Internat. J. of Sci. and Eng., Vol. 4(1):6-10, January 2013, Widayat et al.

ISSN: 2086-5023

Diethyl Ether Production Process with Various

Catalyst Type
Widayat 1 *, Achmad Roesyadi 2, Muhammad Rachimoellah 2
1
Dept. of Chemical Engineering
Diponegoro University, Jl. Prof. Sudharto, Kampus UNDIP Tembalang, Semarang 50239, Indonesia
2
Department of Chemical Engineering, Industrial Technlogy Faculty
Institute of Technology Sepuluh Nopember Surabaya Indonesia

e-mail: yayat_99@yahoo.com

Abstract - Several H-zeolite and HZSM-5 catalysts was preparated ethylene. The result showed that H-modernite with ratio of
and their characters have also been investigated. H-zeolit Catalyst SiO2/Al2O3 90 is more stable than H-modernite with
was preparated from Natural Zeolite that obtained from Malang SiO2/Al2O3 20[5]. Haber, et al [6] has a research about ethanol
District and Gunung Kidul District. Diethyl ether was produced by dehydration process with Kalium saline and silver from
Ethanol with concentration of 95%. This research use fixed bed
reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure
tungstophosphoric acid (HPW) by varying the type and the
and temperature 140oC as the operating condition. Ethanol vapor number of cation KxH3−xPW12O40 and AgxH3−xPW12O40. In his
from vaporization tank was driven by 200 ml/min Nitrogen stream. research, value of x was varied in the range of 0<x<2 for
The responds in this research is liquid product concentration; diethyl KxH3−xPW12O40 and 0<x<3 for AgxH3−xPW12O40. The result
ether, ethanol, methanol and water concentration. The results showed that the catalytic activity of the both process was
showed that the largest ethanol conversion was produced by the use improved. This result shows that catalytic activity has a
of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was relation to proton acid and proton that is produced by silver
produced by the use of alumina and H-zeolite catalyst. The larger cation. In a high temperature (T > 573K), the highest yield of
ratio between natural zeolite with HCl solvent will produce the larger acetaldehyde from dehydrogenation ethanol oxidation is
surface area of catalyst and ethanol conversion. The largest ethanol
conversion was produced at reactan ratio 1:20.
produced by using AgxH3−xPW12O40 catalyst [6]. Zaki[7],
studied about the effect of transition metal from Fe2O3 and
[Keywords: catalyst; ethanol conversion; dehydration process; yield Mn2O3 in catalytic ethanol dehydration process. The result
of diethyl ether; natural zeolite]. showed that there was an improvement in ethylene selectivity
[7]
.
I. INTRODUCTION Varisli et al [8], also studied diethyl ether and ethylene
Diethyl ether is one of the most important commercial production process with dehydration ethanol reaction on
ether. In industry, Diethyl ether is often used as a solvent of various catalysts. In this research, TPA
organic reactions such as oil, fat, latex, micro cellulose, (tungstophosphoricacid), STA (silicotungsticacid) and MPA
perfume, alkaloid solvent. This ether is also used as a separator (molydophosphoricacid) catalyst was used. The result showed
of organic compound from its natural material sources. In that the highest Selectivity of ethylene (>0.75) was produced
addition, diethyl ether is identical to anesthesia in medical at 250oC with TPA catalyst. At temperature 180oC, the main
science [1]. product was diethyl ether. Furthermore, the presence of water
Diethyl ether can be produced using homogenous vapor decreased the catalyst activity. Trends of Polyacid
catalyst (sulfuric acid/Barbet process) and heterogeneous catalyst activity can be arranged from the largest value as
catalyst. The difficulty of Catalyst separation becomes the STA>TPA>MPA [8].
weakness of Barbet process. Furthermore, the corrosive The recent research is objected to investigate the type of
behavior of Barbet process causes this process becomes costly. catalyst in ethanol dehydration process to produce diethyl
The second process, heterogeneous catalyst, uses alumina ether. The types of catalyst, which are used in this research, are
catalyst. In this process, ethanol conversion per pass and its alumina, HZSM-5, and H-zeolit. In addition, H-zeolite is
yield is 60-80 and 90% respectively [1]. Butt, et al [2] and de made of natural zeolite from Kabupaten Gunung Kidul district
Boer, et al [3], studied kinetic reaction of this process. and Malang district.
Evidently, the use of alumina catalyst in ethanol
dehydration process produces a low ethanol conversion and II. MATERIALS AND METHODS
diethyl ether yield. Therefore, researchers develop the type of Zeolite is synthesized from natural zeolite, whereas
catalyst that can be used for ethanol hydration and dehydration chloride acid is produced from Brataco. AgNO3 is used as
process such as Alumina, MgO, alumina silica and WO3 indicator of chloride ion washing. Materials to create HZSM-5
catalyst [4]. In addition, zeolite can also be used for this catalyst are aquadest, waterglass, alumonium sulphate,
process. Takahara, et al [5] used H-modernite type of zeolite for sulphate acid, natrium hydroxide and amonium chloride.
ethylene production. In this production process, ethanol was Materials for diethyl ether production process are tehnical
dehydrated to be diethyl ether and subsequently becomes ethanol (95%) and nitrogen gas. ZSM-5 catalys is produced

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Internat. J. of Sci. and Eng., Vol. 4(1):6-10, January 2013, Widayat et al. ISSN: 2086-5023

based on Latourette, et al method [11]. Solution A which (Temperature Conductivity Detector) with helium gas as gas
contains alumonium sulphate, sulphate acid and water is carrier with flow rate 20 ml/menit, temperature 125- 250oC
mixed with solution B which contains waterglass and aquadest. and detector temperature 275 oC. Components which are
Solution C contains NaOH 40% which is added to solution A analyzed are diethyl ether, ethanol, water and methanol.
and B. Afterwards, this solution is strirred to make a
homogenous solution at PH 9.5. After this step, the solution is III. RESULTS AND DISCUSSION
placed and stirred in an autoclave with a heating at Characteristics test is analyzed with X-ray Diffraction
temperature 150oC within 24 hours. The produced crystal is (XRD). Figure 2 shows the analysis result of the difractogram
washed, dried and calcinated. In order to get HZSM-5, the ion analysis for zeolite catalyst with raw material from Gunung
of the product is exchanged with amonium chloride and Kidul district (KZ A) and Malang District (KZ B). It can be
continued with the washing, drying and calcinating. observed that KZ A has more peak than KZ B at degree of
In this experiment, alumina catalyst/alumonium oxyde theta 20-30. With a domination of Si composition, Catalyst
from a merck which have specification of surface area in the tends to have a form as Silicate for KZ A and Modernite for
range of 190 m2/gram is used. As stated before, H-zeolite is KZ B. Intensity of KZ B catalyst is higher than KZ A catalyst.
produced from natural zeolite which is obtained from The diference of peak can also be observed at degree 2 theta 13
Wonosari district, Gunung Kidul district and Malang district. and 15, where the intensity of KZ A is higher thatn KZ B
Characteristic of zeolite is shown in a result of the research of catalyst.
Widayat, et al [12]. The catalyst is produced with chemical
treatment, washing, drying and calcination process. The
chemical treatment is processed in three-neck flask which is
equpped with cooler, water heater, and magnetic stirrer.
Washing is processed to remove the Cl- ion. Drying is 800

processed with an oven at temperature 110oC. Calcination is 700

processed with furnace which is equipped with temperatur 600

control. Catalyst product which is produced from natural 500
KZ A
zeolite of Gunung Kidul district is called KZ A, whereas the
Intensity

400
catalyst product from natural zeolite of Malang district is
called KZ B. In addition, H-zeolite catalyst is shyntesized by 300

variying the ration og the weight of zeolite and chloride acid 200
solvent. 100
KZ B
Catlytic test equipment is shown in figure 1. Fixed bed
0
reactor is placed in a furnace. Feed/ethanol vaporizer tank and
nitrogen gas is used as gas booster and inert. The condensorr is -100
0 10 20 30 40 50 60
used to cendense the is reaction producet. The dimension of o
2 theta
the fixed bed reactor is ½ inci of diameter and 1 gram of
catalyst weight. In order to create catalyst bed, the reactor is
eqipped with mesh buffer and glasswool on the both side Figure 2. Difractogram of H-Zeolite catalyst product

Cristality analysis result for variation of natural zeolite

weight and solvent volume ration is shown in figure 3. Figure
3 shows that the all catalyst product have similar peaks. Most
of each point in degree 2 theta have the similar peaks. This
result is produced for both calcination or pre-calcination
process. In addition, the peak height difference show the
difference of concentration.
XRD analysis result can be seen in figure 4. this figure
shows standart and systetic difractogram HZSM-5 pattern.
Figure 1. Ethanol dehydration process equipment The specific peak of HZSM-5 is observed at value of 2θ
between 7-90 and between 22-250 . Based on the comarison
Diethyl ether production is processed with 1 gram of KZ A, between difractogram pattern of synthetic and standart
KZ B, HZSM-5 and alumina catalyst at initial temperature analysis, it can be concluded that both of analysis give the
140oC, within 15 minutes. Ethanol vapor is boosted with same result. Therefore it can also be concluded that the
nittrogen gas flow with a flow rate 200 ml/min. During 15 product of synthesis is HZSM-5. XRD analysis result from
minutes, the product is condensed and analyzed with gas figure 3 have an amorphous form and show an intensity at 2θ
chromatography. between 22-250 .
The characteristics is analyzed in intrumentation The next zeolite catalyst character analysis to investigate
laboratory of Chemical Engineering Department FTI ITB. the surface area and total pores volume. Measurement of
Cristalit characteristic with X ray Difraction (XRD) is surface area and total pores volume using Quantachrome
analyzed in Research Center ITS. The product is analyzed in NOVA 1000 High Speed Gas Sorption Analyser dengan Po =
chemical analysis laboratory Politeknik Negeri Malang by gas 711,65 mmHg and nitrogen gas as adsorb gas/inert. Analysis
chromatography. The chromatography gas uses TCD detector result is hown in Table 1.
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Internat. J. of Sci. and Eng., Vol. 4(1):6-10, January 2013, Widayat et al. ISSN: 2086-5023

also shows the escalation of surface area and total pores

colume. The highest escalation id produced at ratio of Zeolite
and HCl of 1:20.
Test result of Production process shows that the produced
700
products contains methanol, water, diethyl ether and ethanol
600
residue. This is shown in figure 5 and 6. Figure 5 shows
500 chromatogram result for standart solution where water
component is detected at retention time 3.38 min, methanol
Intensity

400

r a tio H C l: Z A = 1 :2 0
300 (RT 5.89 min), ethanol (RT 7.18 menit) and diethyl ether (RT
200 9.86 menit).
r a tio H C l:Z A = 1 :1 5 b e fo r e c a lc in a tio n
100

0 r a io H C l:Z A = 1 :1 5 a fte r c a lc in a tio n

0 10 20 30 40 50

o
2 th e ta

Figure 3. XRD difractogram result of H-Zeolite catalyst: the

effect of reactant ratio

Figure 5. Chromatogram of standart solution

Chromatogram of dehydration process product is shown in

figure 6. Figure 6a is chromatogram of diethyl ether
production process result using alumina catalyst, whereas
figure 6.b is using KZ A catalyst, figure 6.c using KZ B
Figure 4. Analysis result of XRD HZSM-5 syntethic and catalyst and 6.d using HZSM-5 catalyst. Alumina and
HZSM-5 standart. H-zeolite catalyst (KZ A and KZ B) produces diethyl ether.
Alumina catalyst is often used in ethanol dehydration process
[2],[3]
Table 1. Analysis results of surface area and total pore volume . KZ A catalyst is silicalite, where its mainly component is
silica that can be used as catalyst in diethyl ether production
Specific surface Pore volume process. KZ B catalyst is zeolite with mordenite type that
Catalyst type contains silica and aluminum that can be used for ethanol
area ( m2/g ) (cc/g) x 103
dehydration process. HZSM-5 catalyst does not produce
KZ A 184,5240 108,243
diethyl ether, but produce a lot of water. From the reaction of
KZ B 130,2086 75,272
ethanol conversion reaction, it can be analyzed that ethylene
KZ A: 1/10 59,8937 35,511
might be produced when HZSM-5 catalyst is used. Therefore,
KZ A: 1/15 135,7537 81,191
production process with HZSM-5 catalyst does not produce
KZ A: 1/20 172,9295 101,763
diethyl ether but produce ethylene. This is caused by the
KZ A: 1/30 70,4280 40,678
addition of water concentration in analysis result of gas
HZSM-5 149,918 -
chromatography (figure 6.d).
Alumina 200 -
The next catalytic test of ethanol dehydration is data
processing to calculate ethanol conversion and diethyl ether
Table 1 shows that escalation of dealumination time have
yield. The used of equation is as follow.
no significant effect to the surface area and total pores volume.
In general, surface area of natural zeolite is around 20
m2/gram[12]. Dealumination and calcination make some
changes to the surface arean and total pores volume. (1)
Alumination causes escalation of Si/Al ration and aluminasi
menyebabkan peningkatan perbandingan Si/Al dan dissolving (2)
of impurity CaO. The escalation ration of n SiO2/Al2O3 causes
a changes of zeolite structure. This changes is caused by The result of calculation is shown in table 2. Table 2 shows
Hydrolisis reaction and calcination process. The highest that the largest ethanol conversion for natural zeolite from
specific surface area and largest total pores volume are Gunung Kidul district is produced by KZ A 10 catalyst,
produced at dealumination time of 10 hours. Surface area of whereas the largest ethanol conversion for natural zeolite from
KZ B is smaller that KZ A catalyst product. In addition, table 1 Malang district is produced by KZ B 15 catalyst.

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Internat. J. of Sci. and Eng., Vol. 4(1):6-10, January 2013, Widayat et al. ISSN: 2086-5023

therefore the possibility of reaction is larger than the use of the

other catalyst. In addition, Yield value of diethyl ether is
smaller than dehydration process with alumina catalyst. Yield
of KZ B is smaller than KZ A since the ration of Si/Al for KZ
B >KZ A and surface area of KZ B is smaller than KZ A. Yield
of diethyl ether for production process with HZSM-5 catalyst
is 0 since there is no diethyl ether produced in the product.
Table 2 shows that the natural zeolite weight and chloride
acid volume ratio affect to ethanol conversion. The higher
reactant value the higher ethanol conversion. However, the
conversion decrease after reactant ration of 1:20. The largest
ethanol conversion is produced with ratio of zeolite weight
and HCL volume is 1:20. This result follows the trend of
catalyst surface area, but does not follow the trend of Si/AL
a. alumina catalyst ratio. This phenomenon shows that surface area and Si/All
ratio has an effect to ethanol dehydration process. Therefore,
these two parameters need to be investigated into more detail.

Table 2. The result of ethanol conversion and DEE

Ethanol
Catalyst type Yield DEE (%)
conversion (%)
KZ A 10 4,68 1,78
KZ B 15 5,34 0,14
alumina 11,59 2,41
HZSM-5 56,44 0
b. KZ A KZ A: 1/10 15.27 2.98
b. KZ A
KZ A: 1/15 34.66 0.21
KZ A: 1/20 39.28 0.85
KZ A: 1/30 6.78 1.35

IV. CONCLUSIONS
Result of this research can be concluded as follows; XRD
analysis result of catalyst product showed that KZ A catalyst is
H-zeolite with silicalite type and KZ B is H-zeolite with
modernite type. The highest Specific surface area and total
pore volume is 184,52 m2/gram and 108,243 x 10-3 cc/gram
respectively at dealumination time 10 hours for KZ A catalyst.
Production proess result of diethyl ether showed that alumina
c. KZ B
catalyst, KZ A and KZ B, can be used to produce diethyl ether.
However, HZSM-5 could not be used to produce diethyl ether
and only increase the amount of water and might produce
ethylene. The largest yield of diethyl ether was produced
alumina, KZ A and KZ B in decreasing order. The largest
ethanol conversion of 56.44% was produced by using
HZSM-5 catalyst. The higher value of natural zeolite and
chloride acid solvent ratio the higher surface area and ethanol
conversion. The highest ethanol was produced at reantant
ration of 1:20.

ACKNOWLEDGMENTS
The author would like to convey the acknowledgement to
Dr. Suminar for the XRD analysis assistance, also sincere
d. HZSM-5 thank to Dr. Ir. Melia Laniwati as chief of instrumentation
Figure 6. Khromatograph of liquid product ethanol laboratory of ITB Bandung for the BET analysis assistance.
dehydration Special thank to Mr. Kalyawan from Polytechnic Malang for
the gas chromatography assistance. The writer also
This is because KZ A catalyst has the largest surface area, acknowledge to DP2M DIKTI as the sponsor of this research.

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Internat. J. of Sci. and Eng., Vol. 4(1):6-10, January 2013, Widayat et al. ISSN: 2086-5023

REFERENCES of Catalysis 207, 296–306

[1]. Ullmann, 1987, “Encyclopedia of Industrial Chemistry”, Vol. A.10, 5th [7]. Zaki, T., (2005), “Catalytic dehydration of ethanol using transition metal
edition, VCH Verlagsgesellschaft, Weinhem Federal Republic of oxide catalysts”, Journal of Colloid and Interface Science 284, p;
Germany. 606–613
[2]. Butt, J. B., H. Bliss, and C. A. Walker, 1962, “Rates of Reaction in a [8]. Varisli, D, T Dogu, and G Dogu, 2007, “Ethylene and diethyl-ether
Recycling System Dehydration of Etanol and Diethyl Ether Over production by dehydration reaction of ethanol over different
Alumina”, AIChE-J, 8, 42-47. heteropolyacid catalysts”, Chem Eng Sci
[3]. De Boer, JH, RB Fahim, BGLinsen, WJ Vissere and WFNM [9]. Kick-Othmer, (1965), “Encyclopedia of Chemical Technology”, Vol. 8, 3rd
deVlesschauwer, 1967, “Kinetics of the Dehydration of Alcohol on edition, John Wiley and Sons, Inc., United States of Amerika
Alumina”, Jounal of Catalysis, 7 pp163-17 [10]. Fessenden, Ralp J. dan Joan S. Fessenden, (1997), “Kimia Organik”, jilid
[4]. Smith, J.M. 1981. “ Chemical Engineering Kinetics”. McGraw-Hill 1 edisi ketiga, terjemahan oleh : Aloysius H. P, Penerbit Erlangga,
Book Co, Singapura Jakarta
[5]. Takahara I, M Saito, M Inaba, and K Murata, 2005, “Dehydration of [11]. Latourrette, B dan C., Magnier (1990), Preparation of Zeolite of type
ethanol into ethylene over solid acid catalysts”, Catalysis Letters, Vol ZSM-5, US Patent No. 4891199,
105, pp 249-252 [12]. Widayat, Mustafa, A Roesyadi and HM Rachimoellah, (2008),
[6]. Haber J., K. Pamin, L. Matachowski, B. Napruszewska, and J. Pol_towicz, “Pengaruh Konsentrasi HCl Dan Jenis Reaktan Dalam Pembuatan
2002, “Potassium and Silver Salts of Tungstophosphoric Acid as Katalis Zeolit Untuk Proses Dehidrasi Dari Zeolit Alam”, Prosiding
Catalysts in Dehydration of Etanol and Hydration of Ethylene”, Journal Seminar Nasional Rekayasa Kimia dan Proses 2008 Semarang,

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