Energy Balance April 06th, 2018

FINAL PROJECT: Activated carbon from

Agave bagasse

Laura Hetzalli Zenteno Figueroa A01373724, Ian Guerrero Miranda A01373647.

a
Instituto Tecnológico y de Estudios Superiores de Monterrey, Campus Estado de México, México.

1.1 Justification

In Mexico there are plenty generation of agroindustrial waste. A very iconic process in the mexican industry is the
Tequila production, same that produces tons of agave bagasse annually. (González García, González Reynoso, &
Nungaray, 2005). According to the article Utilización de subproductos de la industria tequilera. Parte 11.
Compostaje de bagazo de agave crudo y biosólido provenientes de una planta de tratamiento de vinazas tequileras,
the industrialization of agave heads has increased from 412 900 tons in 2003, to 998 400 tons in 2011. (Rodríguez,
Jiménez, del Real, Salcedo, Zamora & Íñiguez, 2013). So the amount of waste has been duplicated in just seven
years. When noticing this problem, scientists all around the world has suggested different uses of the bagasse, such
as biopolymers, biofuels, carbohydrases, an so on.

Mainly, “Activated carbon is the most widely used adsorbent around the world with applications in diverse areas as
an adsorbent for a variety of pollutants from both gas and liquid phases. Due to the large number of applications, the
production and characterization of activated carbon is of great interest in both scientific and industrial applications.”
(Nieto & Rangel, 2011). The activated carbon most common use is for water and air purification. This type of
carbon is selected over others because its physical characteristics, for example considerable adsorption capacity,
high specific surface, therefore high contact area, high porosity, among others. (Manjarrez, 2007).

● Economic impact
In 2011, 998 thousand tons of agave were ground in Mexico for tequila production. Approximately 40% of that
weight corresponds to bagasse, equivalent to 399 thousand tons of fresh bagasse (70-80% humidity).
(Crespo, González, Rodríguez, Rendón, del Real, & Torres; 2013).
The graphic below represents the amount (in tons) of agave used in the tequila production, which is actually raising.
(CRT, 2018).
 Figure 1. Graph Agave consume for tequila production.

In 2014, the brands registered in de CRT generated 240, 000 tons of bagasse, but only the 59% of it had a secondary
treatment, probably as compostable products.
Even when the reactants used for activating the carbon may seem to be expensive, the generation of activated carbon
out of a waste that is not used (referring to the approximated 40% that has not secondary treatments), may open the
doors to new companies for the production of this product.

● Environmental impact

For this subject, the environmental problem they faced was a big one. In the Mexican production of tequila and
mezcal, agave bagasse was created as a consequence from the distillation process. This implied an issue because, at
the time, this material was only considered waste, they had no good use for it, consequently, they resorted to burn
this waste creating a bigger problem that they initially had, environmentally speaking.
Later on, they started a procedure in which this waste was used in a better way, unfortunately it did not have big
impact on society and users to commercialized it in a big scale. Therefore, they continued to investigate ways in
which they could give a better application of agave bagasse.
As new investigators around the world where looking for new raw materials in the activated carbon production from
the agricultural byproduct, this research joined with the one of giving a use for agave bagasse, and with a chemical
reaction phase they found a way in which activated carbon could be created with this industrial waste. (Nieto, 2011).

1.2 Process description and Material and Energy Balance

For the development of activated carbon there is a large number of parameters that are involved, as: the
concentration of activating agent, the activation temperature and the activation time, being the most important
factors. (Nieto & Rangel, 2011).

The first part of the process is to grind the agave bagasse. Afterwards, these fibers are blended with phosphoric acid
(in aqueous mix) at 1M in a mixer, resting there 12 hours. The next step is the pyrolysis in an inert atmosphere,
using Argon for these purpose. The outlet is heated from 500°C to 580°C, until the phosphoric acid is evaporated
and separated from the mixture. This new mixture is cooled down till 25°C, in order to control the substances easier.
Two washes are suggested in order to clean the carbon and remove any rest of phosphoric acid: First, from one to
three washes with tridestilated water; the second with Chlorhydric Acid 1M. (Nieto & Rangel, 2011).
PBD

Figure 2. Process Block Diagram

PFD

Figure 3. Process Flow Diagram

Assumptions of the process calculations
● The carbonization by pyrolysis has a efficiency of 100%
● The Agave Bagasse is conformed by Lignin, Cellulose, Hemicellulose, Water and Ashes.
● The products of the pyrolysis are just Carbon, Water and Hydrogen.
● The ashes are solid, they are just heated. The Cp’s for Sodium Carbonate and Potassium Carbonate are
constant. (Values obtained from Perry’s tables).
● The entire process is at 1 atm.

Equipment required for the process

Table 1. Units.

Unit operation Code

 Grinder G-101

Mixer M-101

Reactor R-101

Heater H-101

Tank A T-101A

Tank B T-101B

Condenser C-101

Material and energy balance

The energy balance in reactive units was calculated with the Heat of formation methodology. Including the
corresponding Cp’s, heats of formation, and heats of vaporization, respectively; in each case the reference state is
indicated below the table.
Basis of calculation: 82.08 moles of Bagasse & 10 moles of Phosphoric acid.
PM of mixture (in): 45820.1 g/mol
Inbagasse: (82.08mol)(45820.1g/mol)=3760.9138 kg
● Around mixer
The Ek is neglected because it is not a constant mixture, the bagasse and the phosphoric acid just remain there 12
hours resting.
Table 2. Balance around mixer
Compound nin (mol) nout (mol) Molar composition

Bagasse 82.08 82.08 0.8914

-Lingin (C9H10O2 ,
C10H12O3 , C11H14O4)
-Cellulose [(C6H10O5)200]
-Hemicellulose
[16(C6H12O6) , 42(C5H10O5)
[lineal] , 23(C5H10O5)
[cycle]]
-Water (H2O)

Phosphoric acid (H3PO4) 10 10 0.1086

● Around reactor
Table 3. Balance around reactor.
Compound nin (mol) ΔHin(kJ/mol) nout (mol) ΔHout(kJ/mol) Molar Molar
composition composition
input output
H3PO4(aq) 10 -1278.6 - - 0.0909 -

P2O5 - - 5 -6480.7825 - 0.0444

Lingin 16.29 -5268 - - 0.1481 -

(C9H10O2 ,
C10H12O3 ,
C11H14O4)

Cellulose 37.71 -98101.2 - - 0.3428 -

[(C6H10O5)200]

Hemicellulose 10.89 229024 - - 0.099 -

[16(C6H12O6) ,
42(C5H10O5)
[lineal] ,
23(C5H10O5)
[cycle]]

H2O 17.19 -285.84 54.72 -225.0612 0.1563 0.4864

NaCO3 3.96 -1130.9 3.96 -1073.425 0.036 0.0352

K2CO3 3.96 -1130.61 3.96 -2963.0175 0.036 0.0352

C - - 34.67 6.6555 - 0.3082

H2 - - 0.19 13.8319 - 0.0017

Ar 10 0 10 0 0.0909 0.0889
REF. STATE: 25°C, 1 atm., C, H2,O2, Na, K, Ar, P
Cp: P2O5=-10.0083[kJ/mol*K](Perry), NaCO3=-3.7931[kJ/mol*K](Perry), K2CO3=-3.8577[kJ/mol*K]
(Perry),Ar=0[kJ/mol*K](Perry)
★ Heat absorbed in the Reactor
Q=ΔH=Σnout*ΔHout - Σnin*ΔHin
Q=(-60703.57366kJ)-(-1317795.781kJ)
Q=1257092.216kJ

● Around heater
Tinitial=500°C; Tfinal=580°C
Table 4. Balance around heater
Compound nin (mol) ΔHin(kJ/mol) nout (mol) ΔHout(kJ/mol) Molar
composition (in
& out)
P2O5 5 -6480.7425 5 -7281.4065 0.0488

H2O 54.72 -225.0768 54.72 -221.9832 0.5339

NaCO3 3.96 -1073.425 3.96 -1063.745 0.0386

K2CO3 3.96 -2963.0175 3.96 -3271.6335 0.0386

C 34.67 6.6555 34.67 6.1749 0.3382

H2 0.19 13.8319 0.19 16.2083 0.0019

REF. STATE: 25°C, 1 atm.,H2O(l),NaCO3(s),K2CO3(s),C(s),H2(g),P2O5(g)
★ Heat released in the heater
Q=ΔH=Σnout*ΔHout - Σnin*ΔHin
Q=(-65503.5401kJ)-(-60470.1994kJ)
Q=-5033.3407kJ
● Around condenser
Tinitial=580°C; Tfinal=25°C
Table 5. Balance around condenser
Compound nin (mol) ΔHin(kJ/mol) nout (mol) ΔHout(kJ/mol) Molar
composition (in
& out)

H2O 54.72 -221.9549 54.72 -285.84 0.5339

NaCO3 3.96 -1063.745 3.96 -1130.9 0.0386

K2CO3 3.96 -3271.6335 3.96 -1130.64 0.0386

C 34.67 6.1749 34.67 0 0.3382

H2 0.19 16.2083 0.19 0 0.0019

REF. STATE: 25°C, 1 atm.,H2O(l),NaCO3(s),K2CO3(s),C(s),H2(g),P2O5(g)
★ Heat needed in the condenser
Q=ΔH=Σnout*ΔHout - Σnin*ΔHin
Q=(-24596.8632kJ)-(-29096.30763kJ)
Q=4499.444428kJ

● Around the Tank 1

Table 6. Balance around Tank 1
nin (mol) nout (mol) Molar composition
Compound (in & out)

Input 1 P2O5 5 5 0.0488

 H2O 54.72 54.72 0.5339

NaCO3 3.96 3.96 0.0386

K2CO3 3.96 3.96 0.0386

C 34.67 34.67 0.3382

H2 0.19 0.19 0.0019

Input 2 H2O 10 10 1
● Around the Tank 2
Table 7. Balance around Tank 2
nin (mol) nout (mol) Molar composition
Compound (in & out)

Input 1 P2O5 5 5 0.0488

H2O 54.72 54.72 0.5339

NaCO3 3.96 3.96 0.0386

K2CO3 3.96 3.96 0.0386

C 34.67 34.67 0.3382

H2 0.19 0.19 0.0019

Input 2 HCl 10 10 1

Mass flow of each stream

Table 8. Stream table

Stream Mass (mol)

1 82.08

2 10
 3 82.08

4 110

5 10

6 112.5

7 5

8 107.5

9 107.5

10 107.5

11 107.5

Energetic requirements
Table 9. Energetic requirements in each unit operation.
Unit operation Heat (kJ)

Reactor 1257092.216

Heater -5033.3407

Condenser 4499.444428

Thermophysical properties
Table 10. Thermophysical properties of the substances involved in the process.
Compounds Density (g/ cm 3 ) Specific Heat (KJ/molK)

Lignin 1.33 -

Cellulose 1.5 .712 (J/kgK)

Hemicellulose 1.52 -
Water 1 4.22 (KJ/kgK)

Sodium carbonate 2.54 3.7931

Potassium carbonate 2.43 3.8577

Carbon 2.26 .0283

Hydrogen 8.38E-5 .0282

Argon .001784 0

Phosphorus pentoxide 2.39 10.0083

Project Management
Table 11. Project management per member
Name Rol Work Description How was the work Timing
made

Laura Zenteno Investigator / Leader Administrate She got the new January 28th-May
important parts of the information for the 1st
new project. As well new project. Also she
investigated important
as look for
parts of the project.
information. Practical Research in papers,
research. scientific articles.

Ian Guerrero Investigator/Manager Investigate for process He investigated on the January 28th-May
and compounds of the selected project. 1st
activated carbon Looked up for new
information and
project. Theoretical
processes.
research. Administration of
project. Format of
document.

Gantt Diagram
 Figure 4. Gantt diagram of the project management.

Costs
Table 12. One day costs of the project
Section Amount ($) Details

Chemical Engineering salary 7000-9000 Initial monthly salary for a recently

graduated C.E.

Project cost 10900 Considering: transportation,

internet, food, how many hours a
day and how many days we worked
on this project.

Agave Bagasse 555.8-6947.3 Price per ton: 8-100 USD.

1 USD=$18.93
3.7 tons for process

Reactor 978.4 $2.802/ kW-h

Used to cool down the reactor
1kW-h=3.6x103 kJ

Heater 4 Used to heat the heater

Reactants 247 Includes Phosphoric acid, argon,

clorhidric acid, tridestilated water

Condenser 3.5 Used to cool down the condenser

In industrial scale, the project is designed to run the process once a day. According to the mexican calendar, we
considered 254 business days. The prices included in the table were obtained for one process, the total cost per year
of the project is attached in the next table. (The costs of the engineers’ basic salary and the costs of work keeps
constant).
Table 13. Annual cost of the project
Section Amount ($) Details

Chemical Engineering basic salary 7000-9000 Initial monthly salary for a recently
graduated C.E.

Project cost 10900 Considering: transportation,

internet, food, how many hours a
day and how many days we worked
on this project.

Agave Bagasse 141173.2-1764614.2 Price per ton: 8-100 USD.

1 USD=$18.93
3.7 tons for process per day

Reactor 248513.6 $2.802/ kW-h

Used to cool down the reactor
1kW-h=3.6x103 kJ

Heater 1016 Used to heat the heater

Reactants 62738 Includes Phosphoric acid, argon,

clorhidric acid, tridestilated water

Condenser 889 Used to cool down the condenser

The total price per one year of production is in a range of $472’229.8 and $2’097’670.8 for one engineer’s work. As
the team project was designed by two, the price would be in a range of $490’129.8 and $2’117’570.8.

Improvement suggestions

The phosphoric acid may be replaced with an activator that is less pollutant, for example, clorhidric acid. Also the
water used in the multiple washes may be recycled and used in the coolers, or filtered and reused in the washes.

As the coolers considered in the process are electrical, it would be a good idea either to obtain the electric energy
from renewable sources, or to change the for recirculation coolers, in order to implement the past suggestion.

In the heater, the regular fuels may be replaced with hydrogen combustion, in order to reduce the production of
carbon monoxide, carbon dioxide and other gases produced in the pyrolysis and combustion.

By a change of pressure, the extreme increases or decreases in temperature may be reduced, therefore they will be
using less energy in heating up this procedures, and this means less money invested.

Recycling . not only water but other materials can be key in order to find a way to get costs lower. If they can reuse
the chemical components they are using, they will be utilizing it at maximum. Maybe not everything can be used in
this particular process, but of course this is not the only process this company work on, so in previous processes this
can be useful. For example, the phosphorus pentoxide can be sold or used in other processes in the same plant.

This companies have to be updated on new technology coming out everyday. Scientists are finding new ways in
which companies can utilize wastes in a good way. For example, we are closer as days pass to get carbon dioxide
useful into fuel. It will indeed be expensive to invest in this new technologies, but in a long term it will help the
company.

References
González García, Y., & González Reynoso, O., & Nungaray Arellano, J. (2005). Potencial del bagazo de Agave
tequilero para la producción de biopolímeros y carbohidrasas por bacterias celulolíticas y para la obtención de
compuestos fenólicos.e-Gnosis, (3), 0.

RODRÍGUEZ, R., JIMÉNEZ, J., del REAL, J., SALCEDO, E., ZAMORA, J., & ÍÑIGUEZ, G.. (2013). Utilization
of by products of the tequila industry. Part 11. Raw agave bagasse and biosolids composting from a tequila vinasses
treatment plant. Revista internacional de contaminación ambiental, 29(4), 303-313. 01st-March-2018.Recovered
from: http://www.scielo.org.mx/scielo.php?script=sci_arttext&pid=S0188-49992013000400008&lng=es&tlng=en.

Nieto, C. & Rangel, J. (2011) Production of activated carbon from organic by-products from the alcoholic beverage
industry: Surface area and hardness optimization by using the response surface methodology. Industrial Crops and
Products. Volume 34. 01st-March-2018.Recovered from:
https://www.sciencedirect.com/science/article/pii/S0926669011001804

Manjarrez, A. (2007) Síntesis de carbón activo a partir de bagazo de agave Tequilana Weber Var. Azul y su
caracterización superficial y funcional. Centro de investigación de materiales avanzados, Chihuahua, México. 01st-
March-2018.Recovered from:
https://cimav.repositorioinstitucional.mx/jspui/bitstream/1004/523/1/050%20MANJARREZ%20NEVAREZ
%20LAURA%20ALICIA%20%281%29.pdf

Crespo, M., González, D, Rodríguez, R., Rendón, Luis., del Real, J., & Torres, J. (2013). Evaluación de la composta
de bagazo de agave como componente de sustratos para producir plántulas de agave azul tequilero. Revista
mexicana de ciencias agrícolas, 4(8), 1161-1173. 01st-March-2018.Recovered from:
http://www.scielo.org.mx/scielo.php?script=sci_arttext&pid=S2007-09342013000800004&lng=es&tlng=es.

Ramos, J. (2017). Impacto de los residuos de la industria tequilera. 01st-March-2018.Recovered from:

http://www.casasauza.com/procesos-tequila-sauza/impacto-residuos-industria-tequilera

Perry, R. (1994) El manual del ingeniero químico. 6° Edición, McGraw Hill, México 1994, Tomo I, p.p. 3-155 – 3-
162. http://depa.fquim.unam.mx/amyd/archivero/Tablasdepropiedadestermodinamicas_12182.pdf

Estudios Geológicos. (2009). Estimating the thermodynamic properties of phosphate

minerals at high and low temperature from the sum
of constituent units. April 01st, 2018. Recovered from: http://digital.csic.es/bitstream/10261/20095/1/661.pdf

Sánchez, F. (2018) ¿Es viable producir biocombustibles a partir de bagazo de agave?. Conacyt. Recovered from:
http://www.conacytprensa.mx/index.php/tecnologia/biotecnologia/20238-viable-biocombustibles-bagazo-agave

Alquera. (2017) Ácido fosfórico. Alquera ciencia. Recovered from: https://alquera.com/acido-fosforico/

CFE. (2018) Tarifas. Recovered from: https://app.cfe.mx/Aplicaciones/CCFE/Tarifas/Tarifas/Tarifas_casa.asp?

Tarifa=DACTAR1&anio=2018

● Figures.
1. Consejo Regulador del Tequila [CRT]. (2018). Información estadística. 01st-March-2018.Recovered from:
https://www.crt.org.mx/EstadisticasCRTweb/