Sulfuric acid production by two different technological routes using elemental sulfur as a raw

material
a
Gina Marcela Arias
b
Freyder Dario Nastul
c
Juan Pablo Varón
a, b, c
Department of Chemical Engineering. National University of Colombia at Manizales

Keywords Abstract
Sulfuric acid Sulfuric acid is one of the chemicals increased production worldwide due to
Elemental sulfur the versatility and variety of applications, for many years the industrial
contact Double potential of a country based on rates of acid production was measured which
Acidithiobacillus boost development technologies that enable process optimization. In this paper
thiooxidans the simulation is effected by the APEN plus software and subsequent
comparative analysis in terms of energy, economic and environmental view of
two technologies for producing sulfuric acid, a process based on the principles
of the method of double contact, widely applied in indutrias due to its high
yields and a bioprocess using oxidative sulfur bacterium Acidithiobacillus
thiooxidans found in Cauca and snowy Ruiz;
for both processes the raw material is the elemental sulfur extracted from the
mine the vinegar located in the municipality of Puracé and distributed by
EMICAUCA S.A.

1. INTRODUCTION

Sulfuric acid is one of the chemicals
manufactured in larger volume worldwide, its
importance is that it is a bulk-chemical or a
chemical platform and therefore is used as a raw
material in different kinds of industries. Such has
been its impact on the economy than in previous
years the level of industrialization of a country
based on the amount of sulfuric acid produced
was measured as an indicator. Because of its
importance over the years it has been gradually
developed technologies to produce sulfuric acid
in a more efficient and cost effective manner.
1.1. Market analysis
Sulfuric acid is one of the chemicals produced due
to the versatility of applications. Globally more
than 200 million tons of sulfuric acid are
consumed on an annual basis, the elemental sulfur
being the main raw material for their production.
The main exporters of sulfuric acid are South
Korea ($ 102 million), Canada ($ 98.3 million),
Zambia ($ 72.6 million), Germany ($ 58.7
million) and Japan ($ 52.1 million). The main
importers are the United States ($ 132 million),
Chile ($ 82.6 million), Democratic Republic of
Congo ($ 80.5 million), Indonesia ($ 53.9 million)
and the Philippines ($ 39.5 million) [1].
Colombia in 2017 made imports for US $ 173,524
major exporting countries being Germany and the
United States. Exports were $ 656,887 and the
main buyers Trinidad and Tobago and Ecuador.
[2] The current selling price in the international
market ranges from 100-400 US $ / Ton for 98%
purity. According to a study by a group of
students from the Technological University of
Santander (UIS), an unsatisfied demand for
Sulfuric Acid in the country in 2020
corresponding to 2500 tons / year is projected;
implement a production plant achieved not only
generate the amount needed to cover the entire
domestic market but also significantly increase
the income received due to exports.
1.2. Transformation path
Choose two optimal technologies for the
production of sulfuric acid will require a heuristic
and qualitative assessment score based on
parameters set out in an article in 2004 entitled
selecting appropriate for the production of fuel
ethanol technologies [3]. The methodology is as
follows; each process step will be described, then
each technology assigned values of 1, 2 or 3,
where 1 is the best rating according to the criteria
followed by their weighting in which 80% of
importance is granted to economic aspects and
20% to environmental, finally defined as the best
technology which has the lowest weighted value.
The criteria used for analysis are: technological
maturity, capital costs, energy consumption,
efficiency and damage equipment.
1.2.1. Camera technology lead
It is old technology capable of producing sulfuric
acid with a concentration between 62 and 78% for
all industrial applications where mean
concentrations of acid are required. The main
stages comprising the manufacture of sulfuric
acid by the method of the lead chambers are [4]:
1. Obtaining sulfur dioxide, SO2, usually from
the main raw material: mineral known as
pyrite, FeS2 of formula. This process is
conducted in a roaster pyrite. Roasting of
pyrite produces a gas containing SO2 in a
ratio of 10%; the remaining 90% are other
gases.
2. Oxidation of SO2 produced sulfur trioxide
SO3, by the action of air in the presence of a
catalyst. The gas from the roaster pyrite, 10%
of S02 passes a second system, called Glover
tower. This tower about 16 meters high, is
filled with porcelain rings. On the top of the
tower a stream enters the call nitrous mixture,
said mixture containing sulfuric acid and
oxides of nitrogen, NO and NO2, mainly,
which are acting as catalysts. The SO2 is
oxidized is that is present in the gas mixture
from the pyrites roaster. Likewise certain
amount of S03 that was produced passing
sulfuric acid. This is called acid Glover,
which has approximately a concentration of
78%, but not the final product.
3. Combination of sulfur trioxide with water to
form sulfuric acid chamber. About 10% of the
initial SO2 becomes acid in Glover tower, the
remaining 90% are in the lead chamber.
These chambers (12 m wide, 18 m high and
30 to 60 m long) reaches the gas mixture
Glover tower. Usually 3 to 6 cameras placed
in series. The cameras perform three
functions: it provides the necessary space for
gas mixing conveniently and out can take
various reactions acid production, remove the
heat produced in these reactions and provide
a condensing surface for the acid which is He
is forming.
4. Nitrous regeneration tower mixture Gay-
Lussac. When the waste gases from the
chambers enter the Gay-Lussac tower, they
are mixed with the sulfuric acid tower Glover.
When the sulfuric acid enters the tower is
mixed with the waste gas stream from the
cameras and the call is regenerated Nitrous
mixture, necessary for catalysis of the
reaction of sulfuric acid production. Thus this
Nitrous mixture produced is recycled to the
tower Glover, making question of a closed
and continuous process. Furthermore, if it is
SO2 or SO3 in the residual gas leaving the
chambers, as is mixed in the tower Gay-
Lussac and recirculated back to the beginning
of the process, is not wasted, but it reenters
the cycle production.
Figure 1. Diagram production process A. Sulfuric
by technology lead chamber (source: [4]).
TECHNOLOGY Oven Glover Lead Gay-
tower chamber Lussac
tower 1.2.4. Method double contact
It is the most convenient process, since it allows
WEIGHTED 2.1 1.7 1.6 1.6 to obtain concentrated sulfuric acid 99.5%.
Process units are similar to the process of simple
contact, double contact method differs from
1.2.2. Vitriol process simple contact method to make use of more than
The process of vitriol is the oldest method of one adsorption column to collect the SO3 in the
producing sulfuric acid, the method is based on final stage. Generally the method uses two double
thermal decomposition of sulphates of natural contact adsorption columns at the end of the
origin, called vitriols. Due to the high process [6, 7].
temperatures required, the process was expensive,
and after the development of alternatives was Already mentioned the difference between the
rapidly displaced. Usually feedstock iron sulfate process by simple contact and double contact, lies
(II) was used. The procedure was expensive and in the separation step, therefore, the reactions and
cumbersome therefore a cheaper alternative was kinetic models employed will be the same in both
needed and thus lead chamber process was cases, reported by (Pernett Bolaño et al. 2016).
developed in the eighteenth century. This process
was cheaper but the maximum concentration Reactions involved in the process
obtained was 78%, while the process of vitriol Sulfur oxidation
obtained concentrated acid and oleum, so was still 𝑆 + 𝑂2 ↔ 𝑆𝑂2
used for more specific purposes. Catalytic oxidation of SO2 to SO3
1
1.2.3. Simple method of contact 𝑆𝑂2 + 𝑂2 ↔ 𝑆𝑂3
2
It is one of the most convenient methods because SO3 absorption in water to form H2SO4
it produces high yields, operates directly with 𝑆𝑂3 + 𝐻2 𝑂 ↔ 𝐻2 𝑆𝑂4
sulfur and has a shorter operation with respect to
other processes such as the method or the process TECHNOLOGY Oven CSTR towers Mixer
chambers vitriol. This process can be
differentiated into several stages [5, 6, 7]: WEIGHTED 1.7 1.4 1.2 1.3

1. In the first of which the sulfur is burned in the

presence of dry air (prevents corrosion of
equipment) to produce sulfur dioxide.
2. In step followed by drying to a gas stream that
will enter the CSTR reactor packed (400 ° C
and 1 bar), wherein the catalytic oxidation is
carried out with vanadium sulfur dioxide to
sulfur trioxide is done,
3. Then, the fourth step is the absorption of
sulfur trioxide to sulfuric acid of low
concentration to 98%
4. Finally mixing with water to produce
concentrated sulfuric acid, which is cooled
and stored. (Forero sf) Figure 2. Process diagram of production of
sulfuric acid by contact (source: [6]).
TECHNOLOGY Oven CSTR Absorption Mixer
towers 1.2.5. Sulfuric acid production for sulfur
oxidizing bacteria
WEIGHTED 1.7 1.4 1.3 1.3 The production of organic sulfuric acid is
produced by a type of sulfur-oxidizing bacteria.
These bacteria use inorganic oxidizing reduced
sulfur compounds (H2S, S0) as electron donors
and energy sources for its metabolism [8]. In
Colombia, this bacterium can be found in Cauca
and Nevado Ruiz, so far only been found in
bacteria oxidizing coal mine Asnazú is
thiooxidans Acidithiobacillus bacteria [9]. The
main steps for the production of sulfuric acid
using an oxidative sulfur bacterium is as follows
[10, 11, 12]:
1. It should put the raw material (mineral sulfur)
for bacteria have a better production of
sulfuric acid; for this was considered that the
most appropriate is to extract the elemental
sulfur to ore least interference from other
compounds so that the oxidizing bacterium
more efficient in producing sulfur. This is
achieved by first cleaning and grinding the
ore in a ball mill until a particle size of about
0.15 mm, then melted and burned and sulfur
is obtained.
2. Initially the bacteria must be vatting so that it
assimilates the medium, this step is
performed at 30 ° C and lasts 12 to 15 days
for bacteria growth A. thiooxidans. The
medium in the reactor is macronutrients or
mineral salts medium commonly used is a 9K
medium containing typically: (NH4) 2SO4,
K2HPO4, MgSO4 · 7H2O, but found that the
concentration of these nutrients not affect
production acid. The medium is inoculated
with the bacteria Acidithiobacillus
thiooxidans approximately 7-10% (v / v). The
pH should be adjusted to 1.8-2 with sulfuric
acid.
3. After the growth stage azufren is added in
concentrations ranging from 10 to 20 g / L
with stirring at 180 rpm. The oxygen required
for the reaction is obtained by feeding air
4. After the reaction time, about 40 hours,
finally to produce sulfuric acid. The medium
can be filtered off.
In this case, as no presence of hydrogen sulfide,
elemental sulfur may be oxidized to sulfuric acid
formation by the following reaction [8]:
𝑡ℎ𝑖𝑜𝑜𝑥𝑖𝑑𝑎𝑛𝑠
𝑆 0 + 𝐻2 𝑂 + 3/2𝑂2 → 𝐻2 𝑆𝑂4
Product
TECHNOLOGY Pretreatment bioreactor separation
WEIGHTED 1,18 1,36 0.95
Analyzing the numerical values of the
weighted for every stage in the studied
technologies can be selected bio process for
oxidizing sulfur bacteria and the process
double contact as the best alternative for the
efficient and economical production of
sulfuric acid industrially due to the proximity
of the weighted to 1 as defined earlier in this
document corresponds to the highest score for
each criterion evaluated. Processes simple
contact and double contact have similar
indicators in three of its four technologies,
however, the implementation of an additional
tower improves the purification section and
therefore the overall process.
The two selected technologies use as
feedstock elemental sulfur, processes such as
lead chamber and vitriol requiring pyrite and
iron sulfate (II) respectively as the sulfur
source, are not as efficient or cost-effective
and are considered obsolete nowadays.
1.3. Raw materials used
For each of the proposed technologies and to be
developed in detail in this work Elemental sulfur
was employed as a raw material for the
production of sulfuric acid.
Sulfur is one of the leading industrial minerals
and is associated with sedimentary, igneous and
metamorphic as well as fossil fuels. In Colombia,
the main manifestations of sulfur are related to
volcanic activity Tertiary Quaternary, especially
in the departments of Tolima, Cauca and Nariño.
Other manifestations of little economic value, are
associated with cretaceous sedimentary rocks, in
the department of Cundinamarca. The only mine
where sulfur is removed in Colombia is El
VINAGRE, located in the NE flank volcano
Puracé. The average annual production of sulfur
in Colombia for 2015 is 63.236 Ton [13]; proved
reserves totaled 5.601 million metric tons. With T [=] K and 𝑘 ′ [=] atm−0.5,.

1.4 Kinetic parameters However, at the beginning of the reaction, the

kinetic rate is undetermined because the partial
1.4.1. Conventional process pressure of SO3 is equal to zero. To solve this
math problem, Flogger [17] reports another rate
- Kinetics of Catalytic oxidation of SO2 for conversions less than 0.05. This kinetic is
to SO3 given by:
In the reactor, SO2 reacts with the oxygen already ′
0,012
in the gas and generally with catalyst –Vanadium −rSO = k [0,848 − ]
2
Kp2
pentoxide, V2O5, to produce sulfur trioxide as
show [15]:
1 With 𝑘 in 𝑘𝑚𝑜𝑙⁄𝑘𝑔 ∗ 𝑠 ∗ 𝑎𝑡𝑚 and
𝑆𝑂2 + 𝑂2 ↔ 𝑆𝑂3 𝐾𝑝 [=] atm −0.5
.
2
o (298)
Hrxn = −298480 J⁄mol SO2

The mechanism of the reaction is suggested to be - Kinetics of SO3 absorption

the following [15]: For this stage, SO3 produced in previous
stage is sent to absorption columns where it is
𝑆𝑂2 + 𝐶𝑎𝑡 − 𝑂 → 𝑆𝑂3 + 𝐶𝑎𝑡 put into contact with water to produced
𝐶𝑎𝑡 + 𝑂2 → 𝐶𝑎𝑡 − 𝑂
sulfuric acid. The process is highly
𝑆𝑂3 + 𝐶𝑎𝑡 → 𝑆𝑂2 + 𝐶𝑎𝑡 − 𝑂
exothermic, the reaction mechanism is given
The kinetics of the reaction was used were as [15]:
established by Eklund [16] in 1956 and analyzed
by Fogler [17] and others [15,18] and it is 𝑆𝑂3 (𝑔) + 𝐻2 𝑂(𝑙) → 𝐻2 𝑆𝑂4 (𝑙)
described as:
2 According to different references consulted [15,
′
PSO PSO3 19, 20]. The rate expression for the production of
−rSO = k√ 2 [PO2 − ( ) ]
2 PSO3 K p PSO2 sulphuric acid is:
Where k is a function of the catalyst and the
geometry, and Pi is the partial pressure of each −𝑟𝑆𝑂3 = k[𝑆𝑂3 ][𝐻2 𝑂]
species. The equilibrium constant is given as:
42311 For the rate constant we have:
K p = 0.003142 exp ( −𝐸0
1.987(1.8(T − 273.15) + 491.67)
𝑘 = 𝑘1 exp ( )
− 11.24) 𝑅𝑇

Also, we observed that the values and magnitude

K p [=] Pa−0.5 , T [=] K for kinetic constant and activation energy were
consistent [19,20]. Therefore, the values used for
For the rate constant we have: constants were:
97782,22
ln(𝑘) = 848,0847 − − 110,1 ln(𝑇)
𝑇 𝐸0 = 3.3 kcal/mol
Whit 𝑘 in 𝑘𝑚𝑜𝑙⁄𝑘𝑔 ∗ 𝑠 ∗ 𝑎𝑡𝑚 𝑘1 = 1ell 𝑠 −1
Additionally, the inverse kinetic constant could be
described as: 1.4.2. Biotechnological process
121442,12
ln(𝑘 ′ ) = 825,6047 − - Kinetics of bacterial growth and
𝑇 sulfate production
− 110,1 ln(𝑇)
For this case, as there is no presence of
hydrogen sulfide (H2S), the A. thiooxidans
bacterium can oxidize the elemental sulfur to
the formation of sulfuric acid according to the
following reaction [21, 22, 23].
In this case, since there is not enough information
for the bacterium A. thiooxidans, the kinetics of
the thiobacillus thiooxidans bacteria were taken.
Here, proposed that model for the specific growth
rate with substrate inhibition can be treated in
form of [22].
𝜇𝑚𝑎𝑥 𝐶𝑆
𝜇=
𝐶2
𝐾𝑆 + 𝐶𝑆 + 𝐾𝑆
𝐼 plant is approximately 437 km which represents a
Where 𝐾𝑆 is the substrate half saturation constant,
𝜇𝑚𝑎𝑥 is the máximum specific growth rate and 𝐾𝐼
is the inhibition constant [22]:
The supplier of the raw material needed for the
production of sulfuric acid will EMPRESA
MINERA INDIGENA DEL CAUCA
(EMICAUCA SA), which since 1940 is
responsible for the exploitation of elemental
sulfur of EL VINAGRE mine, located in the
municipality of Puracé in the department CAUCA
50 km from the city of Popayan, capital of the
department. The product requirement will be 527
tons/month of elemental sulfur bulk and
transported in dump trucks with a capacity of 35
Ton, ie, to ensure monthly delivery will require 16
dump trucks, to be distributed as conditions of the
provider for two deliveries every two weeks or
four weekly installments. The distance from the
exact point of the location of the EL VINAGRE
mine to the proposed location for the production
road trip of 7h 51 min as evidenced in the outline
of the route presented then.

𝜇𝑚𝑎𝑥 = 0,0322 ℎ−1

𝐾𝑆 = 0,5909 𝑔/𝐿
𝐾𝐼 = 152,46 𝑔/𝐿

The expression for specific growth rate of cells

(𝑟𝑔 ) and the specific rate of production of sulfuric
acid (𝑟𝑝 ) can be expressed by the equation of
monod [22, 23]

𝑟𝑔 = 𝜇𝐶𝐶

𝑉𝑚 𝐶𝑆
𝑟𝑝 =
𝐾𝑃 + 𝐶𝑆
Where,
The cost associated with transportation from the
𝑉𝑚 = 432,27 𝑚𝑔⁄𝐿 − ℎ point of dispatch to the plant, calculated
𝐾𝑃 = 5,23 𝑔/𝐿 according to all relevant current rates is 2.176.000
COP each way and tractor-trailer, ie, the total cost
Additionally, it is know the Sulfur to g of cells to transport all the raw material 34.816.000 COP
proportionality constant Y=0,35 g of cell/g of is required [14].
sulfur converted, therefore, the rate specified for
the substrate is expressed as: 1.5. Volume of raw material
1
−𝑟𝑠 = 𝑟𝑔
𝑌 It was decided to use 9% of the national annual
production of sulfur as calculation basis for the
simulation of the two proposed processes. EL
1.4. Basic logistical analysis VINAGRE being the only natural sulfur mine
currently being exploited in the national territory final product through the national territory due to
it can be inferred that EMICAUCA S.A. provide the confluence of the roads leading to the main
all the necessary raw materials guaranteeing the collection and distribution center.
supply of 5691,24 Tons/year or 0,1817 kg / s. In
conclusion based on historical production of
sulfur an input stream for the simulation of 0,1817
kg/s it is proposed.

1.6. Location

Establish an optimum location for the sulfuric

acid plant it requires consideration of several
aspects. Being EMICAUCA the main and only
supplier of sulfur would be logical to set up
production in areas near the mine vinegar located
50 km from Popayan to ensure a continuous
supply and significantly reduce costs associated
with transport, however as looking it directly
impact the region that is home of the National
University belongs, the location area or
surrounding town of Manizales and Villa Maria is
delimited. Plants operating by the double contact
process have the particularity that must warm start
until stable, requiring much energy and
generating the latent risk of expulsion of pollutant
emissions that could undermine the integrity of
the population has been established nearby, is
why secure location area and influence of the
plant to a safe distance from any settlement
should be an aspect of vital importance.
Environmental conditions also achieve influence
many process steps, especially the humidity must
be ensured as small as possible. Access roads to
the plant, the topography and the possibility of
having a continuous water supply service with the
required quality conditions, will affect the
substantial reduction in capital costs.
Evaluating each parameter at the end, it was
decided to locate the Sulfuric Acid production
plant in the industrial zone of the municipality of
Manizales, a sector known as Malteria, which
has a continuous supply of water with very good
physic-chemical characteristics, a specialized
electrical network for supply energy
requirements, access roads paved and in good
condition, an optimal road network from the
vinegar mine to the Km 15 Pan American
Highway vicinity of the industrial park
Juanchito, area of high commercial incidence
because Manizales is one of the main centers of
Colombia and the possibility of distribution of the
The image above shows a satellite view of an area
of the industrial sector Juanchito point at the
crossroads of several industries of great national
importance as ProGel, it is proposed to locate the
plant at 600 m from the current location of
Descafecol SAS.
1.7. Impact
Manizales converge in various industries
positioned in the domestic and international
markets and of great importance and influence in
the development of the region, however, it is one
of the cities with the highest unemployment rate.
By proposing install an industry such as sulfuric
acid it is directly impacting the economy of the
whole area of influence, first by direct and
indirect job and the second by the growth of the
gross national product (GNP) of the region and
thus the national GDP. Sulfuric acid is a chemical
platform whose importance lies in its versatility
of industrial applications, therefore, by
establishing and consolidating the production
plant in such a way that the volumes demanded
are exceeded, a variety of other industries could
be promoted that generate a wide range of value-
added products based on sulfuric acid as raw
material.
1.8. Financing
Being a process belonging to both the field of
research and the industrial sector of the country,
they may be funded through different national and
international entities. These entities can be found
to Fondo Emprender, Colciencias, Fomipyme,
Banks, IDB, World Bank, among others.
However, for the present work the Fondo
Emprender was selected as a possible funding
entity of the project. The financing format is
found in Annex A
2. METHODOLOGY
2.1. Modeling and simulation
As mentioned earlier, the main steps in this
process consist of burning sulfur (S) in dry air to
form sulfur dioxide (SO2), converting SO2 to
sulfur trioxide (SO3) using oxygen (O2) and the
catalyst used is vanadium oxide (V2O5) and
absorbing the SO3 in water (H20) to form a
concentrated solution of acid (>96%) [15].
2.1.1. Conventional process simulation
- Pretreatment - Air drying
For the processes of combustion of elemental
sulfur and catalytic oxidation to form SO3, the
entry of dry air is required in order to avoid
corrosion in the equipment, as air used is taken
from the environment this stream usually contains
water, for the place where the plant is proposed to
be located, the humidity of the environment is
generally 4-5% so a stage of air drying is
necessary. In general, air drying is carried out in
a drying tower (absorption tower) entering the
upper part of tower a liquid stream of
concentrated sulfuric acid between 93% and 98%
at entering temperatures of around 50 °C and 80
°C and humid air stream is entered at a
temperature between 10 - 50 ° C for the bottom of
tower, Water removals greater than 99% are
expected [15, 24, 25]
To simulate this stage a RadFrac column was used
DRYINGTW (observe in Figure 3 the
pretreatment diagram) specified as absorber with
the specifications of table 1. The humid inlet
airflow AIRHUM it was compressed to a pressure
of 7 bar to simulate the uptake of ambient air.
Considering the general air composition of 0,79
mol of N2 and 0,21 mol of O2, the input
compositions shown on table 1 were determined.
Then, the current was entered to an exchanger
until a temperature of 10 ° C to finally be fed to
tower. The acid stream that enters through the
upper part comes from the ABS1 absorption
tower with a concentration of sulfuric acid of 97%
and an exchanger and a pump were required to
condition the current to 60 ° C and 3 atm.
First, the subsequent stages were simulated until
the product was obtained and at the end the inlet
flow of humid air which is found in table 1 was
established. The flow of acid fed was determined
by a sensitivity analysis, finding the amount
needed to remove as much water (>99%) at the
exit of tower.
Table 1. Specifications for the simulation of the
drying tower.
Condition Value
Stages 5
Presion (atm) 3
Air flow mass inlet 2,5 k/s
Sulfuric flow mass inlet 0,3 kg/s
O2=0,22
Air composition N2=0,73
Water=0,05
Figure 3. General scheme used in the simulation
for air pre-treatment (air drying).
- Pretreatment stage - Combustion of
elemental sulfur
First, it must be remembered that 0,1817 kg / s of
sulfur will be processed. This reagent has to be
conditioned, first it must be melted to obtain
sulfur liquid at a temperature of 150 ° C [26]. This
stage was simulated using a RStoic
squequeometric reactor named MELTER as
shown in figure 4, where the following reaction
was entered by establishing a conversion of 1:
𝑆 0 (𝑠) → 𝑆 0 (𝑙)
The combustion of elemental sulphur is typically
carried out in combustion chambers at high
temperature (1100 °C) and atmospheric pressure
[26] is show:
𝑆(𝑠) + 𝑂2 (𝑔) → 𝑆𝑂2
∆𝐻 0 = −296,8 𝐾𝐽/𝑚𝑜𝑙
The combustion air flow is controlled in order to
maintain a composition of 0,1-0,2 molar fraction
[15,18], which will be fed to the oxidation reactor
in the reaction stage. Considering the above, this
stage was simulated using a reactor named
FURNANCE and activating the option of
combustion and the formation of nitrogen dioxide
(NO2). The amount of air required for total sulfur
combustion was determined by a sensitivity
analysis, varying the air inlet to the furnance until
converting all the elemental sulfur to SO2,
therefore, according to figure 4, obtainment of
analysis, the amount of air required for total sulfur
combustion must be greater than 0,9 kg / s and this
was established value.
Figure 4. General scheme used in the simulation
for sulfur pre-treatment.
S-1 - Results Summary
0,13
0,12
0,11
0,10
SULFURE MASS FLOW KG/SEC
0,09
0,08
0,07
0,06
0,05
0,04
0,03
0,02
0,01
0,00
0,25 0,40 0,55 0,70 0,85 1,00 1,15 1,30 1,45
AIRE TOTAL MASS FLOW KG/SEC
Figure 5. Mass flow of sulfur at the outlet of the
furnace.
-
Reaction stage - Catalytic oxidation of
SO2 to SO3
In practice, the feed to the converter (current
coming from sulfur combustion) has to be cooled
down to 420-450 °C. The gas is fed to a four-bed
catalytic converter generally, with V2O5 catalyst,
in which a conversion of 99.5 mol% of sulfur
dioxide is achieved [15, 16, 18], urthermore, at
the outlet of each bed the current is cooled due to
the exothermic nature of catalytic oxidation of
SO2, In general, this temperature is a little higher
than that of feeding to the previous bed [15].
According to the cited references, for feeding
temperatures higher than 600 ° C there are hot
spots inside reactor, so it is not recommended to
operate to these conditions. Table 2 shows the
operating conditions established in the simulation
according to the references [15, 16, 18].
Remembering that for conversions less than 0.05
of SO3 to kinetic presents an indetermination, so
another kinetic is presented for these values. To
simulate this, first a bed reactor called PREOXID
was used as shown in Figure 6, with the
conditions shown in table 2, but it was established
with the kinetics for minor conversions 0.05 and
with the help of flowsheeting options the length
of required bed was calculated to complete this
conversion, what corresponds until obtaining a
molar flow of SO3 of 0,005386 kg/s. According
to the results obtained, the conversion is reached
in a length of 1,04 m, which was established for It is known that the catalysts have a useful life, in
first reactor, from here on, the other simulated the case of vanadium pentoxide, the useful life is
catalytic beds, the kinetics were used as a function 5 years or more [cita]. Then, considering the
of the partial pressures. catalyst mass found above it is possible to
calculate the amount of catalyst used per year as:
The amount of air required for the oxidation and
most adequate length for a higher production of If
so3 were determined by different sensitivity 𝑊 = 2104,72 𝑘𝑔
analyzes, based on the results, we was established Then
that for each bed a current of 0,5 kg/s of air must
be entered and each reactor must have a length of 2104,72 𝑘𝑔
3 meters. 𝑚̇𝑐𝑎𝑡 =
5 𝑦𝑒𝑎𝑟𝑠
Finally, three beds were used (the PREOXID and 𝑘𝑔 𝑘𝑔
OXIDT1 reactors were considered as one, 𝑚̇𝑐𝑎𝑡 = 420,9 = 0,04805
𝑦𝑒𝑎𝑟𝑠 ℎ
therefore, added together they have a length of 3
meters) and the feeding temperature to each one
was 400, 450 and 500 ° C respectively. According Table 2. Operating conditions established in the
to the conditions mentioned above, at the exit of simulation for catalytic oxidation of SO2.
this stage of catalytic oxidation, the SO2 obtained
Parameter Value
a conversion of 0,9911, what agrees with the
theoretical values consulted. Temperature (K) 400
Presion (atm) 2
Additionally, the first reactor was simulated using SO2=0,11
Matlab. It was obtained that the conversion of the Molar fraction O2=0,1
first reactor is lower than the conversion obtained N2=079
by Aspen, this is mainly due to the fact that the
Bed Voidage 0,45
Matlab calculation was not considered the
effectiveness factor, and for this reaction, this Diameter Particle (m) 0,00457
factor has a considerable influence. The codes can Particle density (kg/m3) 541,42
be found in the attached files. Thermal fluid temperature
702,59
(K)
As the volume of the reactor is already known, it Heat transfer coefficient U
10
is possible to calculate the required catalyst mass, (BTU/h-ft2-R)
W, therefore, the catalyst mass can be found as: Reactor Diameter (m) 1

𝑊 = 𝜌𝑐 (1 − 𝜑)𝑉𝑅

Where 𝑉𝑅 is the volume of the reactor that can be

calculated as:
𝑉𝑅 = 𝐴𝑅 𝐿

If the total length of the three reactors is 9 m and

the reactor diameter is 1 m, then:

𝑉𝑅 = 7,06 𝑚3

Then, using the values in Table 2, the catalyst Figure 6. General scheme used in the simulation
mass is: for Catalytic oxidation of SO2 to SO3.
𝑊 = 2104,72 𝑘𝑔
- SO3 absorption
In practice, absorption of SO3 is given in an tower to finally obtain the desired sulfuric acid
absorption column where SO3 reacts with water with a composition greater than 99% sulfuric
to form sulfuric acid, the operating conditions of acid. Finally, each output stream is cooled to 25 °
this column is usually in a temperature range C
between 80 - 120 ° C and at atmospheric pressure
where the SO3 gas is entered by bottom and the
water flow is entered by the upper part at a
temperature of 30 ° C [24, 25]. To simulate this
stage, it was decided to recreate the reaction of
so3 absorption with water to sulfuric acid in an
RCTR reactor named REAC-ABS as seen in
figure 7, it is established with a temperature of 80
° C and with the kinetics shown previously. Then,
the product obtained is divided into two flows and
each stream is entered into a RadFrac column that
will simulate the separation of the acid, generally
the exit concentration of the acid in the first
Figure 7. General scheme used in the simulation
column has a concentration greater than 96% so
for SO3 absorption.
this current is entered into a second obstruction

Figure 8. Scheme using in Aspen to simulate the production of sulfuric acid.

2.1.2. Biotechnological process To know the operating conditions and quantities

Generally, T. thiooxidans is subcultured
aerobically with 9K médium, this is used to
cultivate the strain contained MgSO47H2O,
(NH4)2SO4 and CaCl22H2O. The pH of the
medium is adjusted to 2 using HCl or H2SO4.
Process is carried out for periods of 10-15 days at
30 °C [21, 22, 23].
of the components involved in the
biotechnological process, different scientific
articles were consulted to establish several
references on these values and thus establish the
entry conditions for the simulation. Table 3 shows
the feed and operation compositions according to
some authors consulted. Based on this
information, the concentrations and inflows to the
simulation shown in Table 4 were established,
 considering that the conventional process that With this information and with the growth
wants to treat 9% of the country's sulfur kinetics for the bacteria shown above, the
production, what corresponds to a flow of 0,1817 bioproduction of sulfur in a chemostat was
kg / s. simulated using the Matlab interface. According
to Matlab's results, if you look at figure 9 for
Additionally the amount of air is shown higher concentrations of sulfur at 10 g / L in the
(composition of humid air commented on in the bioreactor the rate in cell generation decreases
conventional process was considered) and water because of inhibition by substrate. On the other
required to obtain a solution volume of 9.1 L / s, hand, in the graphs shown in figure 10, the change
that would be the value of the volume required to in the concentration of the bacteria, the substrate
treat the 0,1817 kg / s of sulfur to obtain a and the product inside the bioreactor is
concentration of 20 g / L of food according to appreciated as bio-oxidation occurs, it is
what has been commented so far. appreciated that for the curve corresponding to a
dilution of =0,007686 h-1 (that corresponds to a
Table 3. Published data for operating conditions residence time of 5,4 days or 130 hours) there is
for oxidation of elemental sulfur by Thiobacillus. the highest production of sulfuric acid, high
Component Ref. [21] Ref [22] Ref [23] concentration of cells and low concentration of
7% sulfur.
Bacteriums (g/L) 0,224 0,1
(v/v)
0
Sulfur (S ) (g/L) 1 – 10 3- 40 2 Now, for the Aspen simulation of the reaction
MgSO47H2O (g/L) 0,1 0,1 - stage of this bioprocess the bioreactor where the
oxidation of sulfur by the microorganism is
(NH4)2SO4 (g/L) 1,5 – 3 2,5 -
carried out was considered as a reactor of yields
CaCl22H2O (g/L) 0,3 0,3 - taking into account the results obtained in the
Sulfuric feed (g/L) - 10 - program developed in Matlab. Therefore,
Sulfuric final (g/L) 10 - 23 30 - 50 40 considering the behavior of the different graphs
Temperature (°C) 30 30 30 the residence time of 10,5 days or 250 h was
established which corresponds to a dilution of D
pH 4 4 4
=0,004 h-1, for these values, the concentrations for
Resident Time
(days)
8- 11 10 7 the biomass, the substrate and the sulfuric acid at
the output of the bioreactor will be of 4,437,
0,1446 and 29,6765 g / L respectively. Finally,
based on these output compositions obtained in
Table 4. Operating conditions for the oxidation
Matlab, the normalized yields that were entered
bioprocess established for simulations in Aspen
into aspen were established and these values are
and Matlab.
Concentration Mass Flow
shown in table 5.
Component
(g/L) (kg/s)
Bacteriums 0,1 0,00090892
Sulfur (S0) 20 0,181784
MgSO47H2O 0,1 0,00090892
(NH4)2SO4 1,5 0,0136338
CaCl22H2O 0,3 0,00272676
Sulfuric Acid 1 0,0090892
Water - 8,900603556
O2 - 0,002672052
N2 - 0,008795518
vsol 9,0914
Temperature (°C) 30
Resident Time
10,5
(days)
 considering the small concentrations of sulfuric
acid in the mixture. But for simulation purposes,
the simulation of water separation and sulfuric
acid were used two flash separators in which all
the contained water simply evaporates. It is clear
that the energy consumption to accomplish this
huge and due to the corrosive nature of sulfuric
acid, it is a difficult process to apply. Finally, the
currents that needed it were cooled down to 25 °
C. Figure 11 summarizes the entire process
proposed for the production of sulfuric acid via
oxidation by a microorganism.

Table 5. Compositions at the reactor outlet used

in the yield reactor
Figure 10. Rate of cell growth as a function of Mass Flow Yield
Component
substrate concentration. out (g/s) Normalized
Bacteriums 40,343 0,0043657
After leaving the bioreactor, the current is fed to Sulfur (S0) 269,803 0,0291969
a filter where the sulfur that has not reacted is MgSO47H2O 0,909 0,0000984
separated, the nutrients and remaining bacterium. (NH4)2SO4 13,634 0,0014754
At to this point no methods are known to separate CaCl22H2O 2,727 0,0002951
the sulfur contained in the mixture because the Sulfuric Acid 1,315 0,0001423
amount of water used is exaggerated (>95%). Water 8900,604 0,9631853
According to the findings, sulfuric acid separation O2 2,672 0,0002892
methods are being developed with the use of
hybrid systems with acid-selective membranes, so
N2 8,796 0,0009518
it is an attractive method for this process
Figure 9. Composition profile of a) Sulfuric acid b) sulfur y c) bacteria inside the bioreactor at different
dilutions D [h-1].

Figure 11. General scheme used in the simulation for production of sulfuric acid via oxidation by a
microorganism.
2.2. Economic evaluation Sulfuric acid 98 % min 0,3 905,162

The economic evaluation for the processes MgSO47H2O 99% min 0,07 3,272
proposed in this work will be done using the
Aspen Process Economic Analyzer package by (NH4)2SO4 99 % min 0,1 49,082
Aspen Plus. To carry out this analysis, we want to CaCl22H2O 97 % min 0,15 9,816
know the amount of raw material used, the
respective price of each, for this, Table 6 and table Water . 0,00059 32040
7 shows the prices of raw materials and the
product for both simulated process. The price for
air was not considered since it is assumed that the Table 8. Some indicators used
air is taken from the environment and for the bio Project currency description
process, the price of the bacteria was not Tax rate 25%
considered since it is worked under the Interest Rate 17%
assumption that they are obtained from
inoculations. Economic life project 10 años
Depreciation method Straight Line
Additionally, some indicators and prices were Operating Hours per period 8766 h/period
modified to obtain results that are consistent with
the reality of the country therefore in the Table 9. Some indicators used
following tables these values are shown. Operating Unit Cost
Operator (USD/h) 2,56
In addition, in order to have a better economic
analysis of the processes, we opted to calculate Supervisor (USD/h) 5,12
the production costs in each stage, in order to Electricity (USD/kWh) 0,14
know the stage that consumes the most costs and Potable Water (USD/m3) 0,59
thus be able to establish the zones that must be Fuel (USD/MWh) 24,58
reevaluated and optimized in order to reduce
costs. Finally, we calculated capital costs or Table 10. Price of used utilities
Capex and operating costs or Opex, this also as an
Utility Specifications
indicator to know the aspects that generate the
most costs and also know where to evaluate the Water cooling (USD/m3) 0,59
cost reduction. Steam (690kPa) (USD/ton) 7,57
Steam(1135kPa) (USD/ton) 8,18
Table 6. Prices used for raw materials and Steam (2760kPa) (USD/ton) 9,86
products for the conventional process
Purity USD/kg Flow kg/h
Sulfur 99 % min 0,07 654,42 2.2. Environmental Evaluation
Sulfuric acid 99 % min 0,5 1971,47
Determine the sustainability of a production
Catalyst 5-8 % 5 0,04805 process on a large scale requires knowledge of
Water - 0,00059 540 environmental impacts generated by currents
products, byproducts and wastes, in other words,
the overall impact of the project on the
Table 7. Prices used for raw materials and surrounding environment.
products for the conventional process
biotechnological process The potential environmental impact system
output per unit time and the impact potential
Purity USD/kg Flow kg/h generated within the system per unit mass of
Sulfur 99 % min 0,07 654,42 product was calculated by evaluating each of the
two simulations for the conventional process and
the bio process in a specialized software
developed by the EPA and called WAR GUI. In
the WAR you get a numerical result of PEI or the
potential environmental impact for each of the
eight major indices and are in their order: Human
Toxicity Potential Ingestion (HTPI) Human
Toxicity Potential Exposure (HTPE), Toxicity
Terrestrial Potential (TTP), Aquatic Toxicity
Potential (ATP) Global Warming Potential
(GWP) Ozone Depletion Potential (ODP),
Photochemistry Oxidation Potential (PCOP) And
Acidification Potential (AP); from the values of
each of the categories a weighted done to
determine the full impact considering the
percentage of weight or level of importance
assigned to each line with the specific
requirements defined by the location of the
project, in this case point , contributions are the
same for all indexes. When simulations developed
in APEN PLUS the imported WAR, substances
that make up each input current and output load,
like the corresponding flows and the overall
energy requirements of the process, this in order
to evaluate aspects such as toxicity of the
compounds and the risk factor environmental,
allowing quantifying the potential environmental
impact (PEI) and generate comparative graphs of
simulations. Sometimes you may experience
problems loading some components are presented
because they are not part of the database WAR or
there are problems with simulation and do not
load or flows or energy requirements in these
cases must be entered manually substances
considering their composition, specify each of the
input streams, output streams and products with a
corresponding flow value and also the total
energy used during the process, in order to
calculate the Potential environmental impact.
2.4. Social Evaluation
For social evaluation of each proposed process it
was considered only to analyze the number of
employees required per 1 kg of acid produced,
therefore, considering that the plant has an
average conditions and using figure 12 the
interception of line B is sought with the Product
production in tons / day and the number of
employees-hours / day is read, finally the number
of employees per kg of product can be obtained.
Figure 12. Curve to obtain the number of
employees-hours / day [27].
3. RESULTS
3.1. Conventional process
3.1.1. Modeling and simulation
If it is considered that the elemental sulfur feed
flow to the conventional process simulated by the
double contact technology is set at 0.1818 Kg / s
and that at the end of the process, 0,5471 Kg / s of
Sulfuric Acid can be generated. with a purity of
99,89%, the overall yield is 3,01 Kg Acid / Kg
Sulfur, that is to say for each gram of elemental
sulfur coming from the mine the vinegar that is
fed gives 3,01 Kg of Sulfuric Acid of high purity.
Table 12 shows the global balance of matter.
Now, in Table 11 shows the values in Watts of the
energy supplied and generated in each equipment,
while Figure 13 shows the energy per zone, and it
is seen that the pretreatment is the one that
consumes the most energy and that is clear from
the combustion stage of the sulfur and the
compression of the air.
When the signal is negative, it refers to a heat
outflow, if the sign is positive, it corresponds to
an inflow. The sum of the heats of each unit to
obtain the energy requirement of the global
process generates a value with a negative sign,
which means that the heat generated is greater
than the heat required during the process,
however, this value is an ideal , since total energy
integration is not guaranteed and therefore all the
heat generated is not used to meet the energy
needs of the system, therefore, to calculate the
Energy that is required per Kg of product are OXIDAT1 -5896,97619
taken into account only the positive values, in the OXIDAT2 -42021,7643
end the result turns out to be 17,349 MJ / Kg
OXIDAT3 -47303,0891
Sulfuric acid.
EXC-3 171795,276
According to literature, all steps in the production EXC-4 84691,0029
of sulfuric acid from elemental Sulphur are REAC-ABS -21456,5898
exothermic. Therefore, heat recovery in these
ABS 1 0
plants is a key aspect both from economic and
environmental point of view. This heat is used to ABS2 0
meet the energy requirements in other locations of Separation EXC-5 -1156114,63
the plants and even to give extra energy for EXC-7 37424,4278
electricity production [15]. This energy is EXC-9 -759001,533
therefore obtained as a subproduct of the own
process and has the additional advantage that no EXC-10 -210732,06
CO2 is produced during the combustion as it is 9,492 MJ/s
TOTAL
normal when oil or natural gas are used as fuel -3,2189 MJ/s
[15].

Table 11. Energetic Requirements of the 8

Equipment. 7
Total energy (MJ/s)
6
Stage Equipment Energy (J/S)
5
MELTER 1076303,08
FURNANCE -2210824,78 4

DRYINGTW 0 3
EXC-1 628555,376 2
EXC-2 -1033683,04 1
Pretreatment
EXC-6 -12872,2923
0
EXC-8 -849515,575 Pretreatment Reaction Zone Separation
COMP1 432508,623 Zone

COMP2 704977,056
PUMP 125,489014 Figure 13. Total energy for stages
Reaction PREOXID -5898,326

Table 12. Global material balance for the conventional process

INLET OUTLET
Units S-SOLID AIRHUM WATER2 WATER TAIL OLEUM
Temperature K 298,15 298,15 298,15 298,15 298,15 298,15
Pressure Pa 101325 101325 101325 101325 101325 101325
Mass Flows Total kg/sec 0,1818 2,5 0,05 0,1 2,2841 0,5476
SO3 kg/sec 0 0 0 0 1,29E-07 8,44E-11
SO2 kg/sec 0 0 0 0 0,002013 5,52E-07
O2 kg/sec 0 0,5534 0 0 0,2818 3,98E-06
 N2 kg/sec 0 1,8216 0 0 1,8216 9,78E-06
H2O kg/sec 0 0,125 0,05 0,1 0,1729 0,0005549
S-SOLID kg/sec 0,1818 0 0 0 0 0
S-LIQUID 0 0 0 0 0 0
ACID kg/sec 0 0 0 0 0,005875 0,5471
TOTAL kg/sec 2,832 2,832

3.1.2. Economic Evaluation

Table 13. Results of sulfuric acid production costs
The results obtained by the economic simulator using the double contact process.
are shown in table 13 and summarized in figure Economic Evaluation
USD/perio
14. It is clear that the main production costs are d
associated with utilities and depreciation of Raw materials cost 406466
equipment, this was expected due to the high Utilities cost 2,80E+06
energy consumption due to the high temperatures Operating Labor cost 179528
during the whole process and on the other hand it
Maintenance Cost 121628
is also known that the sulfuric acid is very
corrosive with the equipment, so the useful life of Operating Changes 44881,9
the equipment is reduced. Plant Overhead 150578
G and A cost 296310
This can be seen in Figure 15 where operating Depreciation 1,21E+06
costs are shown in the three stages of the process,
Total capital 5,21E+06
As expected, the higher production costs are
generated in the pre-treatment stage since it is the Total capital 5,21
stage that consumes more energy, therefore more Product flow 1971,47 kg/h
service fluids between the heating and cooling of work in hours 8766 h
the equipment and, therefore, greater wear on the Production cost of 1 kg USD/kg of
0,30
equipment . of product Product
Acid commercial sales USD/kg of
0,5
From these costs, it was obtained that to produce price Product
1 kg of sulfuric acid has a cost of 0.3 USD or 0,3 Gross Income Margin 39,7%
USD/kg of sulfuric acid; now, compared to the CAPEX 1,72E+07 USD
market price, a gross income margin of 39.7% . USD/perio
OPEX 4,91E+06
d

Finally, the net present value found in figure 16

was analyzed and it was obtained that for the 10
years the NPV recovered at 8 years, so it makes 23,157
53,803
the process profitable to these conditions, but 2,893 5,692
even so the net earnings at the end of 10 years are
15,232 0,862
not very large. Now, according to what was
mentioned in the previous point, due to the fact 2,336
that the production of sulfuric acid is very 7,808 3,449
exothermic, the use of this energy is key to the Raw materials cost Utilities cost
reduction of costs, which is why the Operating Labor cost Maintenance Cost
implementation of a heat exchange network is Operating Changes Plant Overhead
necessary.
G and A cost Depreciation
Figure 14. Summary of production costs. As mentioned above, the flow produced of
sulfuric acid for the conventional process was
0,5471 kg/s=47,27 ton/day with these values
being he read the corresponding value on line B
of figure 12, it was obtained 40 employe-hours /
day and finally is obteained 8,47e-4 employe-
2,00 hours/kg of sulfuric acid, therefore, they are
required 7,4 employe/kg of sulfuric acid.
1,50
mUSD/periodo

1,00

0,50

0,00

Utilities cost Operating Labor cost

Maintenance Cost Operating Changes
Plant Overhead G and A cost
Depreciation 3.2. Biotechnological process
Figure 15. Distribution of production costs in
3.2.1. Modeling and simulation
stages.
1,E+07 According to the balances in the BIOREAC
NPV (USD/period)

5,E+06 reactor, the conditions established, for each

0,E+00 0,1817 kg of sulfur , 0,2663 kg of sulfuric acid are
-5,E+06 0 2 4 6 8 10 produced in the react, that is, for every 1 kg of
sulfur, the bacteria can produce 1,41 kg of sulfuric
-1,E+07
acid. Now if the separation is considered as an
-2,E+07 evaporation of the water in an ideal equipment,
-2,E+07 the sulfuric acid can be lost in the trajectory
Year obtained 0,2512 kg of sulfuric acid. Finally, for
every 1 kg of sulfur fed to the biotechnological
Figure 16. Net present value at 10 years for the process, 1.38 kg of sulfuric acid with a
conventional process. composition of 98% by weight is obtained. Table
15 shows the overall balance for this process.

3.1.3. Environmental evaluation Now, as current outputs we have a stream of

As the analysis of environmental evaluation is a
comparative process, it was decided to perform
the analysis of the results of the two processes
together, so these results can be seen in the
COMPARATION index
3.1.4. Social Evaluation
solids that contains the nutrients and the
microorganism, in practice this current can be
recirculated to the process and thus reduce costs.
For other part, between the outflow currents is
practically pure water, but the problem observed
with this process, is the exaggerated amount that
requires water (approximately> 90% of the
solution is water), although this can be recovered,
the energy costs required to achieve it can be
equally large depending on the technology used
for that purpose. Additionally, it must be Reaction BIOREAC -1896586,46
remembered that for the sulfuric acid-water FILTER 0
mixture as the mixture is more diluted, this is also
FLASH1 22739184,5
more unstable, so corrosion in the teams is more
evident. Separation FLASH2 78457,9083
EXC-1 -22959432,6
Now, for the calculation of energy costs in EXC-4 -40232,2126
process it must be considered that in the reaction
stage it is not possible to determine the real value 47,9 MJ/s
TOTAL
because a stoichiometric reactor was used. It is -1,89 MJ/s
also known that the energy costs required to carry
out the separation may not correspond directly
with the reality because flash equipment was used 50
for its simulation. In the table 14 is show this 45
results of energy organized for stage and figure 17
40

Total energy (MJ/S)

is show this report. It is evident that the separation
35
zone was the stage that consumed the most energy
30
and this is mainly due to the consumption of
energy for the evaporation of water. Thus, it can 25
finally be concluded that to produce 1 kg of 20
sulfuric acid is required 190,68 MJ of energy or 15
190,68 MJ/kg Sulfuric acid. 10
5
Table 14. Energetic Requirements of the 0
Equipment. Pretreatment Reaction Zone Separation
Stage Equipment Energy (J/S) Zone
EXC 185326,513
Pretreatment EXC-2 -2482,898 Figure 17. Total energy by stages.
COMP 3452,0849

Table 15. Global material balance for the biotechnological process.

INLET OUTLET
Units AIR BACTERIA SULFUR NUTRIENT SOLID OUT OLEUM
Temperature K 298,15 298,15 298,15 298,15 298,15 298,15 298,15
Pressure Pa 101325 101325 101325 101325 101325 101325 101325
Mass Flows kg/sec 0,012025 8,9099 0,1818 0,01727 0,08119 8,7837 0,2561
BACTERIA kg/sec 0 0,0009089 0 0 0,03982 0 0
NUTRI-2 kg/sec 0 0 0 0,0009089 0,0008975 0 0
NUTRI-3 kg/sec 0 0 0 0,01363 0,01345 0 0
NUTRI-4 kg/sec 0 0 0 0,002727 0,002692 0 0
SULFUR-L kg/sec 0 0 0,1818 0 3,48E-06 1,25E-05 0,001281
WATER kg/sec 0,0006012 8,9 0 0 0,02357 8,7582 0,003443
O2 kg/sec 0,002662 0 0 0 7,08E-06 2,63E-03 2,52E-11
N2 kg/sec 0,008762 0 0 0 2,33E-05 8,66E-03 5,83E-11
ACID kg/sec 0 0,009089 0 0 0,0007146 0,01415 0,2512
TOTAL kg/sec 9,1209 9,1209
3.2.2. Economic evaluation Total capital 1,17E+07
Total capital 11,70
The economic results for the biotechnological
Product flow 905,162 kg/h
process are shown in table 16 and summarized in
figure 18. For this process, it is appreciated that work in hours 8766 h
the main costs are associated with the service Production cost of 1 kg 1,47 USD/kg of
fluids, This is best seen in Figure 19, where of product Product
Acid commercial sales 0,3 USD/kg of
operating costs are shown in the three stages of price Product
the process, and as it is observed, the costs of the
Gross Income Margin -391,65
utilities are generated mostly in the separation
stage and this is mainly due to the evaporated CAPEX 9,50E+06 USD
water cooling of the Flash equipment. USD/perio
OPEX 1,09E+07
d
Now, from these costs it was obtained that to
produce 1 kg of sulfuric acid via biotechnology
has a cost of 1.47 USD. Now, compared to the
market price, it is clear that the production cost is 0,736
higher, obtaining a gross income Margin - 6,999 0,514 5,508
391.7%, which translates to 391% margin of 0,240
losses. 13,299 0,959
79,702
Finally, we analyzed the net present value found
5,342
in figure 20, and it was obtained that for the 10
Raw materials cost Utilities cost
years the NPV does not recover, on the contrary,
the process becomes less profitable with the Operating Labor cost Maintenance Cost
passage of time. Operating Changes Plant Overhead
G and A cost Depreciation
As mentioned above, the main problem observed
in this technology is related to the separation of Figure 18. Summary of production costs.
sulfuric acid from water because it generates high
energy consumption and high costs related to the
cooling of evaporated water, so it is clear that this
stage must be redesigned and optimized. As a
proposal for cost reduction, we have the 10,00
evaluation of the separation by means of selective
mUSD/periodo

cationic membranes to the -SO4 ion, this can 8,00

generate a great reduction in costs and energy. 6,00
4,00
Table 16. Results of sulfuric acid production costs
using the biotechnological process. 2,00
USD/perio
Economic Evaluation 0,00
d
Raw materials cost 625214
Utilities cost 9,33E+06
Operating Labor cost 112205
60156,7 Utilities cost Operating Labor cost
Maintenance Cost
Operating Changes 28051,2 Maintenance Cost Operating Changes

Plant Overhead 86180,7 Plant Overhead G and A cost

G and A cost 819162 Depreciation

Depreciation 644575
Figure 19. Distribution of production costs in
stages
0,E+00
NPV (USD/period)
0 2 4 6
-1,E+07
-2,E+07
-3,E+07
-4,E+07
Year
Figure 20. Net present value at 10 years for the
conventional process.
3.2.3. Environmental evaluation
As the analysis of environmental evaluation is a
comparative process, it was decided to perform
the analysis of the results of the two processes
together, so these results can be seen in the
COMPARATION index
3.2.4. Social Evaluation
As mentioned, the flow produced from sulfuric
acid for the biotechnological process was 0,2512
kg/s=21,7 ton/day with these values being he read
the corresponding value on line B of figure 12, it
was obtained 35 employee-hours / day and finally
is obtained 1,6e-3 employee-hours/kg of sulfuric
acid, therefore, they are required 14,1
employee/kg of sulfuric acid.
4. COMPARISON
If you compare the mass and energy yields of
each process, the first conclusion is that,
when processing 0.1817 kg / s, a greater
amount of sulfuric acid is produced in the
conventional double-contact process than in
the bioprocess, when relating these values, it
8 10 is obtained that the production of acid in the
conventional process is 2.26 times greater
than the bio process
At the energy level, both processes involve
large amounts of energy, but undoubtedly due
to the amount of water used, the
biotechnological process presents greater
energy consumption in the stage of separation
of water by evaporation, but it should be
noted that the heat generated in the
convectional process is clearly usable.
On the other hand, when buying the processes
economically it is clear that the conventional
process is much better because the production
costs are 5 times less than the production
costs due to the biotechnological process, but
in both cases it should be noted that the higher
production costs are associated with the costs
of utilities
4.1. Environmental evaluation
Looking at the results plotted in Figure 21 it can
be determined that the PEI output per unit time of
bio process is considerably higher than the IEP of
the conventional process, the calculated values
being 1.69 PEI / s and 0.4 PEI / s respectively. A
difference of 1.29 PEI / s in the potential
environmental impact suggests that in general
terms the process proposed by the method of
double contact sulfuric acid production scale is
much more friendly to the environment and
therefore more viable; this is justified and
supported to consider that while a process that
requires a large number of equipment operating at
elevated temperature and the reactions are
strongly exothermic and prone to the generation
of potentially hazardous mist as in the case of
hydration of sulfur trioxide or the oxidation of
sulfur dioxide, the proposed process effective
integration of currents is done in the purification
zone and only two output streams are generated,
one containing sulfuric acid in a high degree
purity and the other can be considered as a waste
stream but mainly composed of oxygen, nitrogen,
water and traces of sulfur trioxide, sulfur dioxide
and sulfuric acid. Although categorized as ATP,
GWP, ODP and PCOP, impacts are similar, the
difference is evident in TTP AND AP where the
impact generated by the bio process is higher,
because the generation of two waste streams are
not reintegrating or advantage in the process, one
of which has an important biological and organic
load consisting mainly of bacteria and nutrients.
High values in HTPI And HTPE due to the toxic
nature of the reactants and products, and the risk
(PEI) assumes a negative value corresponding to
1.91 PEI / kg, while the bio a positive value of
2.59 PEI / Kg, therefore, in terms of
environmental favorability, the proposed process
for obtaining sulfuric acid using the double
contact method generates products with a lower
impact compared to the reagents used.
PEI Output Speed
Conventional Bio
1,8
1,6

IMPACT (PEI/s)
they pose to human health; much attention in the 1,4
1,2
only category where the potential impact is 1
greater for conventional than for bio is HTPE, 0,8
0,6
but this is due to the fact that during the oxidation 0,4
0,2
process of sulfur dioxide, sulfur trioxide 0
emissions or hydration reactor mists can be
produced or generated to obtain sulfuric acid,
which in important parts and with long exposures IMPACT CATEGORIES
can cause problems of health in the personnel that
works in the plant, or the population located in the Figure 21. Comparison Chart Potential
zone of influence. environmental impact (PEI) output per unit of
time.
In the Figure 22 negative values acquired by the
environmental impact generated (PEI) mean that
in the process decreases the potential impact of PEI Generated Within a System
inlet substances through its transformation into Per Mass of Product Streams
less harmful, in other words, the products
Conventional Bio
obtained generate less pollution compared to the
reactants. Although the behavior of PEI into 3
IMPACT (PEI/kg product)

categories as GWP, ODP and PCOP are similar 2

and positive, because the products are generating 1
greater impact than the reactants, the differences 0
can be evidenced in indices as HTPI, TTP and
-1
ATP where behavior impacts for both processes
-2
is opposite, because while the conventional
acquires all negative values, the bio presents all -3
Impact Categories
positive values, suggesting that products bio are
more contaminants than the products of Figure. Graphical comparative of potential
conventional and is understandable since the environmental impact (PEI) generated per unit
solids stream leaving the system contains an time.
important biological and organic concentration
plus residual nutrients, can impact quite important
in these categories. In HTPE and AP although 5. CONCLUSIONS
there are differences values are both positive, this
is due to strongly acid character of the product The modeling or simulation of a production
obtained, in contrast to the reagent employed, in process of sulfuric acid from two different
addition to the possible generation of highly toxic technological routes and the same raw material
mists. Finally the full impact of conventional through a specialized software such as ASPEN
allows to evaluate with the simultaneous use of
tools such as Aspen Process Economic Analyzer
package or the WAR developed by the EPA the
economic, environmental and social impacts of
the project and determine sustainability; being
understood as sustainability that a process is
economically viable, present a potential of zero or
reduced environmental impact and in the social
aspect is characterized by the effective generation
of jobs. This allows us to assess the potential of
ASPEN in the comparative evaluation of a
conventional process based on the double contact
method and a process using the bacterium
Acidithiobacillus thiooxidans as a microorganism
for the production of sulfuric acid from elemental
sulfur.
When evaluating the results of the simulation and
the applied analyzes, it is determined that the
conventional process meets the requirements to
be considered sustainable, compared to the bio,
higher yields are obtained, lower energy
requirements, lower production costs, a faster
recovery of the VNP, lower environmental
impacts and greater employment generation. This
does not indicate that the biotenological process
is not a viable alternative, on the contrary, if a
solution to the main problems is sought, which is
the separation of dilute sulfuric acid in a stream of
water and the performance of the bacteria, this
implies an improvement in the consumption of
energy, therefore in the flow of services and, on
the other hand, a treatment to the outflow
currents, thus improving the environmental
impact generated.
6. REFERENCES
[1] Sulfuric Acid. OEC. Accessed January 16,
2019.
[2] IMPORT & EXPORT SULFURIC ACID.
Nosis trade. Accessed January 16, 2019.
[3] CA Cardona, MI Montoya, JA Quintero
(2004), technology selection suitable for the
production of fuel ethanol, Cali, Colombia
Engineering of Natural Resources and
Environment.
[4] Sulfuric Acid MANUFACTURING:
METHOD OF CAMERAS.
http://www.quimitube.com/produccion-acido-
sulfurico-metodo-camaras-de-plomo.
Consultation Date: September 15, 2018.
[5] Pernett Bolaño, Leda Del Carmen, Ivan
Alberto Ochoa Martinez, Mauricio Eduardo
Robledo Barrios, and Cesar Augusto Durán
Rueda. 2016. "Modeling and simulation of a
catalytic reactor for the oxidation of SO2 to SO3,
using V2O5 as a catalyst." Prospective 14 (1): 39.
[6] Maldonado, Jennifer. 2015. "Jennifer
Maldonado Torres: Sulfuric Acid Production
(Contact Method)". Jennifer Maldonado Torres
(blog). May 1, 2015.
[7] Forero, Edward. sf 'production of sulfuric acid
by the contact process. " Accessed September 18,
2018.
[8] A. Camacho, "Sulfur Bacteria", Encyclopedia
of Inland Waters, pp. 261-278, 2009.
[9] M. Cardona and Marquez, "Biodesulfurization
of two Colombian coals With native
microorganisms", Fuel Processing Technology,
vol. 90, no. 9, pp. 1099-1106, 2009.
[10] S. Street-Castaneda, M. Marquez-Godoy and
J. Hernandez-Ortiz, "Phosphorus recovery from
high Concentrations of low-grade phosphate
rocks using the acid produced by the biogenic
acidophilic bacteria Acidithiobacillus
thiooxidans", Minerals Engineering, vol . 115, pp.
97-105, 2018.
[11] H. Liu, Y. Lan and Y. Cheng, "Optimal
production of sulfuric acid by Thiobacillus
thiooxidans using response surface
methodology", Process Biochemistry, vol. 39, no.
12, pp. 1953-1961, 2004.
[12] S. Street-Castaneda, M. Marquez-Godoy and
J. Hernandez-Ortiz, "Phosphorus recovery from
high Concentrations of low-grade phosphate
rocks using the acid produced by the biogenic
acidophilic bacteria Acidithiobacillus
thiooxidans", Minerals Engineering, vol . 115, pp.
97-105, 2018.
[13] SIMCO, Producción de azudre. Unidad de
planeación Minero Energética UPME. Accessed
January 16, 2019.
[14] Reference cost for transporting heavy loads.
Accessed January 16, 2019.
[15] M. Martin, «Chapter 7 - Sulfuric acid,» de
Industrial Chemical Process Analysis and Design,
Salamanca, 2017.
[16] R. Eklund, «The Rate of Oxidation of Sulfur
Dioxide With a Commercial Vanadium Catalyst,»
Almqvist & Wiksells Boktr, 1956.
[17] S. Fogler, Elements of Chemical Reaction
Engineering, third ed., New York: Prentice Hall,
1997.
[18] M. Gomez y H. Ibarra, Ingeniería de los
reactores químicos con aplicaciones en Aspen
Plus, Manizales, 2015.
[19] R. Hofmann-Sievert y W. Castleman,
«Reaction of SO:, with Water Clusters and the
Formation of H2S04,» American Chemical
Society, vol. 88, nº 15, pp. 3329-3333, 1984.
[20] R. Edwar, D. Hanson y L. Gregory, «Kinetics
and Products of the Gas-Phase Reaction of SO3
with Water,» American Chemical Society, vol.
100, nº 51, pp. 19911-19916, 1996.
[21] S. Castañeda, M. Másquez y J. Hernández,
«Phosphorus recovery from high concentrations
of low-grade phosphate rocks using the biogenic
acid produced by the acidophilic bacteria
Acidithiobacillus thiooxidans,» Minerals
Engineering, vol. 115, pp. 97-105, 2018.
[22] Y. Cheng y Y. Peng, «Mechanism and
Kinetics of Elemental Sulfur Oxidation by
Thiobacillus Thiooxidans in Batch Fermenter,»
Environmental Technology, 199.
[23] R. Gourdon y F. Funtowicz, «Kinetic model
of elemental sulfur oxidation by Thiobacillus
thiooxidans in batch slurry reactors,» Bioprocess
Engineering, p. 241±249, 1998.
[24] F. Risse, A. Newrzella y e. al,
«Procedimiento para purificar ácido sulfúrico».
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[25] J. McFarland, «ABSORPTION AND
DRYING TOWERS». Mississauga, Canada
Patente 4.747.970, 21 May 1988.
[26] F. García, L. de Diego, A. Cabello y e. al,
«Sulphuric acid production via Chemical
Looping Combustion of elemental sulphur,»
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West, “Chaper 6: Cost Estimation,” in Plant
 ANNEX A

Formato Único para Presentación de Propuestas

REGISTRO ELECTRONICO

1. Nombre del proyecto

Producción de Ácido sulfúrico a partir de azufre elemental

2. Resumen del proyecto

2.1. El ácido sulfúrico es una de las sustancias fabricadas en mayor volumen a nivel mundial, su
importancia radica en que es una plataforma para diferentes procesos industriales tales como
industria de fertilizantes, industria petroquímica, extracción de metales, explosivos, control
ambiental, entre otros. Tal ha sido su impacto en la economía, que se ha utilizado como indicador
del nivel de industrialización de los países. El proyecto busca fomentar la producción de ácido
sulfúrico en Colombia empleando el método de contacto doble y a partir del azufre elemental
explotado en la mina el vinagre y comercializado por la empresa EMICAUCA.
2.2. ¿Es su actividad propuesta parte de un proyecto mayor en marcha?

Si
3. Presupuesto del proyecto Indique el financiamiento que requiere. Diferencie entre el
financiamiento solicitado y el financiamiento solicitado a otras fuentes y/o aporte propio (señale las
fuentes).
Costo total del proyecto (en US$) 17200000
Monto solicitado al Concurso (en US$)
17200000

3.1. Rubros del presupuesto

a. Costos directos (sueldos de equipo y consultores) US$:
179528
b. Logística (organización de actividades)US$:
c. Otros costos (gastos administrativos ) US$: 296310

4. Establecimiento de alianzas: (Si su organización de jóvenes cuenta con personería jurídica

pase a la pregunta 4.2)

4.1. Institución patrocinadora:

Describa las actividades principales de la(s) instituciones con la que ha establecido la alianza.
Recuerde que todos los proyectos deben ser ejecutados en alianza con instituciones que cuenten
con personería jurídica y cuenta bancaria, que a su vez será la patrocinadora. (máximo 150
palabras)

5. Información institucional básica

Nombre y apellido del coordinador del proyecto: Gina Marcela Arias Bravo
Nombre de la institución patrocinadora:
Tipo de institución:
Correo electrónico: gmariasb@unal.edu.co
Teléfono: 3147692812
Fax:
Ciudad o Localidad: Manizales
Cantón:
Provincia:

6. Área temática Indique el área temática en la que se

Industria Química
enmarca su propuesta:

7. Área geográfica del proyecto (en la sección PROVINCIA señale aquella donde
mayoritariamente se desarrolla el proyecto)
Ciudad o Localidad: Manizales - Caldas
Cantón:
Provincia: Sector industrial Juanchito

8. Zona de ejecución Defina si el proyecto se ejecutará

en zona rural (menos de 2000 habitantes),
El proyecto se ejecutará en zona urbana
Si
9. Detalles del proyecto lea cuidadosamente las indicaciones para cada campo.

a. Objetivos Describa su idea. ¿Qué es lo que intenta lograr? (máximo 200 palabras)
El ácido sulfúrico es un químico de plataforma altamente producido y comercializado en mercados
internacionales por su valor como insumo o materia prima para diferentes tipos de actividades
industriales. Actualmente se produce en Colombia pero no se logra cubrir la demanda interna, se
estima que el déficit para el año 2020 será de 2500 Ton/año. Se evaluó la producción de ácido
sulfúrico empleando el método de contacto doble a partir de una materia prima nacional, el azufre
elemental explotado en la mina el vinagre por la empresa indígena EMICAUCA, los resultados fueron
prometedores, el proceso es económicamente viable, presenta bajos impactos ambientales y un
potencial importante para la generación de empleos. La instalación de una planta de producción en
la zona industrial Juanchito de la ciudad de Manizales, repercutirá en una generación inmediata de
puestos de trabajo y el incremento progresivo del producto interno bruto de la región, además el
incremento en la producción de ácido sulfúrico impulsaría el desarrollo de otro tipo de industrias
que requieran ese compuesto como materia prima para la obtención de productos de mayor valor
agregado.

b. Grupo objetivo Indique a quiénes está dirigido el proyecto, su número y características (máximo
100 palabras)
El proyecto está dirigido a los industriales que buscan implementar procesos sostenibles y viables
para la producción de ácido sulfúrico a partir del azufre que comercializa la empresa EMICAUCA en
la única mina que actualmente se explota en el país, el vinagre.

c. Plan de trabajo ¿Cuáles son las principales etapas del proyecto y cuándo se van a llevar a cabo?
(Máximo 300 palabras)
Primero que todo es necesario conseguir una financiación para la compra de las tecnologías que se
requieran para la producción del proyecto y establecer una planta de producción. Una vez
establecidos se deben crear alianzas estratégicas con EMICAUCA y otras industrias que puedan
aportar las materias primas necesarias. Se debe conseguir mano de obra especializada para obtener
una buena producción y realizar una transmisión del conocimiento para que grandes industrias se
enteren de que se está produciendo una mayor cantidad de Ácido sulfúrico en el país y le inviertan
al producto nacional.

d. Innovación: ¿En qué reside el carácter innovador de su proyecto? ¿En qué se diferencia su
propuesta de otros proyectos o programas similares? (Máximo 100 palabras)
El carácter innovador del proyecto reside en el planteamiento de la producción de un compuesto
que actualmente se produce en Colombia, pero que no logra abastecer la demanda interna, es un
proyecto con sostenibilidad ambiental que va a incorporar diferentes eslabones económicos,
aprovechando materias primas nacionales.

e. Participación Ciudadana: ¿Al final de los 7 meses cómo mostrarán que la propuesta ha tenido
el impacto que ustedes esperan? (Máximo 150 palabras)
Primero por la cantidad de empleos generados, al contratar mano de obra de la región para
desempeñarse en la planta, segundo, con el volumen efectivo de ácido sulfúrico producido en ese
lapso de tiempo, tercero con el porcentaje en la cantidad de demanda nacional que se ha logrado
cubrir y cuarto con el porcentaje en importaciones para suplir necesidades en mercados
internacionales.

f. Recursos: Señale los recursos propios en dinero, bienes, servicios, infraestructura, etc. que
usaría en el proyecto. Indicar el monto estimado. (Máximo 100 palabras)
No se cuentan con recursos propios

g. Productos: ¿Cuáles serán los productos (demostrables) de su proyecto? (Máximo 150 palabras)
Los productos demostrables son primero un volumen de ácido sulfúrico previamente establecido por
día, segundo una disminución de la tasa de desempleo en el sector ya que se requiere generar
varios puestos de trabajo para un correcto funcionamiento de la planta.

h. Resultados: ¿Qué beneficios se espera alcanzar para el grupo de beneficiarios una vez culminado
el proyecto? ¿Cómo considera que se van a beneficiar? (máximo 150 palabras)
Los industriales se verán beneficiados a nivel económico en tanto que una producción nacional
reducirá los costos de importación del producto y les permitirá fabricar sus propios productos
derivados del ácido sulfúrico, además, el costo de acceso de los ciudadanos a los diferentes
productos se presume será menor. Sumado a todo lo anterior, habrá una generación de empleo que
va a beneficiar a varias familias de la zona.
i. Evaluación: ¿Cómo sabrá que su proyecto ha sido exitoso? Qué indicadores verificables le
permitirán en el futuro evaluar el impacto de su proyecto. (máximo 200 palabras)
Se puede evaluar mediante indicadores económicos del país al observar una disminución en la
importación del producto o incluso de sus derivados, evidenciándose de esta forma que se está
utilizando el producto.

j. Sostenibilidad: Si su proyecto tiene resultados positivos qué haría para que el proyecto
continúe? ¿Cree que su proyecto podría ser auto-sostenible en el futuro? ¿Cómo? (máximo 200
palabras)
El proyecto es sostenible porque tiene alta viabilidad económica generando ganancias importantes
en un tiempo superior a ocho años, además los impactos generados durante el proceso de
producción son muy reducidos en comparación con otras tecnologías propuestas y evaluadas. La
tendencia de la demanda de ácido sulfúrico en el país es creciente, por lo tanto se proyectan,
volúmenes de producción más elevados en un futuro, mediante la generación de relaciones
comerciales importantes, incrementando así el flujo de caja y consecuentemente las ganancias
generadas.

k. Capacidad ejecutiva: ¿Con qué experiencia cuenta su institución o con quienes se ha asociado
para ejecutar su propuesta? (máximo 150 palabras)

10. Provea un breve cronograma de implementación de la/s actividad/es (detalle cada

una de las actividades previstas en la columna izquierda e indique el mes en el que se
llevarán a cabo en la columna derecha).

Cronograma:

Actividades Mes de Ejecución

de cada actividad

Inicio del Concurso:

Fecha límite para la presentación de propuestas:
Entrega de resultados y premios: