Universidad Autónoma de Coahuila

Facultad de Ciencias Químicas

Chemical Engineering

Process Simulation and Optimization

Dra. Lourdes Morales Oyervides

Simulation of the Production and Recovery

Process of Butanol

Team 8:

Luis Diego De Luna Hernández – [email protected]

Daniel Sánchez Udave – [email protected]
Carlos Javier Reyes Solís – [email protected]

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 Saltillo, Coahuila at June / 24th / 2020
1.- Introduction
Currently, concern about to the great environmental impact that fossil fuels are
generating is growing day by day. Therefore, many countries have chosen to
create policies for the use of biofuels to reduce the emissions of pollutants that
they generate in car engines, whereby, it is necessary to investigate new energy
alternatives that can provide a solution to this problem. A possible solution is the
use of bioalcohols such as butanol.
These alcohols are obtained from biomass from energy crops or organic waste;
therefore, they are renewable products. Butanol has been named a promising fuel
for renewable resources, since by using biomass as raw material it makes it
biodegradable and does not compete with food security, being this a great
preeminence.
Butanol has some advantages over other fuels such as ethanol and methanol, due
to its high energy content per unit of mass, reflecting in a high fuel efficiency; Less
miscibility in water and better compatibility with gasoline. Despite presenting great
advantages, there are still unsolved problems in its related production processes,
such as the low concentration of butanol in the fermentation broth. The
aforementioned, causes the energy and economic costs of the process to be
greatly increased at the time of carrying out its recovery.
The production of butanol to sell it as fuel could be profitable and in addition other
products are obtained during the process such as:
- Acetone
- Ethyl alcohol
- Distilled water
It could be said that the plant to produce it is a multiproduct plant, which favors
when making the economic balance so that it is positive.
Some important data to take into account in relation to the production of butanol
and which are important are the following:
- It reaches 95% of energy than the same volume of gasoline, while ethanol
does not exceed 75%.
- It can be mixed with conventional gasoline, without having to make
adaptations in cars, in a higher proportion than ethanol.
- It tolerates water contamination in a better way, and it is less corrosive than
ethanol, so it can be mixed directly with gasoline at the refinery.
Efforts are directed with the aim of integrating a fermentation process that is
adapted to real conditions, and thus removing solvents that prevent growth

2
inhibition and increase the production of butanol and the overall yield of
fermentation.

2.- Methods
2.1 Simulation description
In the present work, a simulation to produce biobutanol from corn is carried out.
The model can be modified to represent conversion of other types of biomass. The
plant scale for the base case has a feedstock flowrate of 80 MT/batch of dry mass
of corn. It is the same as the scale of a similar process for bioethanol production.
The plant works 350 days/year and generates 11.7 MT/batch of fuel-grade butanol,
which is equivalent to 14,400 liters per batch. A total of 86 batches can be carried
out each year.

2.2 Process description

The overall flowsheet is divided into the following sections: pretreatment,
fermentation, and purification. The unit procedure icons of each section are
displayed in a unique color (dark blue for pretreatment, green for fermentation, and
orange for purification operations).

Fig.1 Flowsheet of the system with conventional butanol recovery process

3
2.2.1 Pretreatment

Fig.2 Pretreatment Section.

The flowrate of the feedstock is 80 MT of corn, the composition of corn is showed
in Chart.1. Corn enters to a hammer mill (P-1/Gr-101) to reduce the particle size
and expose the sugars that are about to be fermented. The operation takes 60
minutes. Water is added to the corn in a proportion of 1:10. Then the mixture is
cooked (P-2/R-101) at 250 °F for 1 hour. Although it is not shown in the
fermentation reaction, saccharification occurs in this step to convert the starch to
fermentable sugars.
Chart 1. This chart shows the corn composition. Only the starch (converted to fermentable sugars
in the mash will participate on the fermentation.

Component Composition %
Cellulose 2.6
Hemicellulose 4.4
NFD Solids 6.8
Oil 3.4
Protein 8.3
Starch 59.5
Water 15

4
 2.2.2 ABE Fermentation
Fig.3 Fermentation section.

2.2.3 Seed Fermentation

The clostridium inoculum is prepared in a seed fermentation train. It starts with
a flask (P-4/SFR-101) were 5 kg of media are added. Media consists in a
mixture of 40% glucose and 60% water. The seed fermenters (P-5, P-6, P-
7/SFR-104) and the flask are kept at 32°C for 24h each stage. The reaction
was simplified so 100 g of glucose will produce 60 g of biomass, 20 g of water
and 20 grams of carbon CO2. The reaction is:

.56 C6H12O6  .33 biomass + .45 CO2 + 1.11 H2O

The microorganism will be grown 20 times in each stage to achieve a
concentration of 2.5% when it is inoculated in the main reactor. For this reason,
after the flask, three fermentation stages are needed. And the necessary media is
fed to the fermenters. CO2 is released to the atmosphere.

2.2.4 Fermentation
After cooling, the corn mash is fed to the anaerobic batch fermenter (P-3/FR-101)
and the clostridium produced in the seed fermenters is inoculated. Fermentation
takes 24 hours once the tank is full. The organism can get most of the nutrients it
needs from the corn mash. The only added nutrient is 1 kg. of NH3 per 1000 kg. of

5
corn. Sulfuric acid, 2 kg. per 1000 kg. of corn, is needed for pH adjustment. Lime is
also used for pH adjustment, and the consumption is 1 kg. per 1000 kg. of corn.
As the fermentation is exothermic, glycol is used to cool the fermenter and keep it
at 32°C to achieve maximum productivity.
The stoichiometry of the reaction can be written as:
(C6H10O5)10 + 9H2O  3 C3H6O + 6 C4H10O + C2H6O + 24 CO2 + 16 H2 + biomas
The gasses produced are released through a vent valve and the nutrients were
considered as catalysts. Conversion of the sugars in the fermenter was settled in
99%.

2.2.5 Butanol Recovery

The conventional butanol recovery process was chosen, and it consists of air
stripping columns and a distillation train. Fig.3 shows the fermentation broth was
heated by a heater at 90ºC and sent to the air stripping column to recover acetone,
butanol and ethanol (ABE) and water as top stream (aprox. 35,000 kg/batch). The
stripping column was operated at 1 atm. A minimum of air stream was fed to the
column (47,000 kg/batch)

Fig.4 Heating and stripping section.

The top stream product was cooled at 75ºC in a heat exchanger and fed to the
distillation column to recover acetone as top stream (4648 kg/batch), in this unit
operation the aim was to fulfil 99.5% wt acetone purity and 99.5% wt acetone
recovery. The distillation column was operated at 0.7 atm and with 18 theorical
plates or stages.

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 Fig.5 First distillation train.

The bottom stream (butanol, ethanol, water and some traces of acetone) was
cooled at 50ºC in a heat exchanger and sent to the second distillation column to
recover ethanol as top stream (1783 kg/batch). The goal was to fulfil 68.5% wt
ethanol purity and 99.5% wt ethanol recovery, and the distillation was operated at
0.3 with 18 theorical stages.

Fig.6 Second distillation train.

The last two heat exchanger and the distillation columns were shared to reduce the
purchase cost of the equipment.
According the Fig.6, the bottom stream of the distillation column (butanol, water,
traces of acetone and ethanol) was fed firstly to a degasification section to reduce
the amount of nitrogen and oxygen, where 100% of both was eliminated, and later
fed to an azeotropic distillation section to distillate butanol from water. The stream

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was fed to a decanter, where 1% of water and 99% of acetone, ethanol and
butanol were separated from the phase of high density (mostly water and traces of
ABE).
The high-density phase was fed to an air stripping column where 99.9% of ABE
were pulled apart to obtain a bottom stream of 16,675 kg/batch with 99.99% wt
water purity, a minimum air stream of 20,000 kg/batch was fed. The light phase
was fed to an air stripping column where 99.5% of acetone, ethanol and water
were separated from butanol obtaining a final bottom stream of 11,744 kg/batch
with 99.99% wt butanol purity. A minimum of air stream of 10,000 kg/batch was
fed.

Fig.7 Degasification and azeotropic distillation section.

2.3 Sensitivity Analysis

In this analysis, it was chosen two variables, sales and operation cost, to
predict the annual earnings. As a first case, what increase percentage of sales
it’s needed to aim positives profits if the cost operation is constant.
The second case is like second one, but here is wanted to know what decrease
percentage of cost operation it’s needed to achieve positives profits if the sales
are constants.
As third and last case, which variable has more effect towards the profits if it’s
needed a profitable process.

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 3 Results
3.1 Material Balances
Chart 2. Overall Process data

Annual Operating Time 346.52day

Unit Production Ref. Rate 998,293.26kg MP
Batch Size 11,744.63kg MP
Recipe Batch Time 186.99h
Recipe Cycle Time 96.78h
Number of Batches per Year 85.00
MP = Total Flow of Stream 'Butanol

Chart 3.Overall component balance (Kg/Batch)

COMPONENT INITIAL INPUT OUTPUT FINAL IN-OUT

Acetone 0.000 0.000 4,670.832 0.000 - 4,670.8
32
Ammonium Sulfat 0.000 80.000 80.000 0.000 0.000
Butanol 0.000 0.000 11,921.881 0.000 - 11,921.8
81
Carb. Dioxide 0.000 0.000 29,044.511 32.381 - 29,076.8
92
Cellulose 0.000 2,080.000 2,080.000 0.000 0.000
Clostridium 0.000 0.000 7,116.681 0.000 - 7,116.68
1
Ethyl Alcohol 0.000 0.000 1,234.967 0.000 - 1,234.96
7
Glucose 0.000 3,842.000 30.080 0.000 3,811.92
0
Hemicellulose 0.000 3,520.000 3,520.000 0.000 0.000
Hydrogen 0.000 0.000 863.786 0.897 - 864.683

Lime 0.000 80.000 80.000 0.000 0.000

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 NFD-Solids 0.000 5,440.000 5,440.000 0.000 0.000
Nitrogen 153.996 59,068.076 59,152.486 69.587 0.000
Oil 0.000 2,720.000 2,720.000 0.000 0.000
Oxygen 46.750 17,931.924 17,957.549 21.125 0.000
Protein 0.000 6,640.000 6,640.000 0.000 0.000
Starch 0.000 47,600.000 476.000 0.000 47,124.0
00
Sulfuric Acid 0.000 160.000 160.000 0.000 0.000
Water 0.000 21,263.000 17,312.984 0.000 3,950.01
6
TOTAL 200.746 170,425.00 170,501.75 123.990 0.000
0 6

3.2 Process Scheduling

GR-101
SFR-101
R-101
SFR-104
SFR-102
Main Equipment &CIPSkids

FR-101
HX-101
Legend
C-101
B# 1
HX-102 B# 2

C-102
DG-101
V-101
C-105
C-104
h 8 16 24 32 40 48 56 64 72 80 88 96 104 112 120 128 136 144 152 160 168 176 184 192 200 208 216 224 232 240 248 256 264 272 280 288 296 304 312 320 328
day 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Fig.8 Equipment Occupancy.

3.3 Economic Evaluation

Chart 4. Raw Material and Equipment Costs

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 Total Capital Investment 2,396,000 $
Capital Investment Charged to This Project 2,396,000 $
Operating Cost 4,080,000 $/yr
Net Operating Cost 4,080,138 $/yr
Main Revenue 1,497,000 $/yr
Other Revenues 403,973 $/yr
Total Revenues 1,901,000 $/yr
Cost Basis Annual Rate 998,293 kg MP/yr
Unit Production Cost 4.09 $/kg MP
Net Unit Production Cost 4.09 $/kg MP
Unit Production Revenue 1.90 $/kg MP
Gross Margin 114.60 %
Return On Investment 83.12 %
Payback Time N/A
IRR (After Taxes N/A
NPV (at 7.0% Interest) 17,165,000 $
MP = Total Flow of Stream 'Butanol'

Chart
5.

Executive Summary

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 Chart 6. Labor Cost

Unit Cost Annual Annual Cost

Labor Type
($/h) Amount
(h) %
(
$
)
Operator 40.25 32,814 1,320,749 100.00

TOTAL 32,814 1,320,749 100.00

3.4 Sensitivity analysis

First case:
Chart 7. Behavior of profits with sales increase and operation cost constant.

Increase Operation Cost Sales increase % Sales Profits

0 $4,080,000 - $1,901,000 $2,179,000
1 $4,080,000 100 $3,802,000 $278,000
2 $4,080,000 105 $3,897,050 $182,950
3 $4,080,000 110 $3,992,100 $87,900
4 $4,080,000 111 $4,011,110 $68,890
5 $4,080,000 112 $4,030,120 $49,880
6 $4,080,000 113 $4,049,130 $30,870
7 $4,080,000 114 $4,068,140 $11,860
8 $4,080,000 115 $4,087,150 $7,150

Fig.9 Graphic of behavior of profits with sales increase and operation cost constant.

Third Case:

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 Chart 8. Behavior of profits with operation cost decrease and sales constants.

Decrease Sales Op. Cost decrease Op. Cost Profits

%
0 $1,901,000 - $4,080,000 $2,179,000
1 $1,901,000 30 $2,856,000 $955,000
2 $1,901,000 40 $2,448,000 $547,000
3 $1,901,000 45 $2,244,000 $343,000
4 $1,901,000 50 $2,040,000 $139,000
5 $1,901,000 51 $1,999,200 $98,200
6 $1,901,000 52 $1,958,400 $57,400
7 $1,901,000 53 $1,917,600 $16,600
8 $1,901,000 54 $1,876,800 $24,200

Fig.10 Graphic of behavior of profits with operation cost decrease and sales constants

Fourth Case:
Chart 9. Behavior of profits with percentage of decrease and increase of operation cost and
sales respectively.

Decrease Op. Cost Op. Cost Sales Sales Profits

/Increase decrease % increase %
0 - $4,080,000 - $1,901,000 $2,179,000
1 15 $3,468,000 15 $2,186,150 $1,281,850
2 25 $3,060,000 25 $2,376,250 $683,750
3 30 $2,856,000 30 $2,471,300 $384,700
4 35 $2,652,000 40 $2,661,400 $9,400
5 40 $2,448,000 35 $2,566,350 $118,350

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 Fig.11 Graphic of behavior of profits with percentage of decrease and increase of operation
cost and sales respectively.

4.- Conclusions
Simulation results show that the plant is not profitable. This has multiple causes
and may be a reason why the process has not been implemented on an
industrial/commercial scale.
The costs of producing butanol turned out to be just over twice as much as the sale
price. This is due to a high cost of raw material, a low yield of butanol produced by
each corn kilogram entering the process, low equipment utilization caused by the
bottleneck in fermentations and a long and costly purification process.
Sensitivity analysis gives us information on how sales need to be increased or
operating costs lowered for the plant to start making a profit. In the first case shows
us a separate effect from the increase in sales, concluding that they would start to
make a profit on operating costs only if they were increased by 115%. Another
alternative would be case 3 where operating costs should be reduced by 54%.
Finally, a decrease in costs, combined with sale increase in case 4 where showed
that lower operating costs is more effective than increasing sales for higher profits.
Different strategies are proposed in order to make the process profitable. First, we
should seek to replace corn as raw material, as there are different agro-industrial
wastes that can be used. On the other hand, the production of butanol could be
increased using a fed-batch fermentation instead of the batch fermentation that
takes place. This would allow higher yields, although strategies should be sought
to continuously remove ABE products from fermentation, since, according to the
literature, an accumulation of these inhibits the growth of the strain used. Finally,
modifying the plant configuration by adding equipment available for fermentation
allows to produce more batches per year, which combined with the previously
proposed strategies can contribute to a better process performance.

5.- Bibliography
- Raw materials costs

https://info.aserca.gob.mx/coberturas/maiz.asp

https://www.dsmz.de/collection/catalogue/details/culture/DSM-792

https://www.alibaba.com/product-detail/Acido-Sulfurico-H2SO4_149269986.html

https://www.alibaba.com/product-detail/Desiccant-Lime_218397603.html?bypass=true

https://www.alibaba.com/product-detail/urea_110253429.html?bypass=true

https://www.alibaba.com/product-detail/Ethanol_104043444.html?bypass=true

https://marketplace.chembid.com/en/acetone-72829.html

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https://www.farmprogress.com/blog/bio-butanol-can-be-produced-about-same-cost-ethanol-
optinol-reports

https://www.aguasdesaltillo.com/#/tarifas

https://app.cfe.mx/Aplicaciones/CCFE/Tarifas/TarifasCREIndustria/Industria.aspx

https://www.aiche.org/sites/default/files/node/aiche-student-design-competition/2009-
StudentDesignContent-ABE-Fermentation_0.pdf

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