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carbonate process
The process
In the process shown in Figure 1, DLM is
obtained via the carbonate process from
3-methylthiopropionaldehyde (MMP) and
hydrogen cyanide (HCN), without forming coproducts. The process presented here is similar
to one developed by Evonik Industries AG (Essen, Germany; www.evonik.com), and can be
divided into four main areas: hydantoin production; hydantoin hydrolysis; DLM production and
filtration; and drying. Hydantoin corresponds
to the intermediate 5-(2-methylmercaptoethyl)hydantoin generated in the process.
Hydantoin production. MMP, HCN and an
aqueous solution of carbon dioxide (CO2) and
ammonia (NH3) are fed to the hydantoin primary reactor. A gas stream containing CO2, NH3
and impurities leaves the reactor and is washed
with MMP and water in a scrubbing column.
Purified CO2 is released in the overheads and
used in DLM production. The reaction mixture
is fed to a hydantoin secondary reactor, where
the reaction is completed.
Hydantoin hydrolysis. The hydantoin product
stream and potassium carbonate (K2CO3)
are fed to the hydrolysis reactive column,
which contains zirconium fittings that serve
as catalysts and prevent corrosion. CO2 and
NH3 are liberated in the overhead stream
of the column and recycled to the hydantoin
primary reactor. The bottom stream, containing potassium methioninate (KMET), is sent to
the DLM production portion of the process.
K2CO3 is obtained from the regeneration of a
80
150
90
400
300
580
Global perspective
In the past few years, methionine global
demand has increased at an average rate of
5%/yr, and is expected to increase further.
This expansion of methionine demand is driven
by rising meat consumption and, in particular, growth in global poultry, associated with
population growth and increased purchasing
power, mainly in developing countries. Also,
there has been consolidation in the agricultural
sector, leading to larger, more industrialized
farms with more efficient animal nutrition with
higher inclusion rates of amino acids.
In this context, Asian markets present strong
methionine demand, driving its manufacture
toward that region. This can be observed
through the methionine capacity expansion
planned in this area (Figure 2). n
Editors Note: The content for this column is supplied
by Intratec Solutions LLC (Houston; www.intratec.us)
and edited by Chemical Engineering. The analyses
and models presented are prepared on the basis of
publicly available and non-confidential information.
The content represents the opinions of Intratec
only. More information about the methodology for
preparing analysis can be found, along with terms
of use, at www.intratec.us/che.
CW
CO2 make-up
PW
ST
MMP
MMP+
Impurities
3 ) Scrubbing column
4 ) Hydrolysis reactive column
10
5 ) Decarbonator
K2CO3
make-up
MMP
HCN
CO2 make-up
H2O
NH3 make-up
6 ) DLM reactor
CW
ST
7 ) Vacuum crystallizer
8 ) Vacuum filter
CW
9 ) Dryer
9
1
Methionine to
packaging and storage
CW
11
ST
12
CW Cooling water
ST Steam
PW Process water
Extracting 1,3-Butadiene
from a C4 Stream
By Intratec Solutions
FIGURE 2.
BASFs NMP process plants around
the world. Each
mark in the map
corresponds to an
existing facility
Raffinate-1
Economic performance
An economic evaluation of the process
was conducted, taking into consideration
a unit processing a C4 stream to produce 100,000 ton/yr of 1,3-butadiene
erected on the U.S. Gulf Coast (the process
equipment is represented in the simplified
flowsheet below). The estimated total fixed
investment for the construction of this plant is
about $50 million.
An important feature of the presented
technology is its low susceptibility to impurities, rendering it adequate to process any
C4 stream, regardless of the butadiene
content. Also, plants using this technology
have been shown to operate continuously
for more than four years.
In addition, the BASF NMP process technology is currently applied in several plants
worldwide, as shown in Figure 2. n
Editors Note: The content for this column is
supplied by Intratec Solutions LLC (Houston; www.
intratec.us) and edited by Chemical Engineering.
The analyses and models presented herein are
prepared on the basis of publicly available and
non-confidential information. The information and
analysis are the opinions of Intratec and do not
represent the point of view of any third parties.
More information about the methodology for
preparing this type of analysis can be found,
along with terms of use, at www.intratec.us/che.
1,3-Butadiene product
1. First extractive column
CW
CW
2. Rectifier column
CW
3. Second extractive
column
4. Propyne column
CW
1
C4
mixture
Acetylenes
CW
ST
ST
Heavy
ends
5. Butadiene distillation
column
6. Gas compressor
8
7
7. Cooling column
8. Degassing column
9. Scrubber
ST
ST
CW
FIGURE 1. This 1,3-butadiene extraction process is similar to BASFs NMP process
CW Cooling water
ST Steam
1,4-Butanediol from
Bio-Succinic Acid
By Intratec Solutions
1,4-Butanediol unit
Bio-succinic acid unit
Biomass source unit
he compound 1,4-butanediol (BDO) is a
Milling,
versatile intermediate
Lights
Hydrogen
Sugarcane
treatment and
Biofor the chemical industry. Its
sugar inversion
succinic
largest derivative product is
acid
Cell separation,
Hydrogenation
tetrahydrofuran (THF), which
BDO
Purification
or
Glucose Fermentation
recovery and
reaction
is used to make spandex
purification
fibers, resins, solvents and
printing inks. The second largMilling and
Corn
Water
saccharification
est product is polybutylene
Heavies
terephthalate (PBT), which
is used to make high-perforFIGURE 2. It is possible to integrate 1,4-butanediol and bio-succinic-acid production units
mance materials, electronics
The estimated capital investment (including
are reported in literature). Side products include
and automotive equipment.
total fixed investment, working capital and
THF, gamma-butyrolactone (GBL), and linear
BDO can be produced from different techother capital expenses) to build a plant would
alcohols (n-butanol, n-propanol). The amount
nologies and raw materials. The conventional
be $100 million in the U.S. Gulf Coast region
of each product depends on the catalyst and
method for manufacturing BDO is the Reppe
and $140 million in Brazil.
operational conditions used.
process, starting from acetylene. Other proThe bio-succinic acid is totally reacted,
cesses use propylene oxide, maleic anhydride,
Process perspective
and the unreacted hydrogen is compressed
1,3-butadiene or n-butane as starting points.
and recycled back to the reactor. The product
It may be an interesting consideration to
The newest technologies being developed for
stream is cooled and sent to flash vessels to
control the entire supply chain through the
BDO are bio-based pathways, which mostly
recover unreacted hydrogen and eliminate
integration of a bio-succinic-acid production
rely on bio-based succinic acid derived from
volatile materials.
unit with a BDO unit (see Figure 2). Also, the
biomass or a sugar substrate.
bio-BDO produced must include a premium
Succinic acid is a platform chemical that can Purification. The product from the flash vessels
is sent to a series of distillation columns to
price over its petrochemical counterpart. Both
be used to produce many products. However,
separate BDO from side products. In the first
measures are important to make the venture
its high cost of production from petroleum raw
column, BDO, GBL and water are removed
economically feasible.
sources limits its use to specific applications
from the bottoms and then sent to the drying
In addition, it is also an important research(such as pharmaceuticals and food additives).
column, where most of the water is removed.
and-development goal to find hydrogenation
According to the U.S. Dept. of Energy (DOE),
The columns top fraction is sent to a lights
catalysts that have the following qualities:
bio-succinic acid is a renewable building-block
column, to recover side-products as fuel.
Improved tolerance to impurities generated in
chemical with great potential for the future.
The recovered water is sent to a tank for furthe fermentation process (that produces biother disposal or to be recycled to an integrated
succinic acid). This can help reduce the costs
The process
bio-succinic acid production unit (see Figure
of bio-succinic acid purification
The process depicted in Figure 1 was compiled
2). The drying columns bottoms are sent to a
Increased selectivity of bio-succinic acid to
based on a U.S. patent published by BioAmber
BDO recovery column and further to a heavies
BDO, reducing the formation of side products
Inc. (Montreal, Canada; www.bio-amber.com;
column, where a stream of 99.5 wt.% BDO is
and the costs with BDO purification
U.S. patent no. 2011/0245515). The patent
finally achieved.
Both achievements can reduce investment and
discloses details about the initial reaction,
production costs. n
while the separation process was conceived by
Economic performance
Intratec and is based on well-known practices.
Editors Note: The content for this column is
An economic evaluation of the process was
Hydrogenation reaction. A solution of biosupplied by Intratec Solutions LLC (Houston; www.
conducted based on data from the fourth quarsuccinic acid in water is pre-heated and sent to
intratec.us) and edited by Chemical Engineering.
ter of 2013. The following assumptions were
the fixed-bed hydrogenation reactor. Hydrogen
The analyses and models presented herein are
taken into consideration.
is compressed and also fed in excess to the
prepared on the basis of publicly available and
non-confidential information. The information and
A 55,000-ton/yr BDO production unit (the
reactor. The process uses a bimetallic catalyst
analysis are the opinions of Intratec and do not
process equipment is represented in Figure 1)
consisting of metals (including ruthenium, rherepresent the point of view of any third parties.
Storage capacity equal to 20 days of operanium, tin and others) on a carbon support.
More information about the methodology for
tion for BDO and no storage for bio-succinic
The exothermic reaction product is mostly
preparing this type of analysis can be found, along
acid
BDO (selectivities to BDO of more than 90%
with terms of use, at www.intratec.us/che.
Offgas
Hydrogen
CW
1 ) Hydrogenation reactor
Lights
as fuel
ST
CW
2
Bio-succinic acid in water
CW
ST
Water for
disposal or
recycle
CW
CW
CW
8 ) Heavies column
BDO
5 ) Light-ends column
6 ) Drying column
7 ) BDO recovery column
CW
3
10
3 ) Low-pressure vessel
4 ) High-pressure column
CW
ST
2 ) High-pressure vessel
9 ) Cooling tower
10) Boiler
CW Cooling water
ST
ST
ST
ST
ST Steam
Heavies
FIGURE 1. The 1,4-butanediol process from bio-succinic acid that is shown here
is based on patent disclosures from BioAmber and well-known practices
A solution-based
route to LLDPE
By Intratec Solutions
FIGURE 2.
Each mark on the map
corresponds to an
existing SclairTech
LLDPE plant. The
nominal capacity
of each plant follows
the legend below
The process
LLDPE is produced by copolymerization of
ethylene with alpha-olefins using Ziegler-Natta
catalysts. The most common co-monomers used
in LLDPE production are 1-butene, 1-hexene
and 1-octene.
Figure 1 illustrates the process for butenebased LLDPE production via a solution technology similar to Nova Chemicals (Calgary,
Alta.; www.novachem.com) solution-phase
technology, known as SclairTech (Figure 2).
The process shown is a swing process, which
is also capable of producing different LLDPE
and HDPE grades by utilizing other alphaolefins as co-monomers.
The process can be divided into four main
operation areas: purification and catalyst preparation; reaction; distillation; and finishing.
Purification and catalyst preparation. The cyclohexane solvent, ethylene and comonomers are
sent to fixed-bed adsorption systems to remove
water, oxygen and other polar impurities. The
catalysts used in the process are based on
mixtures of titanium and vanadium compounds,
in conjunction with aluminum alkyls cocatalysts.
These components are mixed with solvent and
pumped to the polymerization reactor.
Reaction. Ethylene and 1-butene comonomer
(in case of butene-based LLDPE) are dissolved
in cyclohexane solvent and sent to the reaction
step. The polymerization is carried out in a
solution phase, at a temperature above the
melting point of the resulting polymer. The reaction system consists of a tubular reactor and a
continuous-stirred-tank reactor (CSTR). The low
residence time of the reactors enables a high
flexibility for grade transitions, as well as verButene
Up to 149,000 ton/yr
Economic performance
An economic evaluation of the solution-phase
LLDPE process was conducted based on data
from the fourth quarter of 2012. The following
assumptions were taken into consideration:
A 350,000 ton/yr unit erected on the U.S.
Gulf Coast (the process equipment is represented in the simplified flowsheet)
Ethylene
to Fuel
RF
CW
Cyclohexane
1. Adsorption system
2. Tubular reactor
3. CSTR polymerization
reactor
4. Separators
5. Extruder and pelletizing
6. Low boiler column
7. Ethylene column
8. Comonomer column
9. Solvent column
10. Grease column
11. Refrigeration unit
12. Heat transfer fluid unit
13. Cooling tower
14. Boiler
BFW
ST
BFW
CW 6
ST
CW
4
9
HF
HF
ST
CW
CW
Additives
3
5
ST
ST
to Fuel
LLDPE
Catalyst and
cocatalyst
10
Deactivator
HF
to Fuel
RF
11 CW
13
HF
12
ST
14
HF
CW
RF
ST
BFW
The process
Adipic acid is produced by a microorganism-based fermentation process that uses a
sucrose solution as the feedstock (Figure 1).
The process described below was compiled
based on information available in the published literature.
Sugar inversion. Sucrose is hydrolyzed to
fructose and glucose, which are the compounds actually consumed in fermentation.
The reaction occurs in an acidic medium,
obtained by adding HCl. After inversion,
the pH is adjusted with Na2CO3, and the
resulting stream is cooled before being sent
to the fermentation stage.
Fermentation. The sugars are converted to
adipic acid through an aerobic fermentation.
The microorganism culture is prepared for
inoculation in a two-stage seed train. An ammonia (NH3) solution from the recovery area
is added to the fermenters to maintain a pH
of about 7. The adipic acid produced in
the fermentation step reacts with ammonium
hydroxide, forming diammonium adipate.
Water make-up
Fixed costs
FIGURE 2. Raw materials costs account for the
half of the operating expenses for a bio-based
adipic acid unit
NH3 make-up
1.
2.
3.
4.
5.
6.
7.
CW
8
To waste
treatment
Na2CO3
CW
Air
CW
HCl
28%
Microorganisms
seed
1
50%
Economic performance
An economic evaluation of the bio-based
adipic acid production process was conducted. The following assumptions were
taken into consideration:
A 83,000-ton/yr capacity plant erected
on the U.S. Gulf Coast
Storage of product is equal to 30 days
of operation, and there is no storage for
feedstock
Outside battery limits (OSBL) units considered: ammonia refrigeration system,
cooling towers and steam boilers
The estimated capital investment (including
total fixed investment, working capital and
other capital expenses) for the construction
of such a plant amounts to about $340
million, and the operating cost is about
$2,150 per ton of product, as depicted in
Figure 2.
Due to the availability of low-cost feed-
Exhaust
gases
Sucrose
Solution
22%
7
8.
ST
To waste
treatment
ST
3
10
CW
CW
RF
Adipic
acid
12.
13.
9
RF
9.
10.
11.
11 CW
12
ST
13
To waste
treatment
FIGURE 1. Bio-based adipic acid production is based on fermentation, ultrailtration and crystallization processes
Hydrolysis reactor
Neutralization vessel
Air compressors
Seed trains
Fermenter
Cells centrifuge
Concentration
column
Ammonia recovery
column
Crystallizer
Dryer
NH3 refrigeration
unit
Cooling tower
Steam boiler
RF Refrigeration fluid
CW Cooling water
ST Steam
Production of Bio-based
Succinic Acid
By Intratec Solutions
The process
In the process depicted in Figure 1, succinic
acid is obtained via microbial fermentation of glucose from sugarcane juice. The
process steps and equipment were compiled
based on publically available information
from the scientific literature.
Sugar inversion. The sugar consumed in this
fermentation-based process is glucose. It is
obtained by the inversion of sucrose through
its hydrolysis to glucose and fructose. This is
achieved by subjecting the juice containing
sucrose to an acidic medium by addition
of hydrochloric acid (HCl). After inversion,
the pH is adjusted with sodium carbonate
(Na2CO3) and the stream is cooled before
being sent to the fermentation step.
Fermentation. Glucose is converted to
succinic acid through an anaerobic fermentation supplied with carbon dioxide.
The microorganism culture is prepared
for inoculation in a two-stage seed train.
Carbon dioxide is compressed, filtered and
Na2CO3
Economic performance
An economic evaluation of the bio-based
succinic acid process was conducted. The
following assumptions were taken into
consideration:
A 77,000 ton/yr unit erected on the U.S.
Gulf Coast (the process equipment is represented in the simplified flowsheet below)
Storage of product is equal to 30 days
of operation, and there is no storage for
feedstock
Outside battery limits (OSBL) units considered: steam boilers, cooling towers and
ammonium refrigeration system
The estimated capital investment (including
total fixed investment, working capital and
other capital expenses) is about $260 mil-
2,500
2,000
1,500
1,000
500
0
Net raw materials costs
Main utilities consumptions
Fixed costs
FIGURE 2. The operating expenses for biosuccinic acid are broken down here
Exhaust
gases
Cane
juice
HCl
$/ton of product
Activated
carbon
CW
Microorganisms
seed
1
Water
4
NH3
77
6
To waste
treatment
CW
CO2
ST
Purge
3
CW
CW
9
Succinic
acid
To waste
treatment
FIGURE 1. Bio-succinic acid is produced via the fermentation of glucose
RF
Process
water
Hot air
RF
HCl
8
10 CW
11
ST
12
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Hydrolysis reactor
Neutralization vessel
CO2 compressors
Seed train
Fermenters
Cells centrifuge
Vacuum column
Crystallizer
Dryer
NH3 refrigeration unit
Cooling tower
Steam boiler
RF Refrigeration fluid
CW Cooling water
ST Steam
The process
The process for cellulosic ethanol production
depicted in Figure 1 is similar to the AVAP
process described in the World Intellectual
Property Organization (Geneva, Switzerland; www.wipo.int) patent published
by American Process Inc. (W.O. Patent
2011/044378A1).
Pretreatment. The biomass is heated with
a solution of SO2, ethanol and water and
then fractionated into its three lignocellulosic
components: hemicellulose, cellulose and
lignin. Hemicellulose and lignin are partially
dissolved, while cellulose remains insoluble.
Cellulose is washed and the filtrate is sent to
the stripping column, where SO2 and ethanol are recovered in the overhead stream,
which is condensed in an evaporator and
sent to a make-up vessel. The column bottoms material is concentrated in the evaporator, generating vapor that is compressed
and used as steam supply for the evaporator and for the columns reboiler.
Cellulose hydrolysis and fermentation. Cellulose is hydrolyzed into glucose monomers
FIGURE 2.
by an enzymatic reaction.
Wood
Wood fractionInsoluble lignin is separated
ation for the
and conducted to the hemimanufacture of
AVAP process (biomass fractionation)
cellulose hydrolysis area
different inal
and glucose is fermented to
products
ethanol. The broth is centrifuged, then the cells are
Cellulose
Hemicellulose
Lignin
treated with sulfuric acid and
recycled to the fermenters.
Hemicellulose hydrolysis
Pulp and paper
Ethanol
Energy
and fermentation. The
products
concentrated stream from the
pretreatment area is mixed
with the lignin from the enzymatic hydrolysis Economic performance
An economic evaluation of the process was
and pumped to the auto-hydrolysis reactor,
conducted, taking the following assumptions
where hemicellulose is hydrolyzed to monointo consideration:
mer sugars, such as xylose. The hydrolyzate
A biomass processing unit producing 58
is neutralized with lime to precipitate the
million gallons of anhydrous ethanol per
soluble lignin. Insoluble lignin is separated
year, built on the U.S. Gulf Coast
and burned to generate steam and energy
Storage of products is equal to 30 days
to supply plant demands. The monomer
of operation, and there is no storage for
sugars are fermented to ethanol.
feedstock
Distillation. The broths from the fermentaThe estimated capital expenses (including
tion steps are mixed and conducted to the
total fixed investment, working capital and
concentration column, where a vapor side
other expenses) for the construction of this
stream with 50% ethanol is obtained. The
plant are about $700 million.
bottoms material from this column is used to
An interesting application to the prewash cellulose. The side stream is fed to the
sented technology is its integration with
rectifying column, generating an overhead
the pulp-and-paper industry. In this case,
stream containing about 93% ethanol. The
the process can fractionate wood into its
ethanol product stream undergoes dehydraprimary components (cellulose, hemiceltion in a molecular sieve unit, leading to
lulose and lignin). Then, each fraction can
ethanol product with 99.5% purity.
be used in different applications, targeting
each toward the most profitable market
Key research features
(Figure 2). n
Regarding its process, American Process
says the following:
The application of enzymes only for celEditors Note: The content for this column is supplied
lulose hydrolysis requires a lower dose
by Intratec Solutions LLC (Houston; www.intratec.us)
and edited by Chemical Engineering. The analyses
of enzymes when compared to processes
and models presented herein are prepared on the baconverting both cellulose and hemicellusis of publicly available and non-confidential informalose by enzymatic hydrolysis
tion. The information and analysis are the opinions of
Intratec and do not represent the point of view of any
The process offers an energy-eficient
third parties. More information about the methodolrecovery of cooking chemicals, resulting in
ogy for preparing this type of analysis can be found,
low expenses with chemical make-up
along with terms of use, at www.intratec.us/che.
1. Cooking digester
Enzyme
Vent
gases
Vent
gases
2. Cellulose washers
3. Stripping column
CW
Biomass
4. Make-up vessel
5. Two-effect evaporator
7
6
CW
CW
11
13
7. Cellulose fermenters
SO2
H2O
8. Auto-hydrolysis reactor
4
Sulfuric acid
Ethanol
Lime
ST
To waste
treatment
Electricity
10
Lignin
9. Neutralization vessel
10. Hemicelluloses fermenters
11. Concentration column
ST
9
ST
To waste
treatment
Ethanol
Vent
gases
8
5
12
CW
15
To waste
treatment
14
CW
FIGURE 1. Cellulosic ethanol production process similar to the AVAP process from American Process Inc.
The process
Ethanol from sugarcane is traditionally
produced by yeast fermentation of sugarcane
molasses. Commonly, raw sugar is obtained
as a co-product, through crystallization of
sugarcane raw juice. The major process steps
in sugarcane ethanol production (Figure 1) are
as follows:
Milling. Sugarcane is delivered from the field
to the factory, where it is weighed, cut and
shredded before being conducted to the mills,
where the raw cane juice is extracted. Sugarcane bagasse is obtained as a residue, and it
is burned to generate steam and electricity to
supply process demands.
Juice treatment. The raw cane juice is clarified
by treatment with phosphate and lime leading
to mud formation, which is separated in a
clarifier. The clarified juice is then concentrated
under vacuum in a multiple-effect evaporator,
forming a sugar syrup.
Sugar crystallization. Sugar crystallization
is accomplished in two vacuum calandrias,
where water is evaporated from the syrup
and crystallization is induced by the addition of a seeding solution. This process forms
a massecuite, a mixture of liquor and sugar
crystals. Next, crystallization is completed by
cooling in a crystallizer. The raw sugar is cen-
800
trifuged, dried and sent to storage.
In a third calandria-crystallizer set,
700
a massecuite is formed that will become the seeding solution to be used
600
at crystallization, and also the molasses for subsequent fermentation.
500
Fermentation. The sugars contained
in the molasses are fermented to
400
ethanol by yeast. Gases released
from the fermentation are washed
300
with recycle water in a gas-washing
column. The final broth is centri200
fuged, and the yeast cells are treated
with sulfuric acid and recycled to
100
the first fermenter. Meanwhile, the
ethanol-containing wine is sent to a
0
distillation apparatus.
Total fixed investment
Other capital expenses
Distillation. The ethanol solution is
Working capital
heated and fed to the concentration
column. The overhead of this column FIGURE 2. Capital expentitures for a sugarcane ethanol
is sent to the gas-washing column
plant erected in Brazil
and the vapor-side product stream,
containing about 50% ethanol, is fed
The electricity surplus generated in the plant
to a rectifying column that generates a 90%
is sold to the electric grid
ethanol vapor stream and recycle water, which
The estimated capital investment (including togoes to the gas-washing column. The ethanol
tal fixed investment, working capital and other
product stream undergoes dehydration in a
capital expenses) is about $670 million.
molecular sieve unit, leading to a product that
The process reported here allows sugis 99.5% pure ethanol.
arcane ethanol manufacturers to balance
ethanol and sugar production yields accordEconomic performance
ing to demand, rendering the activity flexible
An economic evaluation of the process was
to market fluctuations.
conducted based on data from the fourth quarBrazil is the main sugarcane ethanol producer
ter of 2012 (Figure 2). The following assumpand experienced, in the rst semester of 2013,
tions were taken into consideration:
a 7% increase in fuel ethanol consumption when
A 6 million-ton/yr sugarcane processing
compared to the same period of 2012.
unit producing 270 million L of anhydrous
ethanol and 420,000 ton of raw sugar per
year built in Brazil (the process equipment
Editors Note: The content for this column is supplied
is represented in the simplified flowsheet
by Intratec Solutions LLC (Houston; www.intratec.us)
and edited by Chemical Engineering. The analyses
below in Figure 1)
and models presented herein are prepared on the
The unit operates 210 d/yr
basis of publicly available and non-confidential infor Storage capacity equal to 30 days of operamation. The information and analysis are the opinions
of Intratec and do not represent the point of view of
tion for sugar and ethanol
any third parties. More information about the method Sugarcane cultivation and harvesting costs
ology for preparing this type of analysis can be found,
were not considered
along with terms of use, at www.intratec.us/che.
$, million
Vent
gases
ST
1
Sugarcane
Bagasse
Electricity
1.
2.
3.
CW
14
To
waste
treatment
Lime
2
7
CW
ST
CW
10
12
CW
Phosphate
Ethanol
7
Mud
11
CW
4.
5.
6.
7.
8.
9.
10.
5
6
5
6
13.
14.
To
waste
treatment
Sulfuric acid
11.
12.
ST
CW
13
CW
ST
Mills
Clarifier
Multiple-effect
evaporator
Vacuum calandrias
Crystallizers
Sugar centrifuges
Fermenters
Yeast centrifuge
Gas washing
column
Concentration
column
Rectifying column
Molecular sieve
unit
Cooling tower
Energy cogeneration unit
Cooling water
Steam
The process
In the process of producing ethanol via direct
gasification (Figure 1), biomass is converted into synthesis gas (syngas) by partial
oxidation and the resulting stream of gases
is partially burned to produce heat for the
process and partially reacted to produce liquid alcohols. The process can be divided into
the following areas: feedstock handling and
gasification, gas cleanup and conditioning,
alcohol synthesis and alcohol separation.
Feedstock handling and gasification. The
biomass is dried with fluegas from the fuel
combustor in the biomass drier. The dried
biomass is fed into the oxygen-blown direct
gasifier with steam and high-pressure oxygen from an air-separation unit.
In the presence of steam and oxygen at
high temperature, biomass decomposes into
syngas a mixture of mostly H2 and CO,
with CH4, CO2, light hydrocarbons and
water and tar, ash and char. The combustion of a portion of the biomass supplies
the heat for the endothermic reactions. A
cyclone is used at the exit of the gasifier to
remove residual solids from the syngas.
Flue gas
250
Air
BFW
CW
ST
ST
Solid
waste
Electricity
ST
5
O2
ST
BFW
CW
17
CW
CW
CW
CO 2
CW
8
16
To waste
treatment
Catalyst purge
11
100
6
1
150
ST
Biomass
200
50
Economic performance
The capital expense of the process was
estimated based on data from the second
quarter of 2013 (Figure 2). The following
assumptions were taken into consideration:
A biomass processing unit producing 30
Catalyst
Air
300
$, millions
Flue gas
12
10
CW
9
Sulfur
ST
14
13
ST
.
FIGURE 1. Ethanol production from direct gasiication of biomass
15
ST
ST
Higher
alcohols
by-product
Ethanol
1. Biomass drier
2. Air separation unit
3. Gasifier
4. Fuel combustor
5. Tar reformer
6. Catalyst regenerator
7. Quench column
8. Amine absorber
9. Amine regenerator
10. H2S removal system
11. Compression unit
12. Alcohol synthesis reactor
13. Molecular sieve unit
14. Higher alcohols column
15. Methanol column
16. Power generation
17. Cooling tower
BFW Boiler feed water
CW Cooling water
ST Steam
Ethylene Production
via Ethanol Dehydration
By Intratec Solutions
Ethanol
RF
CW
7
By-products
to fuel
PG
ethylene
CW
ST
ST
6
CW
ST
5
2
3
10
FU
ST
RF
Water
Fuel
Cooling water
Refrigeration fluid
Steam
Hydrogen Cyanide
Production
By Intratec Solutions
The process
HCN production via the Andrussow process
is depicted in Figure 1 and described below,
based on information available in the literature. The process can be divided into three
main areas: reaction, ammonia recovery and
product purification.
Reaction. Natural gas, ammonia and air are
fed into the reactor, where HCN is formed
through a catalytic reaction. The product
stream, containing HCN and unreacted ammonia, must be cooled down to avoid HCN
decomposition. This is accomplished in a
waste-heat boiler located below the reactor.
The waste-heat boiler generates steam that can
be used elsewhere in the process.
Ammonia recovery. The product stream is fed
to the bottom of the ammonia absorber, where
phosphate is used to absorb ammonia. The
overhead stream of this column, which contains
mainly HCN, is sent to the purification section.
The bottoms stream, containing ammonia and
a small amount of HCN, is heated and sent to
the first HCN stripper.
In this column, HCN is separated in the overheads and recycled to the ammonia absorber.
The bottom stream is fed to the top of the ammonia stripper, where phosphate is separated
in the bottoms. Part of this stream is mixed with
phosphoric acid and recycled to the top of the
ammonia absorber. Ammonia, now free of
phosphate, is separated as the overhead stream
of the ammonia stripper. The ammonia is then
directed to the dryer, where it is concentrated
1250
1200
Operating expenses ($/ton)
1150
1100
1050
1000
950
900
10
15
20
25
30
35
40
45
50
Economic performance
An economic evaluation of the process was
conducted, taking the following assumptions
into consideration:
A 22,800 ton/yr unit erected on the U.S.
Gulf Coast (the process equipment is represented in the simplified flowsheet below)
Outside battery limits units considered are
the cooling tower and the refrigeration system
No storage was considered
The capital investment (including total fixed
investment, working capital and other capital
expenses) for the construction of this plant is
estimated to be about $80 million, while the
operating expenses are estimated to be about
$1,070 per ton of product. The variation of the
Vent gas
to incineration
CW
2 ) Ammonia absorber
6
Natural
Gas
RF
HCN
7
ST
3
NH3
make-up
ST
ST
1
ST
To waste
treatment
CW
Air
To waste
treatment
5 ) Ammonia dryer
6 ) HCN absorber
7 ) Second HCN stripper
8 ) HCN rectification column
ST
BFW
CW
RF
4
2
9 ) Refrigeration unit
9
5
ST
Phosphoric acid
ST
ST
To waste
treatment
CW
10
CW Cooling water
ST Steam
FIGURE 1. The HCN production scheme shown here is based on the Andrussow process
RF Refrigeration fluid
Methanol-to-Olefins Process
By Intratec Solutions
The process
Figure 1 illustrates an MTO process similar
to one developed jointly by UOP LLC (Des
Plaines, Ill.; www.uop.com) and Norsk
Hydro A/S (Oslo, Norway; www.hydro.
com). This process synthesizes olefins from
methanol using a SAPO-34-type zeolite catalyst in a fluidized-bed reactor. The process
can be divided into three main areas: reaction and regeneration; quench, compression
and caustic wash; and product fractionation.
Reaction and regeneration. Methanol feed is
vaporized, mixed with recovered methanol,
superheated and sent to the fluidized-bed
reactor. In the reactor, methanol is first converted to a dimethylether (DME) intermediate
and then converted to olefins with a very
high selectivity for ethylene and propylene.
During the reaction, coke accumulates
on the catalyst, which is circulated to the
fluidized-bed regenerator system. In the
regenerator, the coke is removed by combustion with air to maintain the catalyst activity.
After leaving the reactor, the reacted stream
exchanges heat with the reaction feed, in
order to recover the heat generated by the
exothermic reaction.
Quench, compression and caustic wash.
The output from the reaction and regeneration is quenched, where most of water
and unreacted methanol is removed.
The water-methanol stream is sent to the
methanol-recovery column, where methanol
is recovered and recycled to the reaction.
Tail gas
RF
Regen gas
RF
RF
8
1
1
Process
water
Methanol
CW
10
7
ST
Ethane
ST
ST
CW
Air
ST
To waste
CW
CW
Caustic
soda
Ethylene
PG Propylene
12
11
ST
ST
RF
Water
13
CW
14
ST
15
ST
Propane
+
4
C byproduct
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Reactor
Regenerator
Quench tower
Compression
Methanol recovery column
Caustic wash column
Deethanizer column
Acetylene reactor
Demethanizer
C2 splitter
Depropanizer
C3 splitter
Refrigeration unit
Cooling tower
Boiler
CW Cooling water
RF Refrigeration fluid
ST Steam
Methanol-to-Propylene
Technology
By Intratec Solutions
The process
The MTP process consists basically of two
reaction steps: an initial one to dehydrate
methanol to dimethyl ether (DME) on an
aluminum oxide catalyst, and a second one
to transform DME and methanol into a variety
of olefins, ranging from ethylene to octenes.
However, using a zeolite-based catalyst (ZSM5), the process yields mainly propylene. A set
of purification columns is necessary to obtain
the polymer-grade (PG) propylene.
Figure 1 illustrates a process similar to the
ones licensed by Lurgi GmbH (the MTP process; Frankfurt am Main, Germany; www.lurgi.
com) and JGC Corp. (Yokohama, Japan; www.
jgc.co.jp) and Mitsubishi Chemical Corp.s
(Tokyo; www.mitsubishichemical.com) DTP
process, which can be divided into three main
areas: reaction and regeneration; quench and
compression; and product fractionation.
Reaction and regeneration. In this stage,
the methanol feed is vaporized, mixed with
recovered methanol and dimethyl ether (DME),
superheated and sent to the DME reactor,
where dehydration occurs.
The product is mixed with recycled hydrocarbons and steam before being fed into the
MTP reactors. The reactors were designed with
several stages to better approach isothermal
conditions. Propylene synthesis is conducted
in multiple reactors: while one set of reactors
conducts the reaction, the remaining ones are
in regeneration or on stand-by mode. The recy-
Economic performance
An economic evaluation of the process was
conducted based on data from the fourth quarter of 2012. The following assumptions were
taken into consideration:
A 560,000 ton/yr unit erected on the U.S.
Gulf Coast (the process equipment is represented in the simplified flowsheet)
There is no storage for feedstock and product
Outside battery limits (OSBL) units considered: propylene refrigeration system
The estimated capital investment (including
total fixed investment, working capital and
other capital expenses) to build the MTP plant
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
U.S. Gulf
Coast
FIGURE 2. Both China and the U.S. are favorable regions for MTP plants because of coal in
China and shale gas in the U.S.
Methanol
RF
CW
Recycle 3
ST
6
1
CW
10
ST
Recycles
1, 2 and 3
CW
ST
Recycle 1
CW
5
ST
PG Propylene
ST
11
CW
CW
CW
3. Quench
4. Compression
5. Methanol recovery
column
6. DME removal
system (col.1)
7. DME removal
system (col.2)
8. Debutanizer column
10. Deethanizer column
ST
LPG
1. DME reactor
2. MTP reactors
9. Dehexanizer column
CW
Recycle 2
China
11. Propylene-propane
splitter
12. Refrigeration unit
9
CW Cooling water
RF Refrigeration fluid
ST
Water
ST
ST
RF
12
FIGURE 1. Propylene production from methanol, according to a process similar to the Lurgi MTP and JGC Mitsubishi DTP processes
ST Steam
The process
Propylene conversion to polypropylene is
achieved through the use of a Ziegler-Natta
catalyst. This process occurs in a continuous
vertical stirred reactor at mild temperatures
(about 80C). The overall yields are typically
>99 wt.%. The process can be divided in three
main areas: purification and reaction; resin
degassing and pelletizing; and vent recovery.
Purification and reaction. The polymerization
catalysts are sensitive to several impurities,
such as oxygen and water. To meet these
Catalyst
Cocatalyst
CW
1
4
H2
300,000
exposure restrictions, purification equipment is used
before the reaction.
250,000
In the polymerizaProject
tion area, fresh purified
contingency
propylene is mixed with a
200,000
Indirect project
recycled monomer stream
expenses
and is fed to the reactor
150,000
Direct project
along with the catalyst,
expenses
co-catalyst and hydrogen.
The heat of polymerization
100,000
is removed from the reactor
by condensing propylene
50,000
gas from the top of the
reactor and recycling
the liquid back into the
0
agitated reactor.
Integrated
Non-integrated
Resin degassing and pelscenario
scenario
letizing. The outlet reactor
stream goes to a discharge FIGURE 2. Total ixed investment according to integration scenario
vessel to be separated.
Economic performance
The polymer powder is sent to a purge vessel,
An economic evaluation of the process was
while the carrier gas goes through a cyclone
conducted based on data from the first quarter
and a filter and is finally sent for recovery.
of 2013 for a plant with a nominal capacity
Nitrogen is used to remove residual monomer
of 300,000 ton/yr, erected in the U.S. Gulf
from the polymer powder and then the N2
Coast region (the required process equipment
gas is also sent for recovery.
is represented in the simplified flowsheet). Two
The polymer powder then goes to a screw
scenarios were analyzed:
extruder, where the powder and additives are
1) Integrated scenario. This case is based on
melted, compounded and homogenized. After
the construction of a plant linked to a propylbeing extruded, the pellets are carried to a
ene supplier. In this scenario, the nearby unit
centrifugal dryer.
continuously provides propylene, and receives
Vent recovery. The carrier gas is compressed
impure propylene for purification. Thus, no
and one portion of it is sent back to the reacstorage for propylene is required. However,
tor. The other portion is sent to a recovery
storage of products is equal to 20 days of
unit. The nitrogen and propylene streams
operation.
from the purge vessel are recovered and
2) Non-integrated scenario. This case corseparated in a membrane unit. The nitrogen
responds to a grassroots unit. Thus, 20 days
is recovered to the process, while the monoof operation was considered for both products
mer goes to a propylene-propane splitter
and raw materials. In addition, this scenario
(inside the purification area of the propylene
includes a propane-propylene splitter.
supplier, if the plant is part of a petrochemiThe level of integration is a key factor in this
cal complex).
process, since it can determine
whether the process is profitable
or not. The level of integration
Propylene
(1) Reactor
causes the total fixed investment
CW
suppliers
(2) Fixed-bed dryers
(Figure 2) and manufacturing
purification
expenses to vary greatly. In terms
area (integrated
(3) Discharge vessel
of manufacturing expenses, in
petrochemical
(4) Purge vessel
process)
non-integrated plants, propylene
is purchased at higher prices,
(5) Extruder
while in integrated complexes, it
Membrane
(6) Centrifugal dryer
can be obtained directly from the
recovery
Offgas
supplier at a lower cost. n
(7) Compression
to flare
system
Edited by Scott Jenkins
N2
2
Additives
6
Fresh
propylene
Polypropylene
pellets
FIGURE 1. Polypropylene production via a gas-phase process similar to that of Lummus Novolen
Editors Note: The content for this column is supplied by Intratec Solutions
LLC (Houston; www.intratec.us) and
edited by Chemical Engineering. The
analyses and models presented herein
are prepared on the basis of publicly
available and non-confidential information. The information and analysis
are the opinions of Intratec and do not
represent the point of view of any third
parties. More information about the
methodology for preparing this type
of analysis can be found, along with
terms of use, at www.intratec.us/che.
CW
CW
2
CW
N2 purge 10
Catalyst and
chemicals
ST
To waste oil
tank
CW
PG propylene
CW
ST
To water
treatment
N2
Additives
6
Propylene suppliers
purification area (integrated
petrochemical process)
Anti-fouling
agent
11
CW
Polypropylene
CW
12 ST
13
FIGURE 1. Over 35% of the world's polypropylene is produced using LyondellBasell's Spheripol (similar to the bulk-phase process shown)
Polypropylene Production
via Gas-Phase Process
By Intratec Solutions
The process
PP is a thermoplastic material formed by the polymerization of propylene, resulting in a macromolecule that contains from 10,000 to 20,000
monomer units. The production of a polypropylene homopolymer via a
gas-phase process similar to Dow Unipol is depicted in the diagram (Figure 1). The process shown is capable of producting homopolymer and
random copolymer PP. For impact copolymer production, a secondary
reaction loop is required. In this process, gaseous propylene contacts a
solid catalyst in a fluidized-bed reactor. The process can be separated
into three different areas: purification and reaction; resin degassing and
pelletizing; and vent recovery.
Purification and reaction. Fresh polymer grade (PG) propylene is sent
to fixed-bed dryers to remove water and other polar impurities. The
purified propylene, a recycle stream from the vent recovery system and
comonomers (in case of copolymer production) are then fed continuously to the reactor. A gas compressor circulates reaction gas upward
through the reactor, providing the agitation required for fluidization,
backmixing and heat removal. No mechanical stirrers or agitators are
required in the process reactor. The overhead gas from the reactor
passes through a cooler for reaction heat removal. Catalyst is continuously fed to the reactor.
Resin degassing and pelletizing. Resulting granular polypropylene is
removed from the reactor by the discharge tanks and sent to a purge
bin where residual hydrocarbons are stripped with nitrogen from the
resin and are sent to the vent recovery system. The resin from purge bin
is combined with additives and then flows to the pelletizing unit. The
pellets are dried, cooled and sent to product blending and storage.
Vent recovery. The vent gas is processed to separate hydrocarbons and
nitrogen purge gas, which is returned to the process. The condensed
components are separated into a propylene stream, which is returned to
the reaction system, and a propane stream.
Economic performance
An economic evaluation of the process was conducted for two distinct
integration scenarios:
Indirect
expenses
Project
contingency
350,000
300,000
$, thousands
olypropylene (PP) is one of the worlds most widely used polymers, second only to polyethylene in terms of global demand. The
global market for polypropylene is over 60 million metric tons per
year, and it is utilized in a broad and diverse range of end-uses from
injection-molding applications to films and sheets, as well as synthetic
raffia and other fibers, among others. Traditionally, the most representative types of propylene polymerization are the following: hydrocarbon
slurry or suspension, bulk (or bulk slurry), gas phase and hybrid (uses
bulk- and gas-phase polymerization reactors).
The Unipol PP process, a leading gas-phase process technology, was
recently offered for sale by Dow Chemical Co. (Midland, Mich.; www.
dow.com). The company is looking to focus on high-margin areas, and is
seeking buyers for its polypropylene licensing and catalyst business.
250,000
200,000
150,000
100,000
50,000
0
Non-integrated scenario
Integrated scenario
1. Fixed-bed dryer
2. Polymerization reactor
3. Gas compression and cooling
5. Purge bin
CW
Additives
1
Propane
purge
PG propylene
8. Centrifugal dryer
9. P-P splitter
CW Cooling water
ST
4
Catalyst and
additives
Polypropylene
pellets
Steam
Propylene Production
via Metathesis
By Intratec Solutions
For
disposal
FIGURE 1.
Fresh ethylene
Fresh butene
1
FU
3'
FU
Lights to fuel
RF
CW
izer column, the overhead stream is recycled back to the reactor and
Edited by Scott Jenkins
the bottom stream is fed to the depropylenizer column, which produces
polymer-grade propylene in the overhead, as well as a heavies product
Editors Note: The content for this column is supplied by Intratec Solutions LLC
stream (four-carbon compounds and greater) that is also recycled.
(Houston; www.intratec.us) and edited by Chemical Engineering. The analyses and
Economic performance
An economic evaluation of the process was conducted for three distinct
locations the U.S. Gulf Coast region, Germany and Brazil and
is based on data from the third quarter of
2011. The following assumptions were taken
FIGURE 2.
into consideration:
Each mark in the
A 350,000 ton/yr metathesis unit erected
map corresponds
to an existing
inside a petrochemical complex (all equipmetathesis plant.
ment is represented in the simplified
The nominal
flowsheet in Figure 1)
capacity of each
Storage cost of the main product is equal
plant follows the
to 20 days of operation, and storage cost
legend below:
for feedstocks was not considered
The excess fuel gas generated in the process is considered to be sold to a nearby
Up to 149,000 ton/yr
chemical plant at natural gas prices
models presented herein are prepared on the basis of publicly available and nonconfidential information. The information and analysis are the opinions of Intratec
and do not represent the point of view of any third parties. More information about
the methodology for preparing this type of analysis can be found, along with terms
of use, at www.intratec.us/che.
1,400
Main utilities
consumptions
1,200
1,000
800
600
400
200
0
US Gulf
Brazil
China
Working
capital
$, millions
600
500
400
300
200
US Gulf
Brazil
China
Global perspective
Recently, conditions in the U.S. have led to the lowest production costs
and the most attractive EBITDA (earnings before interest, taxes, depreciation and amortization) margins (about 30%), due to the availability
of low-cost propane derived from shale gas. Low-cost propane imported
from the Middle East allows China to present favorable EBITDA margins
of about 20%. The optimism about this process is demonstrated by the
recently announced plans for at least six PDH units in China.
Considering the capital-cost requirements presented and an operating
rate of 91%, the internal rate of return is above 30% in the U.S. and
about 20% in China.
On the other hand, South America and Europe do not offer favorable
conditions for PDH units.
Edited by Scott Jenkins
Editors Note:
The content for this column is supplied by Intratec Solutions LLC. (Houston; www.
intratec.us) and edited by Chemical Engineering. The analyses and models presented herein are prepared on the basis of publicly available and non-confidential
information. The information and analysis are the opinions of Intratec and do not
represent the point of view of any third parties. More information about the methodology for preparing this type of analysis can be found, along with terms of use,
at www.intratec.us/che.
Lights to fuel
5
PG propylene
RF
4
RF
CW : Cooling water
ST: Steam
(8) Deethanizer
(9) P-P Splitter
(10) Deoiler
ST
10
FU: Fuel
11
FU
7
(1) Reactors
(3) CCR
CW
Fresh propane
Other
700
Economic performance
An economic evaluation of the process was conducted based on data
from the second quarter of 2012. The following assumptions are assumed for the analysis:
A 550,000 ton/yr PDH unit erected inside a petrochemical complex
(all equipment represented in the simplified flowsheet below)
No storage of feedstock and product is considered
Net raw materials cost is the difference between propane and catalyst
make-up costs and credits from fuel and electricity generated in the
process
Fixed
costs
Heavies
to fuel
Catalyst flow
Sodium Hypochlorite
Chemical Production
By Intratec Solutions
13
odium hypochlorite (NaClO) is the active constituent in chlorine bleach, a strong oxidizer and
bleaching agent. Increases in household bleach
demand are driven mostly by population growth. In
turn, population growth and its corresponding increases
in water consumption coupled with limited fresh
water resources makes water treatment the largest
application for bleach, as well as the fastest-growing
segment of bleach use.
Sodium hypochlorite chemical production is a wellestablished process in the industry, and the principle
behind its operation is also employed for preventing
chlorine emissions in chlor-alkali plants. The chemical
process relies on the acquisition of chlorine and caustic
soda (sodium hydroxide; NaOH) feedstock from external sources, in contrast with the electrochemical process
for bleach, which also involves brine electrolysis.
12
11
10
9
8
7
6
5
20
40
15 C
The process
The chlorination of caustic soda to sodium hypochlorite is an exothermic reaction. The chemical production process depicted below is a
widely used process, similar to the one employed by Solvay Chemicals
(Brussels, Belgium; www.solvay.com), for example. The process is suited
to producing both household bleach (56 wt.%) and industrial bleach
(1015 wt.%), and relies on the chlorination of caustic soda by chlorine
gas within packed columns.
The industrial sodium-hypochlorite plant can be divided into two main
sections: reaction and product discharge; and bleach filtration.
Reaction and product discharge. The chlorine absorption system can
be divided into two parts: in the first, a packed column is operated
with a safe excess of caustic to prevent reduction in pH; the second
part, in turn, receives the liquor from the first column to be postchlorinated, until the desired bleach concentration is reached. Prior
to reaction, caustic soda is diluted with water in the first buffer tank,
along with the first-column bottom stream. Chlorine gas is diluted
with air and fed into the bottom of both columns. Flow to the second
part of the system is established when the finished product is sent to
the filtration steps.
Bleach filtration. Bleach filtration is necessary to meet product quality requirements and is often the last step before storage. Usually, the bleach
filter system consists of pressure-leaf filters. After filtration, the product is
sent to storage. Backwash water containing spent filter aid can be taken
to a dry-cake pressure filter for further processing.
Sodium hypochlorite solutions are very sensitive and special operations must be carried out to prevent its decomposition. Besides pH,
other factors affecting degradation are the initial bleach concentration,
exposure to ultraviolet light, presence of certain metals and elevated
20 C
CW
Backwash
water to
disposal
Chlorine
Air
Water
2
30 C
120
40 C
Global perspective
Selling prices for bleach vary substantially, depending on supply and
demand luctuations of the chlorine/caustic market. Based on the
estimated capital and operating costs, a U.S. Gulf Coast-based bleach
manufacturing venture can reach an internal rate of return (IRR) above
15%, by selling bleach at an average price of $175/ton, a reasonable
value. However, a venture in Germany would not be economically attractive at the same selling price.
Edited by Scott Jenkins
Caustic soda
100
Economic performance
An economic evaluation of the process was conducted for three distinct
locations the U.S. Gulf Coast region, Germany and Brazil and is
based on data from the first quarter of 2012. The following assumptions
are made for the analysis:
A 250,000 ton/yr chemical production unit (NaClO solution, 12.5
wt. %) erected inside a chlor-alkali facility (all equipment is represented in the simplified flowsheet)
Storage of products is equal to 20 days of operation, and there is no
storage for feedstock
The estimated capital investment for such a plant on the U.S. Gulf Coast
is about $35 million, the lowest among the regions compared. Germany
presented a higher capital investment, at $40 million, and the highest
operating costs about $170/ton (compared to $140/ton in the U.S.)
6
1
25 C
80
Offgas to
scrubber
CW
60
Time, days
Bleach
to storage
n-Butanol from
Lignocellulosic Feedstock
The process
The production process for n-butanol from corn stover via acetonebutanol-ethanol (ABE) fermentation is depicted in Figure 1. The feed
handling, pretreatment and fermentation steps were compiled from a
technical report published by the National Renewable Energy Laboratory (Golden, Colo.; www.nrel.gov; NREL/TP-5100-47764, May 2011)
and adapted for n-butanol production. The purification step was based
on typical ABE fermentation processes.
Feed handling. Corn-stover supply trucks send the biomass to weighting
and unloading stations, followed by a short-term queuing storage and
conveyors for feeding the feedstock to the pretreatment area.
Pretreatment. The biomass, composed of cellulose, hemicellulose and
lignin, is treated with dilute sulfuric acid and heated in a screw-feed
reactor to convert most of the hemicellulose into fermentable sugar, such
as xylose. After pretreatment, the solution is flash-cooled, and water is
removed, condensed and sent to the wastewater-treatment area. The mixture is then diluted with water and its pH adjusted by adding ammonia.
Hydrolysis and fermentation. In this step, cellulose is converted to
fermentable glucose using enzymes. The hydrolysis is initiated in a
continuous reactor and completed in several parallel batch fermenters.
The slurry is then cooled and inoculated with microorganisms, which
convert xylose and glucose into acetone, ethanol and n-butanol. The
fermentation beer is then sent to the beer well before being directed to
the purification section.
Purification. The fermentation beer is separated into acetone, ethanol
and n-butanol products by a series of distillation columns, a decanter
and a molecular sieve unit (to purify ethanol to commercial grade). The
bottoms of the beer column, containing water and lignin, is sent to a
filter. The filtrate is directed to the wastewater-treatment apparatus. The
residues from wastewater treatment and lignin from filtration are burned
for steam and electricity generation. The distillate from the n-butanol column is recycled to the acetone column to improve n-butanol recovery.
Corn Stover
n Acrylate
n Glycol ethers
n Acetate
n Plasticizer
n Other
n Amino resins
2%
2%
1%
Economic performance
An economic evaluation of the process was conducted taking into
consideration a facility located on the U.S. Gulf Coast that is capable
of producing 100,000 ton/yr of bio-butanol, 10,000 ton/yr of acetone
and 8,000 ton/yr of ethanol.
The total estimated investment (including total fixed investment, working capital and initial expenses) for this plant is about $450 million,
while the operating expenses are about $1,000/ton of n-butanol.
Global perspective
In the past, the ABE fermentation was used to commercially produce
acetone and n-butanol, but this process fell out of favor because petrochemical processes became more cost-effective.
Still, the production of bio-butanol from ABE fermentation presents
several challenges, such as low n-butanol yield, concentration and productivity, when compared to ethanol biofuel. However, recent research
has been focused on enhancing such issues by developing improved
microorganisms, fermentation techniques and low-energy recovery
methods, in order to reduce production costs.
A good strategy to prove the bio-butanol production technology at
commercial scale is to target the chemicals market, which offers higher
margins and a broad range of applications (Figure 2). Later, consideration could be given to entering the fuels market, which offers far
higher volumes, but lower margins. n
Editors Note: The content for this column is supplied by Intratec Solutions LLC
(Houston; www.intratec.us) and edited by Chemical Engineering. The analyses
and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis can be found,
along with terms of use, at www.intratec.us/che.
CW
15
Filtrate
6
Enzyme
Ammonia
CW
17
Residues
14
Lignin
16
CW
CW
ST
EE
CW
CW
Ethanol
Acetone
9
5%
CW
Sulfuric acid
ST
20%
BFW
2
26%
12%
n Solvent
Water
32%
n Exports
10
13
11
12
ST
ST
ST
ST
n-Butanol
1) Feed handling
2) Screw-feed reactor
3) Flash vessel
4) Ammonia conditioning
5) Continuous hydrolysis
6) Batch hydrolysis/fermentation
7) Beer well
8) Beer column
9) Acetone column
10) Ethanol column
11) Molecular sieve unit
12) Decanter
13) n-butanol column
14) Pressure filter
15) Wastewater treatment unit
16) Energy cogeneration unit
17) Cooling tower
BFW boiler feed water
CW cooling water
EE electricity
ST steam
Sugar Inversion
he substance known colloquially as table sugar is actually sucrose, a disaccharide composed of fructose and glucose. Sucrose
n inis a major agriculturally derived product with an established
dustry for its extraction, processing and supply. It is mainly employed
as
n
a sweetener in industrial and domestic food applications, but also
n finds
additional uses in the pharmaceutical industry, in chemical manufacturn
ing, and as a feedstock for fermentation processes. For example, sugar
n
is used as a feedstock for the manufacture of bio-based chemicals, such
n
as bio-succinic acid.
n
Sugar generally exists commercially as a solid granular product.
However, some food manufacturers prefer to use sugar in a liquid
n form,
due to the ease of handling a liquid product. One commercially available liquid-sugar product is liquid invert sugar, also known as invert
syrup. It is produced from the inversion of sucrose, which refers to the
hydrolysis of the disaccharide molecule into its constituent parts, the
monosaccharides glucose and fructose. The result of this reaction is a
product with greater sweetening power and improved microbiological
stability, when compared to sucrose.
Invert syrups are commercialized with different combinations of invert
sugar and sucrose contents, depending on the degree of inversion performed. Also, invert syrups can be produced by three different inversion
processes: acid hydrolysis with mineral acids; enzymatic hydrolysis; or
hydrolysis by cation ion-exchange resin. The latter process is described
in this column.
The process
The process for sucrose inversion by ion-exchange resin shown in
Figure 1 is similar to the one presented in U.S. Patent 8,404,109, published by European Sugar Holdings S.a.r.l. (Capellen, Luxembourg). An
important feature of this process is the removal of ash from the solution
in the ion-exchange columns.
Sucrose dissolution. Water and steam are mixed to form a hot water
stream. Part of this stream is added to raw sugar (sucrose) before it is
fed to a screw conveyor, which directs wet sucrose to an agitated vessel. The remaining hot water is fed into the vessel, forming a 60 wt.%
sucrose solution.
Sucrose inversion. The sucrose solution is fed to a cation-exchange
column, where some ash is retained and the pH is lowered, allowing
the inversion reaction to occur. Then, part of the inverted solution is fed
to an anion-exchange column, where some ash is removed and the pH
of the solution is increased. Finally, the fully inverted solution is concentrated to 70 wt.% dry matter, forming the final product.
Economic evaluation
An economic evaluation of the sugar-inversion process was conducted,
taking the following assumptions into consideration:
A facility producing 585,000 ton/yr of invert syrup from raw sugar.
The facility was assumed to be located on the U.S. Gulf Coast in the
same location as a plant operating a fermentative process that uses
invert syrup as feedstock
A raw-sugar warehouse with storage capacity equal to 20 days of
operation
Utilities facilities and product storage were not considered in the
analysis
H2O
Raw Sugar
n United States
5%
n Brazil
22%
n India
15%
n European Union
n China
n Thailand
n Mexico
n Others
9%
8%
6%
4%
31%
The estimated total fixed investment for building such a plant is about
$40 million.
Global perspective
Sucrose can be produced either from sugarcane or sugarbeet plants,
depending on climate conditions. Sugarcane is cultivated in tropical
and subtropical regions, while sugarbeets are more suitable in temperate zones.
In 2013, world sugar production was about 177 million tons (in raw
sugar equivalent). About 80% of global sugar production is derived
from sugarcane, and about 20% is from sugarbeets.
Brazil, the worlds largest sugar producer, accounts for about 22%
of global sugar production, with all of its sugar production originating
from sugarcane.
The worlds main sugar producers are shown in Figure 2. The U.S. is
the only country among them that produces sugar from both sugarcane
and sugarbeet in significant amounts. As the worlds sixth-largest sugar
producer, the U.S. produces 56% of its sugar from sugarbeets, while
the remaining 44% comes from sugarcane. n
Editors Note: The content for this column is supplied by Intratec Solutions LLC
(Houston; www.intratec.us) and edited by Chemical Engineering. The analyses
and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis can be found,
along with terms of use, at www.intratec.us/che.
ST
CW
To waste
treatment
5
ST
2
CW
Liquid
invert
sugar
1) Screw conveyor
2) Dissolution vessel
3) Cation exchange resin bed
4) Anion exchange resin bed
5) Evaporator
CW Cooling water
ST Steam
Technology Profile
Green Ethylene Production
By Intratec Solutions
The process
A process for ethylene production
via ethanol dehydration similar to the
processes developed by Chematur
Technologies AB (Karlskoga, Sweden; www.chematur.se) and Petron
Scientech Inc. (Princeton, N.J.; www.
petronscientech.com) is depicted in
Figure 1. The reaction occurs in four
fixed-catalyst-bed adiabatic reactors.
Reaction. Ethanol is vaporized,
heated in a furnace and fed to the
first reactor. During reaction, the temperature drops and the output stream
must be re-heated before entering the
Global perspective
Economic performance
An economic evaluation of the process assumes the following:
A facility capable of producing
300,000 ton/yr of green ethylene constructed on the U.S. Gulf
C2=
1
Lights
to fuel
ST
RF
Ethanol
CW
10
RF
11
ST
12
C2=
PW
2
5
CW
FU
BFW
Caustic
soda
4
CW
To waste
treatment
To waste
treatment
ST
ST
Heavies
to fuel
Ethylene product
(C2=) to heat
integrations
1) Ethanol vaporizer
2) Furnace
3) Reactors
4) Quench column
5) Compression system
6) Caustic washing column
7) Molecular sieve unit
8) Ethylene column
9) Stripper column
10) Cooling tower
11) Refrigerant system
12) Steam boiler
BFW Boiler feed water
C2= Ethylene product
CW Cooling water
FU Fuel
PW Process water
RF Refrigerant
ST Steam
FIGURE 1. Green ethylene production via an ethanol dehydration process that is similar to Chematur and Petron processes
CHEMICAL ENGINEERING
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FEBRUARY 2015
39
Technology Profile
Propane Dehydrogenation: Oxydehydrogenation
By Intratec Solutions
ropylene is a major component of the global olefins market and is widely used as an
intermediate for an array of
chemical and plastic products.
Propylene is produced as a byproduct in steam crackers and through
fluid catalytic cracking (FCC) processes. However, due to the increased
availability of inexpensive ethane from
shale gas, ethane has been preferentially used as a feedstock in steam
crackers over naphtha, a practice that
results in minor propylene production.
In this context, on-purpose propylene production routes are of great
interest to the petrochemical marketplace. Among them, propane dehydrogenation (PDH) technology is an attractive option, and has been applied
in several plants around the world.
The process
The PDH process depicted in Figure
1 is similar to the STAR (steam active
reforming) process (Uhde GmbH; Dortmand, Germany; now ThyssenKrupp
Industrial Solutions; www.thyssenkrupp.com), which applies the oxydehydrogenation principle. Two other PDH
processes were previously discussed
in this column (Chem. Eng., Feb. 2013,
p. 33 and Jan. 2014, p. 27).
The STAR process was the first to
apply the oxydehydrogenation principle
for propylene production, significantly
enhancing performance. In this technology, O2 is added to the system to
react with H2, forming water. This reaction lowers H2 partial pressure, shifting
the equilibrium to higher conversion of
propane into propylene while providing
55
50
45
40
35
Without oxygen
02/HC ratio = 0.05
02/HC ratio = 0.1
30
25
20
550
560
570
580
Temperature (oC)
Economic performance
An economic evaluation of a PDH plant
was conducted, assuming a facility
with a nominal capacity of 450,000
ton/yr of PG propylene erected at a
petrochemical complex on the U.S.
Gulf Coast (no storage for feedstock
and product was considered).
Estimated capital expenses (total
fixed investment, working capital and
initial expenses) for such a plant are
$400 million and estimated operating
expenses are $770/ton of product.n
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented are prepared on the basis of publicly available and
non-confidential information. The content represents the opinions of Intratec only. More information about the methodology
for preparing analysis can be found, along with terms of use,
at www.intratec.us/che.
Lights
to fuel
RF
14
RF
FU
Lights
to fuel
10
2
CW
CW
PG
propylene
ST
CW
12
CO2
BFW
Propane
RF
6
O2/air
ST
13
ST
ST
BFW
ST
Heavies
to fuel
Water
MDEA Piperazine
make-up make-up make-up
600
from the cold box is sent to the fractionation area, which consists of a deethanizer column for removal of lights
and a propane-propylene (P-P) splitter,
where polymer-grade (PG) propylene is
obtained. Unreacted propane from the
splitter bottoms is recycled.
11
Air
590
H2 byproduct
ST
60
ST
1) Depropanizer column
2) Reformer reactor
3) Feed pre-heater
4) Oxyreactor
5) Compression system
6) Absorption column
7) Flash vessel
8) Regeneration column
9) Molecular sieve unit
10) Cold box
11) PSA unit
12) Deethanizer column
13) P-P splitter
14) Refrigeration unit
MDEA Methyl
diethanolamine
BFW Boiler feed water
CW Cooling water
FU Fuel
RF Refrigeration fluid
ST Steam
FIGURE 1. Propane dehydrogenation process similar to the Uhde (now ThyssenKrupp) STAR process
48
CHEMICAL ENGINEERING
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MARCH 2015
Technology Profile
Onsite Enzyme Production
By Intratec Solutions
The process
A typical process for onsite enzyme
production through fermentation is described below, using the enzyme cellulase as an example. Cellulase is used
in the hydrolysis of lignocellulosic material in biomass-based processes, such
as the production of cellulosic ethanol.
Cellulase is industrially produced by a
fungus in an aerobic fermentation in
the presence of a cellulase-production
inducer (Figure 1). The process shown
was compiled from a technical report
published by the National Renewable
1) Medium tank
2) Nutrients tank
3) Pre-fermentation
compressor
4) Pre-fermenters
5) Fermentation
compressor
6) Fermenters
3
Air
Lignocellulosic
biomass
Pretreatment
Nutrients
Fermentation
Distillation
Cellulosic
ethanol
Solid residues
FIGURE 2. A typical cellulosic ethanol production process is shown here
Economic evaluation
An economic evaluation of the process was conducted based on data
5
CW
Enzymatic
hydrolysis
Air
CW
Global perspective
Cellulase enzyme is applied to hydrolyze lignocellulosic biomass, which is
used as feedstock in the production
of cellulosic ethanol (Figure 2). In this
way, cellulosic ethanol costs are highly
related to enzyme costs.
Initially, enzyme costs were too high,
so cellulosic ethanol was not costcompetitive with corn-based ethanol.
Currently, many advances in enzyme
technology have been achieved, lowering enzyme costs in cellulosic ethanol by both enzyme production-cost
reduction and enzyme efficiency enhancement. In addition, onsite production allows the manufacture of the
desired enzyme at lower costs, since
some downstream operations present
in a standalone enzyme unit (such as
purification, formulation and storage),
as well as transportation of the enzyme product, are not necessary. n
For more on industrial enzymes, see Tunable Enzymes and the Leaner, Greener CPI in the January
2015 issue of Chem. Eng. at www.chemengonline.com
CW Cooling water
Glucose
water
Cellulase
1
Cellulase
Cellulase
broth
Editors Note: The content for this column is supplied by Intratec Solutions LLC (Houston; www.intratec.us) and edited by
Chemical Engineering. The analyses and models presented are
prepared on the basis of publicly available and non-confidential
information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis
can be found, along with terms of use, at www.intratec.us/che.
CHEMICAL ENGINEERING
WWW.CHEMENGONLINE.COM
APRIL 2015
Technology Profile
Hydrogen Production from Natural Gas
By Intratec Solutions
The process
In the process described below and
depicted in Figure 1, H2 is produced
from natural gas using an SMR process. The process was compiled
based on information available in the
chemical literature.
Sulfur removal. Natural gas feed-
Natural
gas
H2
Central
facility
Distributed
facility
FIGURE 2. There are three types of hydrogen production facilities, and they differ in location and scale of
production
Economic evaluation
An economic evaluation of the process was conducted based on the
following assumptions:
1) Hydrotreater
2) Desulfurizer
3) Reformer reactor
4) Water-gas shift
reactor
5) Pressure-swing
adsorber system
Air
FU
BFW
ST
4
ST Steam
FU Fuel
BFW Boiler feed water
3
H2
product
5
Semi-central
facility
Hydrogen
point of
use
ST
40160 km
80480 km
CHEMICAL ENGINEERING
Global perspective
There are three kinds of facilities for H2
production: central, semi-central and
distributed facilities (Figure 2). They
differ in their location and scale of production, characteristics that directly
affect H2 cost, competitiveness and
timeframe to market.
Central facilities are located far from
the H2 point of use and are able to produce large amounts of H2, benefiting
from economies of scale. This type of
facility requires high capital investment,
as well as a distribution infrastructure
able to cover large distances.
Semi-central facilities present intermediate H2-production capacity. They present reduced distribution costs, since they
are sited closer to H2 points of use.
Distributed facilities are small facilities located close to or at the point
of H2 use, reducing delivery costs.
These facilities may present production capacities fitted to local demand.
They require less investment than the
other facilities, although unit production costs may be higher.
n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by Intratec Solutions LLC (Houston; www.intratec.us) and edited by
Chemical Engineering. The analyses and models presented are
prepared on the basis of publicly available and non-confidential
information. The content represents the opinions of Intratec only.
More information about the methodology for preparing analysis
can be found, along with terms of use, at www.intratec.us/che.
WWW.CHEMENGONLINE.COM
MAY 2015
Technology Profile
Bio-based Methionine via Fermentation of Glucose
By Intratec Solutions
ethionine is an essential
amino acid that is not produced by animals. Methionine must be obtained
from dietary sources, and its major
use is as an animal nutritional-feed
additive. Methionine is mainly derived
from petrochemical sources. However,
biochemical routes to obtain it have
been researched. For instance, a joint
venture between CJ Bio (cjbio.net) and
Arkema (arkema.com) initiated methionine production using both renewable
and petrochemical raw materials; and
Metabolic Explorer (metabolic-explorer.com), in partnership with Roquette
(roquette.com), developed a process
for 100% bio-based methionine.
cess, which is divided into two phases: batch and fed-batch. Fermenters
are filled with the batch medium, and
fermentation occurs until glucose exhaustion, when the fed-batch phase is
started by adding the fed-batch medium until the end of the fermentation.
Clarification and demineralization.
Culture broth is clarified by the removal of insoluble and soluble organic
impurities by centrifugation and ultrafiltration, respectively. Next, the broth
is demineralized using ion-exchange
resins to remove cations and anions.
Pre-concentration, crystallization
and filtration. L-methionine is concentrated in an evaporator prior to
crystallization under vacuum by water
evaporation. Then, precipitated methionine is sent to a vacuum filter, where
it is separated from the crystallization
mother liquor, which still contains dissolved methionine.
Products recovery. Filtered L-methionine is directed to a dryer, where Lmethionine powder with 99.5 wt.% of
dry matter (90 wt.% of methionine) is
obtained. Evaporated water is sent to
a wash column before being used in
methionine washing during filtration.
Also, the crystallization mother liquor
is acidified with HCl, then concentrated, resulting in the liquid L-methionine
byproduct, which contains 60 wt.% of
dry matter (22 wt.% of methionine).
The process
The production of L-methionine via a
method similar to the one proposed in
patents issued to Metabolic Explorer
and Roquette is described below and
presented in Figure 1. In this process,
L-methionine is produced through a
fed-batch aerobic fermentation, using glucose as the carbon source and
ammonium thiosulfate as the nitrogen
and sulfur source. Products obtained
from this process are L-methionine
powder (final product) and liquid Lmethionine compound (byproduct).
Media preparation. Culture media
used in the fermentation are prepared
by mixing water, corn syrup (70 wt.%
glucose) and aqueous ammonium
thiosulfate solution in medium vessels.
Fermentation. A recombinant microorganism produces L-methionine
through an aerobic fermentation pro-
Economic performance
An economic evaluation of the process was conducted based on data
from Q1 2014. The following assumptions were taken into consideration:
Water
purge
Corn syrup
H20
Ammonium
thiosulfate
solution
Global perspective
Historical methionine-consumption is
presented in Figure 2. Globally, Western Europe, North America and North
Asia are the major consumer regions.
While most regions had similar growth
in methionine consumption (average
growth rates around 5%/yr), North Asia
stands out at 11%/yr. n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
CW
To flare
H20
3
CW
Air
ST
11
9
6
2
Insoluble
impurities
Soluble
impurities
10
CW
Water
purge
ST
HCI
L-methionine
powder
12
L-methionine
liquid compound
CW
5
Corn syrup
H20
Ammonium
thiosulfate
solution
CHEMICAL ENGINEERING
CW
13
ST
14
WWW.CHEMENGONLINE.COM
JUNE 2015
Technology Profile
Green FDCA Production
By Intratec Solutions
Production process
Figure 1 depicts an FDCA production
process from a glucose solution via the
furan pathway in a process similar to
that developed by Avantium Technologies B.V. (Amsterdam, the Netherlands;
www.avantium.com). This process can
be divided into three main areas: furans
production, methoxy methyl furan (MMF)
purification, and FDCA production.
Furans production. The glucose content of the feed is first enzymatically
isomerized to fructose, and the effluent
Glucose
syrup
Global perspective
The main production cost, as in many
commodities-production processes,
is the purchase of raw materials. Not
only is glucose syrup an expensive
source of glucose for this process,
but also the conversion of fructose to
MMF is relatively low, increasing the
raw-material consumption. It would
be beneficial for the profitability of the
process to integrate it with biomass
treatment, in order to obtain raw materials at lower costs. This process
could easily integrate with a biorefinery, where it is possible to achieve a
more efficient valorization of the biomass used as feedstock.
n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
Waste water
Economic performance
An economic evaluation of an FDCA
plant was conducted, assuming a
facility with a nominal capacity of
300,000 ton/yr of purified FDCA constructed on the U.S. Gulf Coast. Included was a storage capacity equal
to 20 days of operation for feedstocks
and products.
Estimated capital expenses (total
fixed investment, working capital and
initial expenses) to construct the plant
are about $600 million, while the operating expenses are estimated at about
$1,550/ton of purified FDCA.
ST
Waste water
2
CW
7
4
Methanol
6
Methanol sol.
Sulfuric acid
CW
CW
14
CW
ST
Water for
recycle
ML
ST
CW
13
CW
ST
Waste water
10
CW
Recovered
catalyst
11
9
12
Water
Hydrogen
ST
ST
ST
ST
Heavies to boiler
Purified FDCA
CW
15
ST
16
1) Isomerization reactor
2) Evaporator
3) Ion exchanger
4) Crystallizers
5) Furan conversion reactor
6) MMF recovery system
7) Oxidation reactor
8) Rotary filter
9) Hydrogenation reactor
10) Crystallizers
11) Centrifuges
12) Rotating dryers
13) Water removal column
14) Acetic-acid-recovery column
15) Cooling tower
16) Steam boiler
ML Methyl levulinate byproduct
CW Cooling water
ST Steam
FIGURE 1. FDCA production process via furans pathway similar to Avantium YXY process
CHEMICAL ENGINEERING
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JULY 2015
33
Technology Profile
Lactic Acid Production via Glucose Fermentation
By Intratec Solutions
The process
Figure 1 depicts a process for lactic
acid production via glucose fermentation similar to that developed by
Purac (now Corbion; Amsterdam, the
Netherlands; www.corbion.com). This
process generates an 88 wt.% lactic acid solution in water that can be
used as the raw material in polymerization processes. Rigorous control of
fermentation conditions and additional
purification steps are necessary to ensure both optically and chemically pure
lactic acid. The quality of the PLA produced from it depends on the purity.
Fermentation. Glucose solution is
fed to the fermenter. It undergoes a
continuous anaerobic bacterial fermentation, and is converted to lactic
acid. The fermentation temperature is
controlled by circulating cooling water
through internal coils, and the pH is
controlled by the addition of CaCO3
solution, which reacts with lactic acid
to form calcium lactate.
Economic performance
An economic evaluation for a lacticacid production plant was conducted,
assuming a facility with a nominal capacity of 100,000 ton/yr of lactic acid
solution (88 wt.%) constructed on the
ST
CW
Calcium
carbonate
1
Biomass
ST
Extractant
solution
3
CW
Calcium
sulfate
10
ST
ST
Waste stream
13%
11%
n Raw materials
n Calcium sulfate disposal
n Utilities
n Fixed costs
n Depreciation
Global perspective
Major production-cost components for
this process are raw material acquisition (mainly glucose and CaCO3) and
CaSO4 byproduct disposal (Figure 2).
Recent improvement efforts focus on
using less costly cellulosic material
to obtain fermentable sugars, and on
developing low-pH-tolerant bacteria
strains, which would decrease both
CaCO3 use and CaSO4 generation. n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
Lactic
acid
11
46%
13%
1. Fermenter
2. Decanter
3. Acidification vessel
4. Rotary filter
5. Belt filter
6. Evaporator
7. Ion exchange beds
8. Solvent extraction system
9. Evaporator
Waste
10. Light end column
stream
11. Heavy end column
Waste stream
12. Hydrolysis reactor
CW
13. Cooling tower
14. Steam boiler
Process water
Glucose
17%
ST
ST
12
CW Cooling water
ST Steam
CW
13
ST
14
FIGURE 1. A lactic-acid production process from glucose, similar to the Purac process
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AUGUST 2015
37
Technology Profile
Production of Polylactic Acid
By Intratec Solutions
Biomass
Calcium sulfate
Biomass
treatment &
hydrolysis
Glucose
fermentation
to lactic acid
Lactic acid
conversion
to lactide
Economic performance
An economic evaluation of a PLA plant
was conducted, assuming a facility
with a nominal capacity of 100,000
ton/yr of PLA constructed on the U.S.
Gulf Coast. Storage capacity for the
final product equal to 20 days of operation was assumed, but raw material storage was not included.
Waste stream
Lactide
ring-opening
polymerization
CW
Global perspective
The recent decrease in oil prices has
reduced the production costs for most
fossil-fuel-based polymers, threatening the competitiveness of PLA projects. Efforts to reduce PLA production
costs must be focused on acquisition
of low-cost raw material. An alternative to allow access to less costly raw
material would be the integration of
PLA production with lactic acid production from a renewable feedstock,
such as biomass (Figure 2; Chem.
Eng. August 2015, p. 37).
In an attempt to reach new markets, some companies are researching methods for producing PLA with
enhanced physical properties. These
methods include the production of a
polymer that consists of a mixture of
poly(L-lactic acid) and poly(D-lactic
acid). This polymer exhibits improved
physical properties when compared
to conventional PLA, produced exclusively from L-lactic acid feedstock. n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
CW
1
ST
Catalyst
ST
ST
Waste stream
Stabilizer
Catalyst
Waste stream
CW
Polylactic acid
FIGURE 2. PLA is
produced from
lactide rings
Waste stream
CW
CW
Lactic acid
Solid waste
1. Oligomerization reactor
2. Depolymerization reactor
3. Drying column
4. Purification column
5. Catalyst melting vessel
6. Polymerization reactor
7. Devolatizer
8. Extruder & pelletizer
9. Dryer
10. Cooling tower
11. Steam boiler
Air
CW Cooling water
ST Steam
CW
10
Polylactic acid ST
11
FIGURE 1. The PLA production process occurs via a ring-opening polymerization process similar to that of NatureWorks
44
CHEMICAL ENGINEERING
WWW.CHEMENGONLINE.COM
SEPTEMBER 2015
Technology Profile
Ethylene Glycol Production
By Intratec Solutions
The process
Figure 1 depicts MEG production
from ethylene via a process similar to
the OMEGA catalytic process from
Shell Global Solutions (The Hague,
the Netherlands; www.shell.com). In
the described process, MEG is produced via EO, which is manufactured
in an integrated plant utilizing Shell EO
technology. An important feature of
the process is the negligible production of diethylene glycol (DEG) and
triethylene glycol (TEG), which occur
as byproducts in other ethylene glycol
production processes.
Ethylene oxide production. Ethylene
and oxygen are fed to a multi-tubular
reactor, forming EO. This exothermic
reaction, conducted in fixed beds in the
reactor tubes, occurs in the gaseous
phase with the use of a silver catalyst
supported on alumina. Steam is generated by the heat of reaction.
Ethylene oxide recovery. The reactor product stream is fed to the EO
absorber for lights removal by water
quenching. Part of this gaseous overhead stream is recycled to the reactor,
while the other part is sent to a carbon-
Location
Lotte Chemical
400
2008
Petro Rabigh
600
2009
Shell
750
2009
Global perspective
Shell OMEGA is the first process to
enable ethylene glycol production via
a fully catalytic process. According
to the licenser, the process is able to
achieve EO-to-EG converstion and
selectivity near 100%, leading to production of MEG only.
However, although 40% of worldwide ethylene glycol production is
derived from processes using Shell
technologies, only three plants in the
world use the new Shell OMEGA technology (Figure 2). As can be seen, two
of these plants are located in Asia,
which is the region of the world responsible by the major share of MEG
global consumption. China alone accounts for about 45% of global demand for MEG.
n
Edited by Scott Jenkins
Economic performance
An economic evaluation of the process was conducted based on data
from the first quarter of 2015, assuming a facility with a nominal capacity
of 750,000 ton/yr of MEG constructed
on the U.S. Gulf Coast.
Estimated capital expenses (total
CO2
Ethylene
O2
Steam
CO2 vent
1
7
CW
8
Water
CO2
10
MEG
ST
Waste stream
ST
Start-up year
ST
Ethylene oxide
9
ST
Catalyst recycle
CW
11
ST
12
CW Cooling water
ST Steam
FIGURE 1. Monoethylene glycol (MEG) production, according to a process similiar to the Shell OMEGA process
44
CHEMICAL ENGINEERING
WWW.CHEMENGONLINE.COM
OCTOBER 2015
Technology Profile
Ethylene Production via Cracking of Ethane-Propane
By Intratec Solutions
The process
The process shown in Figure 1 is a
steam-cracking process for ethylene
production from an ethane-propane
mixture. The process can be divided
into three main parts: cracking and
quenching; compression and drying;
and separation.
Cracking and quenching. Initially, an
ethane-propane mixture is fed to furnaces in which, under high-severity
conditions, it is cracked, forming ethylene, propylene and other byproducts.
The furnace outlet stream is subsequently fed to a water-based quench,
to prevent further reactions and formation of undesirable byproducts.
From a decanter downstream from
the quench tower, heavies, condensed dilution steam, tar and coke
are removed. Cracked gas from the
quench is then directed to compression and separation.
Compression and drying. The compression of the cracked gas is performed across five stages. After the
third stage of compression, carbon dioxide and sulfur are removed from the
cracked gas by caustic soda and water washes in a caustic scrubber. The
compressed cracked gas is cooled
and subsequently dried by molecular
sieves that remove most of the water.
13%
59%
13%
n Polyethylene
n Ethylene oxide
n Ethylene dichloride
n Ethylbenzene
n Others
Global perspective
With a global nominal capacity of
about 155 million ton/yr, ethylene is
among the major petrochemicals produced worldwide. The major part of
ethylene production is consumed in
the manufacture of polyethylene, but
ethylene is also applied in the production of ethylene oxide, ethylene dichloride and ethylbenzene (Figure 2). n
Edited by Scott Jenkins
Editors Note: The content for this column is supplied by
Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
Economic performance
An economic evaluation of the process was conducted based on data
from the first quarter of 2015, considering a facility with a nominal capacity
3
Dilution
stream
8%
7%
4
1
Lights to
fuel
Ethane/
propane
To waste
treatment
6
2
CW
7
Tar and
coke to
disposal
Water to waste
treatment
PG
ethylene
product
10
Heavies
to fuel
11
C4+ to
fuel
PG
propylene
by-product
CW
1. Furnaces
2. Quench column
3. Compression system
4. Caustic scrubber
5. Drying unit
6. Cold box
7. Demethanizer column
8. Deethanizer column
9. C2-splitter
10. Depropanizer column
11. C3-splitter
12. Cooling tower
CW Cooling water
PG Polymer grade
12
FIGURE 1. This process diagram shows an ethylene-production process via the cracking of an ethane-propane mixture
42
CHEMICAL ENGINEERING
WWW.CHEMENGONLINE.COM
NOVEMBER 2015