.

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