See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/272092680

Process Simulation of Ethyl tert-Butyl Ether (ETBE) Production from Naphtha

Cracking Wastes

Conference Paper · December 2013

DOI: 10.13140/2.1.4830.2884

CITATIONS READS

0 1,001

3 authors, including:

Nikhil Palherkar Utkarsh Maheshwari

Marwadi Education Foundation’s Group of Institutions D. Y. Patil Institute of Engineering, Management & Research, Akurdi, Pune
1 PUBLICATION   0 CITATIONS    76 PUBLICATIONS   143 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Residue Upgradation View project

Wasterwater Treatment View project

All content following this page was uploaded by Utkarsh Maheshwari on 11 February 2015.

The user has requested enhancement of the downloaded file.

 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

Process Simulation of Ethyl tert-Butyl Ether (ETBE) Production from Naphtha

Cracking Wastes

Sumeet Ghosalkar1, Nikhil Palherkar1, UtkarshMaheshwar2

1
Post Graduate Student, Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani,
Rajasthan-333031, India.
2
Post Graduate Student, Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani,
Rajasthan-333031, India.
[email protected], [email protected] , [email protected] .
_________________________________________________________________________

Abstract

ETBE is being used worldwide as an Octane Enhancer. Although it is superior to MTBE as an oxygenate, but its
Production vis-a-vis MTBE is costly. The objective of this work was to simulate the ETBE production on ASPEN,
and use the simulation results to develop analternative, high yield platform for ETBE production from Naphtha
Cracking Wastes. ETBE is produced from Isobutylene which is one of the wastes in naphtha cracking process. The
content of isobutylene in the waste is less than 30% weight. The major part of this work was to propose a processto
increase the product value by converting a greater fraction of the wastes into ETBE. The proposed process increased
ETBE production yield by 100% from conventional process with the purity of 97.3% by weight. Theresults obtained
in the simulation provide an excellent opportunity for it to be implemented on an industrial scale.

Keywords—ETBE, Process Simulation, Naphtha Cracking, Aspen Plus, Isobutylene.

1. Introduction : Table 1.Component and Composition of Products

from Naphtha Cracking Wastes
Naphtha cracking is one of the major processes in a Components Weight %
petrochemical processing industry in which naphtha (Based on 100kg
is cracked into shorter chain hydrocarbons. The Ethylene)
major product is ethylene, which had the world Ethylene 100.0
production of 109 million tons in year 2006. The Proplylene 0.3
ethylene production yield is roughly a half and the n-butane 5.20
rest is byproducts. The key byproducts are i-butane 1.30
isobutylene, 1-butene, and 1,3-butadiene as shown 1-butene 16.0
in Table I. This work was aimed to design a process
Cis-2-butene 5.30
to save the environment and to increase the
Trans-2-butene 6.60
production value by upgrading most of the key
Isobutylene 27.40
byproducts into one higher valued product. The
industry can adopt this work to develop the ETBE 1,3-butadiene 37.00
production from naphtha cracking wastes [1]. Methyl Acetylene 1ppm
Vinyl Acetylene 0.30
Ethyl Acetylene 0.10
n-pentane 0.50

1
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

ETBE is one of the most promising products thatcan from biomass fermentation. ETBE is a competitive
be produced from isobutylene. Other byproducts, 1- additive with MTBE (methyl tert-butyl ether) which
butene and 1,3- butadiene, can be converted to is a former popular anti-knocking additive. Even
isobutylene to produce ETBE as well. ETBE is an though the production of MTBE is cheaper, ETBE
anti-knocking additive to petro-oils and the ispreferable as it is higher in octane rating butlower
production of ETBE is environmental friendly [1]. inRVP, oxygen content and water solubility [1].
ETBE is fast degradable in water and soil. ETBE is
also produced from ethanol which can be produced

Figure 1: Schematic diagram for ETBE production from Naphtha cracking waste

the purification of the product and feed for each

reaction unit.
2. Materials and Methods
2.1.Reaction Process
The overall process is illustrated in Fig. 1. Ethylene, Various reaction routes were searched. One possible
adesirable product, was separated from by-products route was conversion of 1,3-butadiene to 1-butene,
by distillation tower T-101. Then, by-products were then conversion of 1-butene toisobutylene and
separated inorder to produce ETBE.1,3-butadiene finally,conversion of isobutylene to ETBE.The series
was first separated from other by-productsusing of reaction can be described as (1)-(3) :
extractive distillation tower T-201 before conversion
to 1-butene in R-301. Solvent for 1,3-butadiene C4H6 + H2 1-C 4H8
extraction was recovered in tower T-401. The rest of 1,3-butadiene Hydrogen 1-butene
the mixture was mostly 1-butene and isobutylene and (1)
there was no efficient method to separate these two
components. 1-Butene and isobutylene were fed into 1-C4H8 i-C4H8
reactor R-501 for converting isobutylene to ETBE
before converting isobutylene in reactor R-601. 1-butene Isobutylene (2)
Isobutylene produced from R-601 was recycled to R-
501. [1]
i-C4H 8 + C2H5OH (CH3)3COC2H5
The main processes were reaction and separation. In Isobutylene Ethanol ETBE
the reaction processes, the major byproducts – (3)
isobutylene, 1-butene and 1,3-butadine had to be
mostly converted to achieve maximum ETBE
production. The separation processes involves with

2
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

2.2 Conversion of 1,3-butadiene to1-butene: 3.1. Ethylene Separation (T-101)

Variouskind of catalysts that can be used Ethylene separation was carried out by using normal
forconversion of 1,3-butadiene to1-butene . The distillation as it had very different boiling point from
hydrogenation of 1,3butadiene could result in various other components. T-101 was optimized so that
C4 products. Pt and Pd based catalysts could be used ethylene recovery and purity were over 99% while
hydrogenate 1,3butadiene. Pt-based catalyst produced the energy consumption was the least by changing
mixture of butane isomers and butanes while Pd- the reflux ratio, number of stage, feed stage, and feed
based catalyst produced higher selectivity towards temperature. The design equations were based on
butenes and had good activity, stability and Fenske-Underwood-Gilland equation. The optimal
selectivity to 1-butane [8]. design column had 22 stages, feed stage of 10,
condenser pressure and temperature of 28.6 bar and -
2.3. Conversion of 1-butene to isobutylene 15.3oC, reboiler pressure and temperature of 29.3 bar
1-butane can be converted to isobutylene through and 124.1 oC, reflux ratio of 2.95and distillate to feed
isomerisation reaction.Alumino-silicate was one of ratio of 0.5 [6].
the catalyst that can be used. It was assumed that the
polymerization of isobutylene was negligible. The 3.2. Butadiene Extraction (T-201) and Solvent
rate of reaction can be expressed as shown in Recovery (T-401)
kmol/s.kg cat. 1,3-butadiene could be separated through extractive
distillation using DMF as a solvent. The extractive
distillation column in this study used the column of
೎ೌ೗
ఴబబల
೘೚೗
.಼ ‫݌‬ா 78 stages, reflux ratio of 1.4 kg/kg, and solvent to
‫ݎ‬௕ = 6.10 ݁ି ೃ೅ ቀ‫݌‬ସ − ቁ݊ feed ratio of 7.5 kg/kg at ambient pressure [9]. In this
‫ܭ‬
work, the optimization parameters were solvent to
2018.76 feed ratio, distillate to feed ratio, and the reflux ratio
݈݊‫ = ܭ‬−1.4507 + in order to reduce the amount of solvent usage.
ܶ

2.4. Conversion of isobutylene to ETBE As shown in Fig. 2, the recovery of 1,3-butadiene

was maximum at the ratio of 4 kg solvent (DMF)/kg
The kinetics studies of ETBE production from feed. This could come from the fact that the larger
isobutylene and ethanol have been studied through amount of DMF that came out of the distillate stream
several publications. The chosen catalystswere
of T-201 was significant enough to bring larger
Lewatit K2631 and Amberlyst-15.Ethylene and amount of 1,3-butadiene with. However, the weight
ETBE could be separated easily because their boiling fraction of 1,3-butadiene in the extract compared to
points are very different.
key C4 components reached over 99% at 5 kg solvent
(DMF)/kg feed. In conclusion, column T-201 had 78
3. Results and Discussion stages, DMF feed stage of 1, feed stage of 55,
condenser pressure and temperature of 1 bar and -
Aspen Plus was used to simulate and to design the
process. The thermodynamic model was NRTL. All 8.3 oC,reboiler pressure and temperature of 1.7 bar
distillation towers were RADFRAC model. The and 45.5oC,reflux ratio of 2.5, and distillate to feed
ratio of 0.34. After the extraction, DMF was
results and discussions were carried on in two
sectionsunit operations and overall process as extracted through a normal distillation column (T-
illustrated in Fig. 1. The basis of the work had feed 401) due to its different boiling point from others.
mass of 206,000 kg/hr with 50% ethylene and 50% The optimized design column had 22 stages, feed
byproducts. Byproduct compositions are shown in stage of 7,condenser pressure and temperature of 6.4
Table 1. bar and 42.6oC, reboiler pressure and temperature of
7.1 bar and 241.2oC, and reflux ratio of 1 [1].

3
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

Figure 2: Weight fraction of 1,3-butadiene for 1,3- Figure 3: Molar ratio of outlet 1-butene and 1,3
butadiene recovery in T-201 and for 1,3-butadiene in butadiene per inlet 1,3- butadiene versus molarratio
bottom stream of T-201 compared to key byproducts of feed hydrogen to feed 1,3-butadiene to reactor R-
301
3.3. Conversion of 1,3-butadiene (R-301)
1,3-butadiene conversion process was established in 3.4. ETBE Production (R-501) and ETBE
order to produce 1-butene to produce isobutylene for purification (T -501)
ETBE production.1,3-butadiene was converted to 1- This unit consisted of a packed-bed reactor (R-501)
and a distillation column (T-501) for purification.
butene through hydrogenation process. To achieve
Isobutylene, 1- butene and ethanol were feed into R-
low concentrations of 1-butene and hydrogen, a 501 reactor. There was noefficient way to separate
packed bed reactor was simulated with partial feed to isobutylene and 1-butene. As the conversion of 1-
enter small amount of feed along the reactor in Fig.1. butene to isobutylene was reversible, the presence of
The feed fraction to each point was equal forboth C4 isobutylene was counter-productive for 1-butene
feed and hydrogen. The reactor temperature range conversion [10]. Therefore, 1-butene was converted
was from 200-280 oC. The acceptable feed into isobutylene after the ETBE production
stage.Aspen Plus simulations were performed to
temperature was 250oC because the utility was not
determine the most desirable catalysts and operating
too high while the conversion reached 100%. Fig. 3 conditions. Purification of ETBE was simulated in
shows the effects of ratio of hydrogen feed to C4 feed distillation tower T-501.The separation was quite
on the ratio of outlet 1-butene and 1,3-butadiene to simple as ETBE, ethanol and other C4 components
the inlet 1,3-butadiene at 250oC.Fig.3 shows that at have very different boiling points [1].The purity of
hydrogen feed ratio of 1.03, 1-butene ratio was ETBE was 97.3 % weight for the product stream.
maximum and 1,3-butadiene ratio was almost Column T-501 had the configuration of number stage
of 18,feed stage 13, condenser pressure and
zero[4]. When 1,3- butadiene was completely temperature of 6.7bar and 57.1 oC, Reboiler pressure
consumed at hydrogen feed ratio of 1.06, 1-butene and temperature of 7.4 bar,139.1oC and reflux ratio of
started to drop and dropped drastically at hydrogen 1.5.
feed ratio of 1.1.
4. Conclusion

Process design of ETBE production from naphtha

cracking wastes was simulated using Aspen Plus. The
proposed process converted 1-butene and 1,3-
butadiene to isobutylene which is the feedstock for
ETBE production. The simulated conversion for the

4
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

proposed process was 2 mole of ETBE / mole of

isobutylene which was twice higher than the
conventional process. This process was promising for
the industry to develop further as it coulddouble the
conversion of wastes to product to save
theenvironment and to increase the profitability of
naphthacracking process.

References

[1] P. Traiprasertpong, A. S. Ariyaskul, Process Simulation of

Ethyl tert-Butyl Ether (ETBE) Production from Naphtha
Cracking Wastes. World Academy of Science, Engineering
and Technology, 64, 2012.
[2] F. Vigné, J. Haubrich, D. Loffreda, P. Sautet, F. Delbecq,
Highly Selective Hydrogenation of Butadiene on Pt/Sn Alloy
Elucidated by First-Principles Calculations, Journal of
Catalysis, 275, 2010, 129-139.
[3] A. Schmidt, S. Reinhard, Kinetics of 1,5-Cyclooctadiene
Hydrogenation on Pd/α-Al2O3, Industrial &Engineering
Chemistry Research, 46, 2007, 1677-1681.
[4] H. Zhao, E. K. Bruce, Hydrogenation of 1,3-Butadiene
onTwo Ordered Sn/Pt(111) Surface Alloys, Journal of
Catalysis, 234, 2005, 24-32.
[5] D. C. Lee, H. K. Jae, J. K. Woo, H. K. Jung, H. M. Sang,
Selective Hydrogenation of 1,3-Butadiene on TiO2-Modified
Pd/SiO2 Catalysts, Applied Catalysis A: General, 244, 2003,
83-91.
[6] Z. Lei, Z. Rongqi, D. Zhanting, Process Improvement on
Separating C4 by Extractive Distillation, Chemical
Engineering Journal, 85, 2002, 379-386.
[7] D. Seth, A. Sarkar, T. T. N. Flora, L. R. Garry, Selective
Hydrogenation of 1,3-Butadiene in Mixture with Isobutene
on a Pd/α-Alumina Catalyst in a Semi-Batch Reactor,
ChemicalEngineering Science, 62, 2007, 4544-4557.
[8] I. M. Smirnova, V. ShFel’Dblyum, T. A. Tsailingol’d,
Reaction Kinetics of Isomerization of N-Butenes to
Isobutylene, Petroleum Chemistry U.S.S.R., 21, 1981, 7-13.
[9] X. Yang, X. Yin, O. Pingkai, Simulation of 1,3-Butadiene
Production Process by Dimethylfomamide Extractive
Distillation, Chinese Journal of Chemical Engineering, 17,
2009, 27-35.
[10] D. Menezes, E. Weber, R. Cataluna, Optimization of the Etbe
(Ethyl Tert-Butyl Ether) Production Process, Fuel Processing
Technology, 89, 2008, 1148-1152.

View publication stats