DIETHYL ETHER

Background of the Study

Diethyl ether (C4H10O) or commonly called as ether or ethoxyethane is a flammable,

volatile, and colorless liquid with a sweet taste and characteristic odor (Sethuraman &

Dyer, 2016). It is an organic compound belonging to a functional group called ethers. Its

molecular structure consists of two ethyl groups linked through an oxygen atom (“Ethyl

Ether”, 2019). Moreover, according to New World Encyclopedia (2017), diethyl ether is

an isomer of butanol.

Diethyl ether is mostly used as a solvent in numerous processes including fragrance

and pharmaceutical chemical processes and as well as in explosives synthesis (Phung &

Busca, 2015). It is one of the most important commercial ether and often used as a solvent

in organic reactions such as oil, fat, latex, micro cellulose, and perfume. Diethyl ether is

also used to separate organic compounds from their natural sources, Moreover, it is

similar to anesthesia in medical science (Widayat, Roesyadi, & Rachimoella, 2013).In

addition, Diethyl ether is a valuable chemical and an attractive motor vehicle fuel alternate

(Kito-Borsa et al., 1998).

Bagasse is the residue remaining after all the sugar juice has been squeezed from

the sugarcane and washed with clean water for multiple times (Du et al., 2018). According

to Encyclopædia Britannica (2016), Bagasse also called as megass and It is burned as

fuel in the sugarcane mill or used a source of cellulose for the production of animal feeds.

Sugarcane bagasse starts a potential lignocellulosic substrate for the production of

bioethanol, since bagasse contains high sugar content, is renewable, and is inexpensive
and readily available (Amores, Ballesteros,I., Manzanares, Saez, Michelena, and

Ballesteros, M.,2013).

Diethyl ether is mostly produced through byproduct of ethanol synthesis through

ethylene hydration processes or by dehydration of bioethanol with sulfuric acid or in gas

phase over alumina catalysts thus producing a renewable chemical (Phung & Busca,

2015). According to New World Encyclopedia (2017), preparation of diethyl ether in

laboratories is very seldom since it is hazardous and nowadays it is easy to authenticate

laboratories.

Objectives

The main objective of the study is to produce a well-designed plant producing diethyl

ether to be set up in the Philippines. Moreover, the researchers also aim to select the

most efficient process for the production of diethyl ether considering its marketability,

sustainability, health & safety, environmental aspect, and economic performance, to

design the process flow diagram, heat & material balance, and piping and instrumentation

diagram of the plant, and to execute market analysis of diethyl ether.

History

According to New World Encyclopedia (2017), Diethyl ether was discovered by the

alchemist Raymundus Lullus in 1275 C.E. Valerius Cordus first synthesized it in 1540 and

called it “oil of sweet vitriol” (oleum dulcis vitrioli). Diethyl ether was discovered by

distillation of mixture of ethanol and sulfuric acid and since sulfuric acid is known as “oil

of vitriol”, diethyl ether was called “oil of sweet vitriol”. Furthermore, Theophrastus
Bombastus von Hohenheim known as Paracelus discovered the analgesics properties of

ether at about the same diethyl ether was synthesized.

In 1846, ether was used as an anesthetic which then marked the start of a modern

age in anesthesiology. Despite of its abandoned used in the developed world, ether was

safely and effectively used as an inhalation anesthetic for over one hundred years

(Change, Goldstein, Agarwal, & Swan, 2015).

A Boston dentist named William T.G. Morton, exhibited the first true demonstration of

ether as an inhalation anesthetic on October 16. 1846. As Morton searched for relief for

the painful dental procedures, he discovered the anesthetic properties of ether. Prior to

1846, Patients often avoid surgical intervention since anesthesia was not yet used during

surgical procedures.

MANUFACTURE

Some of the various methods in the production of diethyl ether are the following:

i. Ethylene and diethyl-ether production by dehydration reaction of ethanol

over different heteropolyacid catalysts

In this study by Varisli, Dogu, T., Dogu, G., (2007), Ethylene and diethyl ether

was produced by dehydration reaction of ethanol over different heteropolyacid

catalysts. There are three different heteropolyacid catalysts used namely

silicotungstic acid (STA), molybdophosphoric acid (MPA), and TPA. Effects of

temperature and water content of ethanol on product selectivity and ethanol

conversion was also studied.

 The reactor used was a differential tubular flow reactor placed in a tubular

furnace. Fresh catalyst was added before the start of each experiment in the

middle of the stainless-steel tubular reactor of ¼ inch in diameter and supported

by quartz wool from both ends. Into the evaporator, Liquid ethanol of known

composition was pumped and mixed with the helium gas to adjust the reactor feed

composition. Flowrate of the vapor stream was kept constant. The composition of

the reactor effluent stream was analyzed using a gas chromatography and a

Poropak T column was used to analyze the product stream.

Varisli, Dogu, T., Dogu, G., (2007) concluded that an increase in reaction

temperature caused a significant increase in yield of ethylene while a decrease in

temperature the main product is diethyl ether. In using the TPA catalyst, there is a

decrease in ethanol conversion with an increase in feed mole fraction of ethanol.

Among the three HPA catalysts used (STA, TPA, and MPA), STA showed the

highest activity in ethanol dehydration. This was supported by higher number of

protons and higher stability of STA and TPA at temperatures over 200˚C.

ii. Diethyl ether production during catalytic dehydration of ethanol over Ru-

and Pt- modified H-beta zeolite catalysts

In this study by Kamsuwan, Praserthdam, & Jongsomijit (2017), the

ethanol dehydration was studied in a fixed-bed flow microreactor to measure

the ethanol conversion and diethyl ether yield. This study also aimed to

investigate the characteristics as well as the catalytic properties of HBZ with

Ru and Pt to increase the yield of diethyl ether at low temperature.

 The process of catalytic dehydration of ethanol was done in a fixed-bed

continuous flow microreactor which is made from a borosilicate glass. 0.01

g of packed quartz wool and 0.05 g of catalyst were placed in the reactor.

The catalyst was then preheated in argon at 200˚C for about one hour under

atmospheric pressure to remove any moisture present on the surface of the

catalyst. Liquid ethanol was vaporized in a flowing argon. The dehydration

process of ethanol was done at temperature of about 200 to 400 ˚C. The

products were analyzed using a gas chromatograph with flame ionization

detector (FID) using capillary column (DB-5). In the gas chromatograph,

nitrogen was used as a carrier gas.

The ethanol conversion of all the catalyst at different temperatures were

given at figure 1. It was observed that all the conversion of the catalysts

increased with increasing reaction temperature and at 400 ˚C, they all

exhibited the highest ethanol conversion. At temperature between 250 and

300 ˚C, Ru- and Pt- modified HBZ catalysts enhanced the conversion of

ethanol. However, at higher temperature the effect of these catalysts is less

distinct.

At figure 2, it shows the product selectivity for all the catalysts. For

diethyl ether, its selectivity decreases with increased temperature. At

250˚C, Ru modification increased slightly the selectivity of the diethyl ether.

Even if all the catalysts exhibit the highest diethyl ether selectivity at 200 ˚C,

ethanol conversion at this temperature is lowest and thus it is still necessary

to consider the diethyl ether yield for each temperature.

Diethyl ether yield for all the catalyst is shown in figure 3. The highest yield

is at 250˚C for all the catalysts. Therefore, this is the most suitable

temperature for the production of diethyl ether. At this temperature, both Ru

and PT modifications can increase the yield of diethyl ether.

Figure 1. Ethanol conversion of all catalysts at different temperatures. Reprinted from

“Diethyl ether production during catalytic dehydration of ethanol over Ru- and Pt- modified

H-beta zeolite catalysts” by Kamsuwan, T., Praserthdam,P.,&Jongsimijit, B.,(2017).

 Figure 2. %Selectivity of products. Reprinted from “Diethyl ether production during catalytic

dehydration of ethanol over Ru- and Pt- modified H-beta zeolite catalysts” by Kamsuwan,

T., Praserthdam,P.,&Jongsimijit, B.,(2017).

Figure 3. Diethyl ether yield for all catalysts at different temperatures. Reprinted from

“Diethyl ether production during catalytic dehydration of ethanol over Ru- and Pt- modified

H-beta zeolite catalysts” by Kamsuwan, T., Praserthdam,P.,&Jongsimijit, B.,(2017).

Kamsuwan, Praserthdam, & Jongsomijit (2017) concluded that modification

of HBZ with Ru and Pt is promising to enhance the yield of the product at

low temperature. To increase the diethyl ether yield, the ethanol dehydration

must be carried out at low temperature in order to maintain high selectivity

of diethyl ether. Thus, in this study Ru and Pt are found to be essential to

increase the yield of diethyl ether.

iii. Diethyl Ether Production as a Substitute for Gasoline

 Diethyl ether is produced by dehydration reaction of ethanol with fixed

bed reactor using nanocrystalline ɣ-Al2O3 catalyst in this study by Alviany,

Wahyudi, Gunardi, Roesyadi, Kurniawansyah, & Prajitno (2018). The

procedures performed were ɣ-Al2O3 catalyst synthesis through precipitation

method, ɣ-Al2O3 characterization, and production of diethyl ether.

The production process of diethyl ether was done through adsorption

process using an adsorption column and then through dehydration of

ethanol in a reactor. A fixed-bed microreactor was used as the reactor in

dehydration of ethanol with an inside diameter of 0.5 in. and length of 30

cm. 10 grams of molecular sieve was placed into the adsorption column

and 3 grams of catalyst into the reactor. Liquid ethanol was vaporized in a

flowing nitrogen at a flow rate of 200 ml/min. The process was done in

various temperatures (125,150, 175, 200, 225°C). The products of the

condenser were analyzed using a gas chromatography. The set up used for
the production of diethyl ether is shown in figure 5 below.

Figure 5. Diethyl ether production equipment. Reprinted from “Diethyl Ether Production as

a Substitute for Gasoline” by Alviany, Wahyudi, Gunardi, Roesyadi, Kurniawansyah, &

Prajitno (2018).

Alviany, Wahyudi, Gunardi, Roesyadi, Kurniawansyah, & Prajitno (2018)

concluded that based on this study, the catalyst prepared through

precipitation method showed a higher ethanol conversion and diethyl ether

yield than ɣ-Al2O3 catalyst.

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