Bioresource Technology Reports 13 (2021) 100615

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Bioresource Technology Reports

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Deacidification of natural gas in stationary state using

Aspen HYSYS
Furkan Kartal, Uğur Özveren *
Department of Chemical Engineering, Marmara University, Goztepe Campus, 34722 Kadikoy, Istanbul, Turkey

AR T I C L E I N F O A B S T R A C T

Keywords: Natural gas drags undesirable components from the reservoirs such as: Sulfihydric Acid (H2S), Carbon Dioxide (CO2)
Natural gas and water in the gaseous phase, so it is said that the gas received is a humid, bitter and hydrated gas. ; bitter due to the
Gasification acidic components it contains, moist due to the presence of liquid hydrocarbons and hydrated due to the presence of
Aspen HYSYS water that drags from the reservoirs.
Bubbling bed gasifier
Thermodynamic analysis The natural gas de-acidification process plays a very important role in the processing of this hydrocarbon. Because the
presence of these acid components causes corrosion problems both in transport lines or pipelines and tanker trucks, as
well as in the equipment implemented for their processing. So its elimination is necessary.

In this work, the natural gas de-acidification process was evaluated through simulation at Aspen Hysys, in order to
analyze and determine the best operating conditions for the equipment. This is intended to determine the appropriate
operating conditions for the process, which will allow studying the final characteristics of natural gas through the most
important parameters of the process. With the realization of the simulation in Aspen Hysys, it is planned to obtain a
product with acceptable specifications for its transport and suitable use, whether industrial or commercial.

1. Introduction Turkey compensates for the majority of its energy requirements by

The increase in the world population, makes energy consumption
ever greater to satisfy the requirements that allow guaranteeing the
continuity of its development, one of these main sources of energy that
has existed for many years, which is currently used and The most likely
one of the most important in the future is natural gas, coming from oil
gas fields. One of the great concerns that the natural gas industry
presents is the removal of the pollutants that it brings with it from the
subsoil, these pollutants are called acid gases, their presence generates
problems of bad odor, toxicity, corrosion, reduction of calorific value
and some components from certain concentrations in the environment
mortally threaten the life of living beings.
Many processes, over the last 130 years, have been developed with
the sole purpose of obtaining the removal of these acid gases,
especially CO2 and H2S, among the most important is the absorption
process with physical and chemical solvents. and mixed; consumable
cyclic processes, membranes and direct conversion processes. (Perea-
Moreno et al., 2019).
coal and natural gas (Melikoglu, 2017). However, Turkey has insuffi-
cient natural-gas reserves to supply for its increasing energy demand
(Melikoglu, 2013), and taking necessary precautions is a key to avoid
foreign dependence. Compared to various renewable energy sources,
biomass is seen as having a significant stake for Turkey.
The total recoverable bioenergy potential is predicted to be of about
16.92 Mtoe according to Kaygusuz (Kaygusuz and Türker, 2002),
including livestock farming wastes, forestry and wood processing
residues, municipal wastes, and primary agricultural residues.
Considering all these reports, increasing the share of biomass energy
utilization possesses strategic importance for Turkey to reduce foreign
energy dependence.
Many thermochemical techniques are employed to convert biomass
into favorable gaseous products, however the gasification is a promising
method with its high efficiency, the availability of diverse solid fuels, the
ability to produce at various capacities, and the low concentrations of
hazardous emissions (Pauls et al., 2016). Furthermore, gasification is a
less complex and more inexpensive method than biochemical routes
(Sikarwar et al., 2017). Gasification is a thermochemical conversion

* Corresponding author.
E-mail address: ugur.ozveren@marmara.edu.tr (U. Özveren).

https://doi.org/10.1016/j.biteb.2020.100615
Received 9 October 2020; Received in revised form 2 December 2020; Accepted 3 December 2020
Available online 8 December 2020
2589-014X/© 2020 Elsevier Ltd. All rights reserved.
 F. Kartal and U. Özveren
2. Methodology
2.1. Feedstock characteristics
Here are certain considerations that must be followed to simulate
processes, then this methodology is explained in a general way:
2.2. Process Flow Diagram
The flow diagram of the process to be simulated must be prepared and
obtained, which must contain all the data and streams that comprise it, as
well as their numbering to reflect the interrelationship between the major
teams in the process. In the case of an evaluation, the results obtained
from the simulation should be compared with the data suggested by the
bibliography.
2.3. Simulation strategy
The methods for the calculation of the thermodynamic and physical
properties are defined.
The sequence to be followed by the simulation is also established, in order
to make it as simple as possible and to adequately resolve the recycles of
matter and energy.
2.4. Analysis of the results
The results generated by the simulation are analyzed in order to verify
their reliability
and to compare the simulation scheme that has been chosen to represent
the plant process. At the process level there are several simulators on the
The authors aimed to produce hydrogen by blending petroleum waste
with biomass. The researchers used air and superheated steam miXtures
as gasifying agents and evaluated gasifi- cation parameters like
temperature, syngas chemical composition, and gas yield. Milani et al.
(2017) aimed to propose and analyze alternative options for hybridizing
Concentrated Solar Power (CSP) with biomass, through gasification for
power generation. The authors mentioned the hybrid CSP-biomass
power plant through gasification is an innovative concept that allows the
integration of a combined cycle for power generation, sun-biomass
hybridization, and syngas storage. In addition, the technical and economic
performance that belongs to the hybrid system was reported by the
authors. However, the bubbling bed gasifi- cation characteristics of
different biomass wastes have not been reported using Aspen HYSYS in a
comparative study until now.
The objective of this study is to investigate the gasification charac-
teristics of different biomass using the Aspen HYSYS process simulator.
Received 9 October 2020; Received in revised form 2 December 2020;
Accepted 3 December 2020
Available online 8 December 2020
2589-014X/© 2020 Elsevier Ltd. All rights reserved.
Bioresource Technology Reports 13 (2021) 100615
market, such as: PRO II. PROVISION, CHEMCAD, ASPEN HYSYS, among
others.
2.5. SELECTION OF THE THERMODYNAMIC MODEL
The design of the dehydration and sweetening system was carried out
through the ASPEN HYSYS 8.8 simulator, where all the components
involved in the process are loaded. This simulation package has different
thermodynamic methods to calculate the properties of hydrocarbons and
other substances.
2.6. Package Properties for Amines
For the de-acidification process in this simulator, the package called "Acid
Gas" is selected, which is the amine package that contains the
thermodynamic models developed by D.B.Robinson & Asociados. The
database of physical and chemical properties is restricted to amines and
the following components: acid gases (CO2, H2S, COS, CS2),
hydrocarbons (CH14 - C7H16), olefins (C2, C3), mercaptans (m-
mercaptan, emercaptan), no hydrocarbons (H2, N2, O2, CO, H2O). Caloric
effects are an important factor in amine treatment processes and are taken
into account in this model. Correlations for heats of solution are
determined as a function of composition for heats of solution are
determined as a function of composition and amine type.
Correlations were generated from existing published values or derived
from solubility data using the Gibbs-Helmholtz equation. (ASPEN Hysys)
Table 1
Gas Conditions in the Plant Feed Stream
Conditions Values
Temperature °C 35.00
Pressure (Kg/cm2) 58.00
Molar flow MMSCFD
(million cubic feet per day)
10.00
F. Kartal and U. Özveren Bioresource Technology Reports 13 (2021) 100615

• The entire gasification system was operated in steady-state and Char complete combustion : C + O2→CO2 ( — 393 MJ/kmol) (3)
isothermally.
• Tar and other heavy hydrocarbons were neglected in the syngas Water — gas reaction : C + H2O ↔ CO + H2 ( + 131 MJ/kmol) (4)
composition.
• All reactions occur fast and reach the chemical equilibrium. Hydrogenation : C + 2 H2 ↔ CH4 ( — 75 MJ/kmol) (5)
• Char only contains carbon.
The “TEE-100” block splits the gaseous components produced in the
• Since ash is an inert component and does not react, biomass was
defined on an ash-free basis. “GBR-103” reactor (Gas-1) into “Gas-11” and “Gas-12” streams. The
“Gas-12” stream does not flow into the “GBR-100” reactor, flows directly
• All sulphur and chlorine compounds were formed into H2S and HCl.
to the “MIX-101” block, and contributes to the product gas “ProdGas”.
• Reactors were operated at atmospheric pressure, and pressure drops
were neglected. Thus, methane gas can be observed in syngas, otherwise methane will
reach chemical equilibrium and be depleted in the “GBR-100” reactor
The gasification process was simulated with two Gibbs reactors. This which was operated at high temperatures. Table 2 briefly explains the
modeling method, called non-stoichiometric because of the information descriptions of the blocks in the bubbling bed gasifier model.
on any reaction in the process is not fully known, seems an appropriate
approach to be used for a complex phenomenon such as gasification
(Ramos et al., 2019). Gasification reactions occur based on a chemical
method called Gibbs free energy minimization. Gibbs free energy of a
system is minimized by performing the Lagrange multiplier method in
Aspen HYSYS process simulator as follows:

∂L ∑k
∂ni = ∆Gf ,i + RTlnαi + j=1 λiaij = 0 (1)
0

Fig. 1. Aspen HYSYS flowsheet diagram of the desatification process.

F. Kartal and U. Özveren Bioresource Technology Reports 13 (2021) 100615

3. Results

3.1. Model validation

To measure the accuracy of the newly developed bubbling bed
gasifier model, syngas compositions were compared with the
results of experimental studies in the literature. The gasification
process was simulated under the identical conditions in
experimental studies by using input variables such as gasifier
temperature, characteristics of biomass, the flow rate of solid fuel
and gasification agent, etc. A com- parison of syngas compositions
in experimental studies and newly developed bubbling bed gasifier
model results in Table 2
d have unique physicochemical properties and experiments
were conducted under different operating conditions, the bubbling
bed gasifier model was able to simulate the gasification process.
However, the fact that the model is independent of the design
parameters, neglecting reaction kinetics and fluid mechanics, and
the no residence time in the reactor (rapid reaction occurrence and
reaching chemical equilibrium) cause syngas composi- tions to
differ from experimental results. The deviation of the simulation
outcomes from literature results is calculated by implementing the
relative error. The relative error can be described as:
Simulation output — Experimental output
Relative Error
Experimental output
In particular, the conversion of hydrocarbons into hydrogen,
carbon monoXide, and carbon dioXide gases in chemical equilibrium
makes the prediction of methane gas difficult. In addition, the
presence of methane in the syngas with small concentrations
resulted in a large relative error (%). This challenge was observed in
other equilibrium models and re- ported by other researchers (Han
et al., 2017; Tavares et al., 2020).

Table 2
Results simulation
Recirculación Sour gas Sweet gas Richamine
Vapor 0.0000 1.0000 1.0000 0.0000
Temperature [C] 43.33 35.00 43.51 46.53
Pressure [kg/cm2] 57.98 58.00 57.28 57.28
Molar Flow [MMSCFD] 16.29 10.00 9.691 16.60
Mass Flow [kg/h] 23677.135 11625.11 11030.96 24271.29
Std Ideal Liq Vol Flow
[m3/h] 23.35 31.60 30.68 24.26
Molar Enthalpy
[kJ/kgmole]
-303965.297 -85320.83 -83562.31 -3009.27
Molar Entropy
-235.9 -149.6 -152.7 -231.8
[kJ/kgmole-C]
Heat Flow [kJ/h] -246644.42 -42495.5 -40334.03 -2488.54
MDEAmine 0.1102 0.0000 0.0000 0.1081
H2O 0.8887 0.0000 0.0028 0.8705
CO2 0.0001 0.0110 0.0019 0.0056
H2S 0.0010 0.0207 0.0000 0.0134
Methane 0.0000 0.6931 0.7132 0.0011
Ethane 0.0000 0.1524 0.1566 0.0004
Propane 0.0000 0.0693 0.0713 0.0001
i-Butane 0.0000 0.0083 0.0085 0.0000
 F. Kartal and U. Özveren Bioresource Technology Reports 13 (2021) 100615

Initial and Final Composition of Natural Gas

0.8

0.7

0.6
Concentration

0.5

0.4

0.3

0.2

0.1

i- n-
MDEA H2O CO2 H2S Metha Ethane Propan i- n- Pentan Pentan
mine ne e Butane Butane e e

gas amargo 0 0 0.011 0.0207 0.6931 0.1524 0.0693 0.0083 0.025 0.0075 0.0127
gas dulce 0 0.0028 0.0019 0 0.7132 0.1566 0.0713 0.0085 0.0257 0.0074 0.0124

Fig. 2. Comparison of Sour Gas / Sweet Gas Compositions

4. Conclusions

compare the first results of Pressure, Flows and Temperature of the

The temperature of the regenerated amine stream and the CO2
Process with different ones to be able to observe their behavior and in the
concentration in that stream are sensitive to pressure changes. Faced with
final results we observe that the CO2 of 0.0019 increases its concentration
an increase in pressure, the concentration of CO2 decreases and in turn
to 0.0047, the results change notoriously with respect to to CO2 and so on,
the temperature increases proportionally.
you can continue to make comparisons and find the most optimal one to
be able to put it into practice.
The MDEA presents a stable behavior at high pressures and low
temperatures which allows to reduce its consumption and save on
A comparison was made with the research work of the University of Jujuy
operating costs.
and we observed that they obtain a 100% CO2 removal, but a DEA
regeneration of 31.94%, compared to our MDEA regeneration was 99.96%,
The results obtained in table 4.5 of chapter 4, allow us to determine the
that is The advantage of using MDEA can be reused after regeneration.
ranges with which they start and how they end, we observe that in the
In this way, it is possible to verify the alternative hypothesis, in which it is
tests we obtained a removal of 100% H2S and 17% CO2 with a
proposed that the steady state simulation of the natural gas sweetening
regeneration of MDEA of 99.96%. and in the end they meet the defined
process is possible using MDEA as an absorbent.
quality requirements, less than 4 ppm to be able to transport natural gas
without corrosion problems.
F. Kartal and U. Özveren Bioresource Technology Reports 13 (2021) 100615

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