Applied Catalysis A: General 277 (2004) 167–171

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Synthesis of diethylene glycol ethyl ether with diethylene glycol

and ethanol by the catalysis of heteropoly acid
Jun Feng Liu*, Yuan Liu, Ping Gui Yi
Department of Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan Province, Hunan 411201, PR China
Received 6 December 2003; received in revised form 27 August 2004; accepted 8 September 2004
Available online 14 Ocotober 2004

Abstract

A Keggin-type heteropoly acid revealed high catalytic activities for the etherification of diethylene glycol with ethanol to synthesize
diethylene glycol ether in the homogeneous phase. The catalytic activities of heteropoly acid were higher than those of conventional acid
catalyst such as sulfuric acid and phosphorous acid at the same catalyst concentrations or the same proton concentrations. When a heteropoly
acid is used as the catalysts the conversion of the etherification of diethylene glycol with ethanol is 92% and the selectivity for diethylene
glycol ethyl ether is 73.5% under the following conditions: the ratio of diethylene glycol to ethanol is 2:1 (mol), temperature is 180–200 8C,
pressure is 5.0 MPa, the concentration of 12-tungstophosphoric acid is 1.5–2.0% (wt), and the reaction time is 2.5 h.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Heteropoly acid; Catalyst; Diethylene glycol ethyl ether; Synthesis

1. Introduction [10,11]. HPA exhibited greater catalytic efficiency than the

Heteropoly acids (hereafter abbreviated as HPA) pos-
sesses the dual catalytic function of strong acidity and
oxidizing ability. Onoue et al. [1] have reported that HPA
catalyzed olefin hydration in a dilute aqueous solution much
more efficiently than the ordinary acid such as sulfuric acid
and phosphoric acid, and this knowledge led to the
development of a new commercial process for the direct
hydration of propene. HPA will be expected as an alternative
acid catalyst to improve several organic processes which
employ conventional acids [2–4].
The authors have recently reported homogeneous acid
catalysis of HPA [5,6]. In the homogeneous etherification of
alcohol [7,8], HPA revealed a catalytic activity higher than
p-toluene sulfonic acid, sulfuric acid or phosphoric acid
under identical proton concentration and ionic strength. It
was suggested that the dissociated heteropoly anions in the
aqueous phase might play a key role in accelerating the
reaction [9]. The rates of dehydration and etherification are
directly proportional to the total acidity of heteropoly acid
* Corresponding author. Tel.: +86 732 8290568; fax: +86 732 8290568.
E-mail address: liujunf@xtpu.org.cn, liujunf168@163.com (J.F. Liu).
conventional acids for non-aqueous homogeneous reactions
such as alcoholysis of epoxides [12], in which HPA worked
presumably in the non-dissociated form. Such efficient acid
catalysis of HPA in the non-aqueous phase also may be due
to certain specific properties of the heteropoly anion.
This paper aims to discuss the synthesis of diethylene
glycol ethyl ether from the dehydration between diethylene
glycol and ethanol with catalysis of heteropoly acid. Also,
the technology of the reaction has been discussed, and the
homogenous acid catalysis of HPA in connection with the
properties of heteropoly acid has been studied through some
etherifications in which the difference in acid catalysis
between HPA and other acids can be clearly reflected.
2. Experimental
2.1. Materials
All organic reagents used were highest purity commercial
products (>99%). 12-Tungstophosphoric acid (H3PW12O40

25H2O), 12-tungstosilicic acid (H4SiWo12O40
26H2O), 12-

0926-860X/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.09.008
168 J.F. Liu et al. / Applied Catalysis A: General 277 (2004) 167–171

Table 1
The material balance of the reactant with the catalysis of 12-tungstophosphoric acid at different temperatures (reaction time 3.5 h)
T (8C) DG (put in) DG (after reaction) DGEE Dioxane DMD TEG Conversion SDGEE SDioxane
(mol) (mol) (mol) (mol) (mol) (mol) (%) (%) (%)
140 2.0 1.16 0.62 0.20 0.02 0 42.0 74.0 24.0
160 2.0 0.70 0.95 0.32 0.02 0 65.0 73.0 24.5
180 2.0 0.20 1.31 0.45 0.03 0 90.0 72.5 25.0
200 2.0 0.16 1.32 0.48 0.03 0 92.0 72.0 26.0
220 2.0 0.12 1.20 0.56 0.12 0.06 94.0 64.0 30.0
DG: diethylene glycol; DGEE: diethylene glycol ethyl ether; DMD: 1.3-dimethyl dioxolane; TEG: tetraethylene-glycol; SDGEE: selectivity of diethylene glycol
ethyl ether; SDioxane: selectivity of dioxane.

molybdophosphoric acid (H3PMo12O40
28H2O), 12-molyb- 3. Results and discussion

dosilicic acid (H4SiMo12O40
12H2O), sulfuric acid (98%) and
phosphorous acid (85%) were of commercially available
purity. The amount of structural water of HPAwas determined
by thermogravimetric analysis.
2.1.1. Reaction procedure
The etherification of diethylene glycol with ethanol
proceeds in a 400 mL autoclave, with electromagnetic stirring
and electric furnace heating through a temperature controller.
Also, there is a sampling tube connected to the autoclave. The
autoclave and sampling tube are made of stainless steel.
Reaction method: diethylene glycol, ethanol and catalyst
are placed into autoclave, at first, put in nitrogen to 1.7 MPa,
than raise the temperature up to 200 8C, the pressure will go up
to 5.0 MPa. The reaction occurs under stirring after 2.0–2.5 h.
2.2. Product separation
The products were separated by distillation.
2.3. Product analysis
The composition and the content of the product were
determined with the internal standard of a thermal
conductivity detector of 1102G-type gas chromatograph
made in Shanghai Analysis Instrument Factory. The
chemical structure of the products was determined with a
GC–MS instrument made in Japan.
2.4. Account for result
The definitions of conversion and selectivity are given
below:
reacted amount of diethylene glycol
conversion ð%Þ ¼
putted amount of diethylene glycol
selectivity of diethylenegly colethylether ð%Þ
diethylene glycol ethyl ether ðmolÞ
¼ sulfuric acid catalyst rapidly decreased with reaction time
reacted amount of diethylene glycol ðmolÞ
(Note: the amount of diethylene glycol ethyl ether includes
mon- and di-ethylene glycol ethyl ether but does not include
diethyl ether in the selectivity.)
Hydrated HPA, which usually contain 11–28 water
molecules per Keggin unit at ambient temperature, are
moderately soluble in polar organic solvents such as alcohol,
ether, ketone, carboxylic acid and ester, whereas anhydrous
HPA is scarcely soluble therein. It is therefore to use
hydrated HPA for examining their homogenous acid
catalysis in organic media.
3.1. The material balance of the reactant
The material balance of the reactant has been given as in
Tables 1–3.
3.2. Technology of etherification of the diethylene glycol
with ethanol
3.2.1. Catalysis of different catalysts on the reaction
The reaction was performed in the homogenous liquid
phase. The acid catalysts employed were the Kiggin-type
heteropoly-tungstic and molybdic acids, sulfuric acid and
phosphorous acid were also contained. All of the HPA used
maintained their Keggin structures in the course of the
reactions, this was conformed in each case by examining IR
spectra.
As shown in Table 4, the results from the etherification of
diethylene glycol with ethanol indicate that HPA catalysts
are far more efficient than sulfuric acid and phosphorous
acid.
Regardless of the used catalysts, the etherification of
diethylene glycol with ethanol at 200 8C gave the normal
dehydrating diethylene glycol ethyl ether. It should be
noted that the catalytic activities of sulfuric acid and
phosphorous acid are low (Fig. 1) even though the acid
concentration was 103 times higher than that employed for
HPA. The low valves are probably due to an acidity loss
resulting from the formation of the sulfuric and phosp-
horous ester of alcohol. Indeed, as shown in Fig. 2, the
electrical conductivity of a reaction medium containing
owing to the decrease of the acidity; in contrast, no change
was observed with tungstophosphorous acid catalyst. The
decrease in the catalytic activities of sulfuric acid and
phosphorous acid might closely relate to the decrease in
 J.F. Liu et al. / Applied Catalysis A: General 277 (2004) 167–171 169

Table 2
The material balance of the reactant with the catalysis of 12-tungstophosphoric acid in different reaction times (temperature 200 8C)
t (h) DG (put in) DG (after reaction) DGEE Dioxane DMD TEG Conversion SDGEE SDioxane
(mol) (mol) (mol) (mol) mol mol (%) (%) (%)
1.0 2.0 0.90 0.80 0.28 0.02 0 55.0 73.0 25.5
1.5 2.0 0.72 0.95 0.31 0.02 0 64.0 74.0 24.5
2.0 2.0 0.50 1.13 0.34 0.03 0 75.0 75.0 25.0
2.5 2.0 0.20 1.31 0.46 0.03 0 90.0 73.0 25.6
3.0 2.0 0.16 1.35 0.46 0.03 0 92.0 73.5 25.0
3.5 2.0 0.14 1.37 0.47 0.02 0 93.0 73.5 25.0
DG: diethylene glycol; DGEE: diethylene glycol ethyl ether; DMD: 1.3-dimethyl dioxolane; TEG: tetraethylene-glycol; SDGEE: selectivity of diethylene glycol
ethyl ether; SDioxane: selectivity of dioxane.

Table 3
The material balance of the reactant with the catalysis of 12-tungstophosphoric acid at different catalyst concentrations (temperature 200 8C)
Concentration DG (put in) DG (after reaction) DGEE Dioxane DMD TEG Conversion SDGEE SDioxane
(%) (mol) (mol) (mol) (mol) (mol) (mol) (%) (%) (%)
0.2 2.0 1.30 0.53 0.16 0.01 0 35.0 76.0 23.0
0.5 2.0 0.80 0.88 0.29 0.03 0 60.0 73.5 24.0
1.0 2.0 0.25 1.28 0.44 0.03 0 87.5 73.0 25.0
1.5 2.0 0.12 1.34 0.50 0.04 0 94.0 71.5 26.5
2.0 2.0 0.08 1.34 0.54 0.04 0 96.0 70.0 28.0
2.5 2.0 0.07 1.33 0.55 0.05 0 96.5 69.0 28.5
DG: diethylene glycol; DGEE: diethylene glycol ethyl ether; DMD: 1.3-dimethyl dioxolane; TEG: tetraethylene-glycol; SDGEE: selectivity of diethylene glycol
ethyl ether; SDioxane: selectivity of dioxane.

electrical conductivity. On the other hand, HPA does not
form its ester with an alcohol, and consequently it can easily
effect the etherification. Diethylene glycol with ethanol
readily underwent etherification at 200 8C in the presence of
HPA (Table 4). The normal etherificating diethylene glycol
ethyl ether was predominantly obtained. 12-Molybdopho-
sphoric acid was less effective in the etherification. As
illustrated in Fig. 1, 12-molybdosilicic acid was indeed more
active than sulfuric acid and phosphorous acid at an early
stage of the reaction, but its activity gradually decreased
after the turnover number (mol of converted alcohol per mol
of catalyst) exceeded 50, and at the same time a blue
insoluble solid which then changed into black was deposited
in the reaction medium. Although this precipitate has not yet
been identified, it seems to be an HPA that contains a few
molecules of alcohol in place of some structural water of
Keggin unit, since the IR spectrum of the recrystallized
unknown substance showed a clear absorption peak at
1100 cm1 (C–O) in addition to the characteristic absorption
of HPA.
3.2.2. Technology of the etherification
Fig. 3 shows the results from the etherification of
diethylene glycol and ethanol with the catalysis of 12-
tungstophosphoric acid at different temperatures. As Fig. 3
shows, with temperature raising the conversion increased,
but the selectivity for diethylene glycol ethyl ether
decreased. In order to get high productivity of the ether,
the suitable temperature is 180–200 8C.
Fig. 4 shows the results from the etherification of
diethylene glycol with ethanol by the catalysis of 12-
tungstophosphoric acid in different reaction time. The figure
shows that the conversion increased as the reaction time was
extended. The effect of the reaction time on the selectivity
for diethylene glycol ethyl ether was not obvious. The
increase of the conversion is small when the reaction time is
over 2.5 h, so the suitable time is 2.5 h.

Table 4
Etherification of diethylene glycol with ethanol (200 8C, 1 h)
Catalyst Cat. con. Conversion (%) Selectivity of diethylene
(103 mol/L) glycol ethyl ether (%)
H3PW12O40 1.6 60 75
H4SiW12O40 1.6 56 78
H4SiMo12O40 1.6 48 76
H3PMo12O40 1.6 30 77
H3PO4 1240.0 20 46
Fig. 1. Results from etherification of diethylene glycol and ethanol (200 8C,
H2SO4 1620.0 18 41
diethylene glycol 0.8 mol; ethanol 1.6 mol).
170 J.F. Liu et al. / Applied Catalysis A: General 277 (2004) 167–171
Fig. 2. Variation in specific conductivity of ethanol solution at 200 8C.
Fig. 3. Results from the etherification of diethylene glycol and ethanol with
the catalysis of 12-tungstophosphoric acid at different temperatures.
Fig. 4. Results from the etherification at different reaction times.
Fig. 5. Results from the etherification of diethylene glycol and ethanol with
the catalysis of tungstophosphoric acid in different concentrations of the
catalyst.
Fig. 5 shows the results from the etherification of
diethylene glycol with ethanol by the catalysis of 12-
tungstophosphoric acid in different concentrations of the
catalyst. The conversion increased when the concentration
of the catalyst was raised, and the selectivity for diethylene
glycol ethyl ether decreased slowly. When the concentration
of the catalyst is over 2.0% (m), the conversion increased
very slowly, so the suitable concentration of the catalyst is
1.5–2.0%.
3.2.3. Separation and purification of the product
Diethylene glycol ethyl ether and diethylene glycol
diethyl ether were obtained (purity 98.5%) after separating
the other products such as dioxane and ethyl ether in the
reaction mixture by distillation.
3.2.4. Recovery and reusing of the catalyst
In the course of distillation, the reaction mixture has not
been completely dried, and one could add about 2% fresh
catalyst (to total quantities of the catalyst) into the system to
supply the loss in the process so as to keep the reaction
proceeding at a suitable rate, then putting use a noun into the
next reactants; thus the catalyst is reused. The results from
the experiments indicated that the activity and selectivity of
the catalyst for the etherification did not decrease obviously
after 25 reaction recycles.
3.3. Characterization of acid catalysis by HPA
Acidity appears to be essential to the acid catalysis of
HPA in the present homogeneous etherification of alcohol,
because neutral HPA salts such as Na3PW12O40 and
Ca2SiW12O40 did not catalyze the reaction at all. The
catalytic activities of HPA were much higher than sulfuric
acid and phosphoric acid on the basis of molar concentration
of catalyst or the proton concentration, where HPA was
assumed to behave as a tri- or tetra basic acid. Hence, the
remarkable difference in catalytic efficiency between HPA
and other acids should be attributed to a certain qualitative
difference in acidic properties. The present study employed
polyhydrated HPA, 85% phosphoric acid and 98% sulfuric
acid as catalysts instead of anhydrous acid, because the
concentration of sulfuric acid and phosphoric acid are 103
times higher than HPA throughout all reactions, and the
water content order of the reaction medium is the following:
H3PO4 > H2SO4 > HPA, the catalytic activity order is:
HPA > H3PO4 > H2SO4. It was conformed from separate
experiment that the variation in water content between the
systems of HPA and other acids is never a critical cause for
the differences in catalytic activity.
The acidity of HPA in ethanol at various concentrations
was qualitatively estimated by use of Hammett indicators.
H3PW12O40, H4SiW12O40, H3PMo12O40, and H4SiMo12O40
showed an acidity range in terms of H0 function between
8.2 and 3.7 even at 0.01 mol/L, but H2SO4 and H3PO4
revealed the same range of H0 function only at 0.1 mol/L.
 J.F. Liu et al. / Applied Catalysis A: General 277 (2004) 167–171
Thus, the strong acidity of HPA in ethanol should be
responsible for the high catalytic efficiency in the ethe-
rification.
4. Conclusion
HPA shows high activity and selectivity for the
etherification of diethylene glycol and ethanol to synthesize
diethylene glycol ethyl ether. The conversion of the reaction is
92% and the selectivity for the diethylene glycol ethyl ether is
73.5% under the following conditions: the ratio of diethylene
glycol to ethanol is 1:2 (mol); temperature is 180–200 8C;
pressure is 5.0 MPa; the concentration of 12-tungstopho-
sphoric acid is 1.5–2.0%; and the reaction time is 2.5 h.
Diethylene glycol ethyl ether and diethylene glycol diethyl
ether can be obtained (purity  98.5%) after separation of the
by-products such as dioxane and ethyl ether in the reaction
mixture by distillation.
Adding about 2% (to total of quantity of the catalyst) fresh
catalyst, then reusing the catalyst, we found that the activity
171
and the selectivity of the catalyst for the etherification did not
decrease after 25 reaction recycles.
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