United States Patent 1191

1111

Reiche et al.

[45] July 20, 1976

3,970,711

[54] METHOD OF PRODUCING GLYCOLS

Primary ExaminerJoseph E. Evans

[75]

Inventors: Charles Ronald Reiche; Jerry A.

Heckman, both of Beaumont, Tex.

Attorney Agent or Flrmlrwm M stem; John E

Cu?ey

[73]
[22]

Assignee: PPG Industries, Inc., Pittsburgh, Pa.

Filed:
July 19, 1971
r

[57]

[21] APPL N03 163,579

A method of improving the quality of ethylene glycols,

[52]

us. c1. ............................ .. 260/635 E; 203/41;

260/6] 5 R; 26O/6I5 B. 260/637 R

[51]
[58]

Int. c1.2 .................. .. c07c 29/00; c07c 29/24

Field 61 Search .................. .. 260/635 E, 637 R;

particularly monoethylene glycol which is derived

fmm ethylene Oxide Produwd by the direct Oxidation
of ethylene with air or oxygen is described. The novel
method involves the removal of certain impurities
from the ethylene Oxide Producing reaction System

203/41

[56]
2,135,271

ABSTRACT

prior to the ?nal processing of the ethylene oxide pro

duced to glycol products. In a particular embodiment

References Cited

contaminating impurities are removed from a purge

UNITED STATES PATENTS

BOlCal' ........................... .. 260/635 E

stream taken from the ethylene ox1de reaction system

and which is utilized in the ethylene glycols reaction
System Removal of the impurities by the preferred

32:223.? ________________'

g4];

method of carbon adsorption produces in the ethylene

11.... 2601635 E

glycol? reactlm systemiglywls whlch have mpmved

11/1938

2,756Z241

7/1956 C0urtet......

2839588

Parker . i _ _ _ I

_'.u

Ultravlolet

transmittance.

In

particular;

mOno

3,311,544

3/1967

Ri?hl 6:61 .... ..

.260/637 R

ethylene glycol having an ultraviolet light transmit

3,367,847
3,408,267

2/1968
10/1968

Pierson ........ ..
Miller et al.

..... .. 203/41
...... .. 203/41

tance rendering it suitable for use in ?ber making pro

cesses is produced.

3,458,583

7/1969

Taul et al ..... ..

.. 260/637 R

3,576,890

4/1971

Binning ......................... .. 260/635 E

4 Claims, 1 Drawing Figure

OTHER PUBLICATIONS

Kirk-Othmer, Ency. of Chem. Techn., vol. 8, 2nd

ed., (1965), pp. 534-545.

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U.S. Patent _July 20, 1976

3,970,711

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3,970,711
1

utilized in the glycols reaction system usually have an

ultraviolet light absorption characteristic such that they

METHOD OF PRODUCING GLYCOLS

are not suitable for use in the manufacture of polyester

BACKGROUND OF THE INVENTION

Ethylene glycols (monoethylene glycol, diethylene

?bers. This limits the use of the product. Polyester

5

?bers may be produced by reaction of ethylene glycol

and terephthalic acid for example and limitation on the
use of the glycols produced for this purpose presents a
serious problem to the producer of glycols since a sig
ni?cant and desirable product market is thus lost.

glycol and triethylene glycol) are prepared commer

cially by several methods. One of these methods in
volves a two-stage reaction system, the ?rst stage of
which requires the direct oxidation of ethylene with air
or elemental oxygen over a suitable catalyst, typically a

THE PRESENT INVENTION

In accordance with the instant invention it has been
discovered that waste water from an ethylene oxide,

silver-containing catalyst, at elevated temperature

(100 to 500C. is typical) and at superatmospheric
pressure (2 to 25 atmospheres).

direct oxidation reaction system which contains ethyl

ene glycol also contains contaminating impurities
which, when utilized in the glycol producing stage of a

Ethylene oxide produced in these reactors, which

may be ?xed or ?uid bed reactors as typi?ed by US.

Pat. Nos. 2,125,333 and 2,430,443, is removed from

the reactors in a gas stream and is passed into an ab

glycol producing plant using ethylene oxide produced

sorbing vessel where it is contacted with water to ab

sorb the ethylene oxide content thereof. The gases

by direct oxidation of ethylene, causes the glycol prod

(which still contain appreciable quantities of ethylene)

light transmittance values rendering it unsuitable for

uct produced in the glycol stage to have low ultraviolet

use as ?ber grade glycol. Impurities discovered in these

ethylene glycol-water streams which have been identi
oxide containing water in the absorbing vessel is passed
?ed are mesityl oxide and ethylene carbonate. While
to a stripping column. In the Stripping column steam or
not certain of the exact compound which is causing'the
hot water is introduced and contacted usually counter
current to the ethylene oxide fed thereto to remove 25 low ultraviolet transmittance, it is theorized that mesi
tyl oxide is the most likely compound. This theory is
ethylene oxide product overhead. The water dis
based on the fact that when this compound is removed
charged from the stripping vessel is recirculated to the
from streams containing it,-the ultraviolet light trans
absorbing vessel for use in absorbing ethylene oxide
mittance of the stream is improved. Further, when
therein.

In other systems a steam heated reboiler is employed 30 mesityl oxide is added in minute quantities (1 ppm or
less) to pure monoethylene glycol having a good ultra
to heat water in the bottom of the stripping column and
violet transmittance, the transmittance is immediately
boil it. This generates steam internally in the'stripping
affected and is much lower than it was before addition.
column. While this eliminates a water build-up problem
are then recycled to the reactor while the ethylene

In performing the instant invention the impurities in

glycolsstill accumulate in'the column and must be
purged to the evaporation and/or recovery systems of 35 the ethylene glycol-water stream causing low ultravio
let light transmittance in monoethylene glycol product,
the glycolproducing unit.
for example, produced in a plant using this stream are
As will be readily understood by the skilled artisan,
removed from the stream prior to feeding them to the ,
the introduction of water into the stripping column and
glycol reaction system. Effectiveness of the removal of
the closed recycle system between the stripping vessel
and the absorbing vessel causes a buildup of water in 40 impurities in the particular method employed is easily
the system requiring a purge to remove excess water.

determined by measuring the ultraviolet light transmit

This purge stream contains appreciable quantities of

ethylene glycol in it and is usually of such value that it
cannot be discarded. Further, since it contains ethylene
glycol, it cannot be easily disposed of due to the fact
that ethylene gylcol has a deleterious effect of the total

tance of monoethylene glycol manufactured in the

plant using the contaminated water-ethylene glycol

45

streams. Ultraviolet light transmittance is determined

by comparison of the percent transmittance of ultravio
let light through the glycol sample at wave lengths of

oxygen demand of bodies of water in which this mate

220, 250, 275 and 350 nanometers compared to per

rial might be discharged. Similarly, where heated strip

cent light transmittance at the same wave lengths

through distilled water.

ping vessels are used glycol buildup in the columns
50
In accordance with the preferred mode of performing
required a bleed of water-glycol from the system.
the instant method, an ethylene glycol-water stream
In a typical glycol plant in which ethylene oxide is
hydrolyzed in a reaction zone with water at elevated
temperature and pressure as the second stage of a reac

recovered from an ethylene oxide reaction system

tion system. and in which system glycols are subse

oxygen is treated before passage into a glycol reaction

quently evaporated and distilled to produce the pure

glycols those waste streams are fed to the glycol reac

tion system to avoid the overall loss of glycols that

using direct catalytic oxidation of ethylene with air or

55

system producing ethylene glycols from the ethylene

oxide made in the ethylene oxide reaction system by
passing the ethylene glycol-water stream through a bed

of activated carbon. Passage of the stream through a

bed of activated carbon reduces the mesityl oxide con
this second stage reaction system which is typically 60 tent of the stream substantially or eliminates it. The bed
also reduces or eliminates the ethylene carbonate con
provided with a glycol reactor in which the oxide feed
tent of such stream. The ethylene glycol-water mixture
is converted to glycols, an evaporation system in which
upon emerging from the carbon bed is found to have a
the glycols are concentrated and a still system in which
high ultraviolet transmittance and the mixture may be
all water is removed and in which monethylene glycol,
diethylene glycol and triethylene glycol are separated 65 fed to the glycol reaction system for recovery of its
ethylene oxide content. It is also found that glycols
from each other.
.

accompanies disposal of glycol containing streams.

These streams may be fed to any of several places in

It has been found that the glycols produced when

these water streams containing ethylene glycol are

produced in a glycol reaction system utilizing an ethyl

ene glycol-water stream treated as described with acti

3,970,711
4

vated carbon, produced monoethylene glycol having

While carbon, and activated carbon in particular, is

ultraviolet absorption characteristics rendering it suit

- described as-the adsorbent used in practicing the in

stant invention, recourse to the use of other adsorbents

able for use in ?ber making. The carbon bed utilized is

further found to remove the bothersome impurities

may be had without departing from the spirit of the

causing low ultraviolet transmittance in the produced

glycols for long periods of time before becoming ex

invention. Thus utilization of silica, silica gels, alumina, .

Fullers earth, porous glass such as leached borosilicate
glass, diatomaceous earth and the like are contem

haus'ted. The carbon beds after exhaustion may be

regenerated by use of high pressure steam or by re

plated.

course to heat treatment in a furnace if desired.

'

For a more complete understanding of the invention,

Ethylene glycol-water streams containing the con

taminating impurities may be treated in accordance

reference is made to the accompanying drawing which

diagrammatically illustrates one method of producing

with this invention by recourse to several procedures

other than the preferred method above described.

glycols utilizing the instant invention.

1
In the drawing ethylene and air are fed to a reactor 3

Thus, these streams may be heat treated at elevated

through lines 1 and 2, respectively. The reactor 3 is a

conventional ?xed bed reactor'containing a plurality of

temperatures to eliminate the contaminating impurities

by the thermal decomposition. Ethylene glycol-water

tubular reactors ?led with a silver catalyst. The ethyl

ene and oxygen react in the presence of the catalyst at
temperature typically in the range of 100 to 500C.,

streams containing the contaminating impurities can be

heated under pressure (2 to 10 atmospheres or more)
at temperatures of 250 to 400C. to accomplish the

decomposition. As reported in Whitmore, Organic

preferably in the range of 200 to 360C. The ethylene

20

Chemistry, at page 277, D. Van Nostrand Company,

lnc., mesityl oxide may also be treated with HOCl to

produce Me2C (OH )CHClCOMe. This product can be

reacted with alkali to produce an insoluble epoxide that

oxide produced is then passed to an absorber 4 via line

5 where it is contacted with water entering column 4
vialine 6.. Product ethylene oxide in water is removed
via line 8 and is passed to a stripping vessel 9. ln vessel
9 the ethylene oxide-water mixture is contacted with

25 steam introduced in column 9 via line 10 and product

can then be ?ltered from the stream. I
- In the preferred mode of operation to remove the
ethylene oxide is removed via line 11 where it is passed

impurities deleteriously affecting glycol ultraviolet

to a fractionator, not shown, for further processing and

fed to glycol reactor 16 via line 110. This portion of a
conventional ethylene oxide process is shown in Kirk

transmittance, monoethylene glycol in particular, a bed

of adsorbent material is utilized. This method of re~
moval has been found to require a minimum of equip
ment and material and accomplishes the result in an

Othmer, Vol'. 5, pages 919-920, lnterscience Publish

ers, lnc., New York, N. Y., 1950.

effective as well as economical manner. While the sew

7 Water recovered in column 9 is recirculated in line 6

ering of ethylene glycolwater mixtures containing con

taminating impurities will prevent the introduction of

to column 4 where further quantities of ethylene oxide

those particular impurities into a glycol reaction sys

tem, the ethylene glycol-water streams representing a

35

valuableprocess stream are thereby lost. This intro

duces a serious economic loss in the overall process.

Still further, sewering of these materials represents a

serious pollution problem in that they contain materials
that seriously affect the biological oxygen demand and

are absorbed in it. The vsteam addition in line 10, cou

pled with the recirculation of process waters, requires a
bleed of water from the system vin order to maintain a
water balance. This stream is taken from line 6 in line
12 and since it-contains typically from 0.2 to 3 or more

percent ethylene gylcol in it, it is conventionally sent to

40

a glycol producing plant via lines 12a and 11a to the

ethylene oxide feed line- 15 of reactor 16 for recovery.

even possibly the chemical oxygen demand of the water

bodies into which sewer waters are normally dis

This stream may also be fed in a conventional manner

charged.

I The system 19 is typicallyamultipleeffect evaporator

via line 12b to the evaporator system 19.

The carbon beds utilized in the preferred mode of 45 system for steam economy purposes and in the pre
puri?cation contemplated may contain any form 'of
ferred operationvof thissystem with the ethylene oxide
adsorbent carbon. Activated carbon has been found to
plant- shown, the water stream in line 12b is fed to the
be particularly effective for use in this puri?cation and
third effect evaporator of the evaporator system 19 as
any activated carbon appears to be effective. The mesh
re?ux to that evaporator effect. Typically system 19 is
size of the activated carbons of the preferred embodi 50 a triple effect evaporator system.
ment'does not appear to be of particular signi?cance
Water is fed to the glycol reactor 16 via line 18 and
and generally carbons ranging between 4 to 100 mesh
the ethylene glycol products made in reactor l6
are used. It is preferred that carbon in a size range of 4
(monoethylene glycol, diethylene glycol and triethyl
ene glycol) are removed via line 21 and fed to the
The process streams treated in accordance with this 55 evaporator system 19. _
'
invention'are typically in a temperature range of be
From the evaporator system 19 the product glycols
tween 80 to 140F., but preferably are maintained at a
are passed in line 22 to a monoethylene glycol still 23.
temperature of 85F. or more, usually 85 to 95F. It
In this still monoethylene glycol product is removed
has been found that at temperatures below 80F. the
overhead in line 24. The bottoms of still 23 are sent to
removal of the impurities from the ethylene glycol 60 a second still 25 via line 26 and in this still diethylene
water streams causing the ultraviolet transmittance
glycol is removed overhead in line 27. The bottoms of
this still are sent via line 28 to a third still 29 where they
dif?culties' is erratic in that the monoethylene glycol

to 40 mesh be utilized.

produced in the plant using these streams is acceptable

some times 'and unacceptable other times with respect

to ultraviolet transmittance. Thus, it is important that

the temperature of the stream entering the carbon
absorption system be above at least 80F. and prefer
ably above about 85F.

are processed and triethylene glycol product is re

moved via line 30. The bottoms of this still are removed
65 via line 31 for further processing.

'

1n the glycol distillation system illustrated, it is typical

at atmospheric pressure to operate column 23 at bot
toms temperatures of 230 to 250C. and overhead

3,970,711
23 was monitored for its ultraviolet transmittance using
distilled water as the reference liquid in a Beckman

temperatures of 190 to 200C. Column 25 is operated

at bottoms temperatures of about 260 to 283C. with
overhead temperatures of 220 to 250C._and column
29 is usually operated with bottoms temperatures of
277 to 308C. and overhead temperatures of 260 to
283C.
ln practicing the preferred embodiment of the instant
invention with a glycol production unit using ethylene
oxide produced by a direct oxidation system, the ethyl
ene gylcol-water mixture in line 12 coming from the
ethylene oxide plant is ?rst treated in unit 31 to remove

Model DU 2400 Spectrophotometer. The results of the

treatment on the purity of the monoethylene glycol
produced while the carbon bed was employed are
shown below in Table I:
TABLE I
Wavelength (nanometers)

impurities therein to a level that does not contaminate

the monoethylene glycol product to the extent that its

ultraviolet absorption speci?cations are unacceptable

for ?ber grade use. This treatment in the preferred
mode of operation constitutes an adsorption of the

Run*

220

250

275

350

l
2
3
4
5
6
**Standard

80
80
82
81
8l
79
75

89
9]
92
90
9]
90
88

92
94
94.5
94
93
92
90

100
I00
I00
I00
I00
100
98

Each run was sampled over a 16 hour period. Runs l. 2, 4, 5 and 6 were sampled
every 2 hours and Run 3 was sampled every 3 hours. The bed was used continuously
with the runs not being monitored between midnight and 8 A. M.

impurities in the product on an activated carbon bed.

The ultraviolet light absorption characteristics of the

"Monoethylcne glycol having transmittance values shown is acceptable for ?ber

water entering the bed 31 and leaving the bed 31 are

measured. In addition the ultraviolet light characteris

grade use. Higher numbers than those shown are improvements over the standard.

tics of the monoethylene glycol recovered in line 24 of 20 The carbon bed above described was used to treat
the still 23 are measured to insure good bed operation.
ethylene glycol-water mixtures recovered from a direct
The water removed from this bed may be fed to the
oxidation of ethylene oxide until the bed no longer
glycol reaction system via line 13 to the glycol reactor
produced acceptable ultraviolet light transmittance in
16 or via line 17 to the evaporation system 19, prefer
monoethylene glycol produced in a plant using such
ably the third effect of a triple effect evaporator as 25 mixtures. The bed was found capable of processing 1.8
re?ux therein.

million gallons of such process ethylene glycol-water

In general it has been found that transmittance of

mixtures before it became exhausted.

ultraviolet light in the water stream in lines 13 or 17 of

'

While the invention has been described with refer

ence to certain speci?c embodiments, it is not intended
to be limited thereby except insofar as appears in the

at least 94 or more at wave length of 250 nanometers

will provide for a monoethylene glycol product from

accompanying claims.

still 23 having a transmittance within an acceptable

range for ?ber grade use, i.e., 75 to 76 at 220 nanome
ters, 88 to 90 at 250 nanometers, 90 to 92 at 275 nano
meters and 98 to 99 at 350 nanometers.
For a more complete understanding of the instant

We claim:

1. 1n the process of producing ethylene glycol in an

ethylene glycol reaction system by hydrolysis of ethyl

ene oxide wherein ethylene oxide, which is produced
by direct oxidation of ethylene, is absorbed in water in

invention, reference is made to the following example

which illustrates the instant invention utilized to pro

an absorbing vessel to form an ethylene oxide-water

duce monoethylene glycol of ?ber grade quality from a

mixture, ethylene oxide is stripped from the ethylene

glycol installation using ethylene oxide produced by air

oxidation of ethylene and recovering ethylene glycol

oxide-water mixture in a stripping vessel, and ethylene '

glycol-containing
water streams from the ethylene oxide plant as part of 40 recycled to the
which comprises
the feed to the glycol plant.
glycol-containing
EXAMPLE

water from the stripping vessel is

absorbing vessel, the improvement

removing a portion of the ethylene
water as a purge stream, improving

the ultraviolet light transmittance of ethylene glycol

containing water purge stream by'contacting it at a

A purge stream 12 containing ethylene glycol-water
mixture from an ethylene oxide plant such as illustrated 45 temperature of at least 80F. with an adsorbent se

lected from the group consisting of carbon, silica, silica

gel, alumina, Fullersearth, porous glass and diatoma
ceous earth, forwarding ethylene glycol-containing

in the accompanying drawing and which averaged 30 to

35 gallons per minute in volume ?ow was passed into
the top of a carbon bed contained in a 6 foot diameter

pressure vessel. The bed was packed with a Pittsburgh

Activated Carbon, Type Cal, 12 to 40 mesh in size,
manufactured by Calgon Corporation to a depth of 4

water of improved ultraviolet light transmittance to the

50

the ethylene glycol reaction system.

feet. The vessel 31. was 8 feet in height and the bed was
placed on a screen about 1 foot from the bottom of the
vessel 31. The process glycol-water mixture. in line 12
was passed through the bed and the vessel 31 was ?lled
and maintained at an internal pressure of 125 psig. The
process water after passage through the carbon bed was
utilized as re?ux in the evaporator system 19 in the
third effect evaporator of a glycol plant as illustrated

and which used theethylene oxide produced in the

reaction system shown as feed to the glycol reaction

ethylene glycol reaction system and recovering ethyl

ene glycol that is suitable for ?ber manufacture from

2. The process of claim 1 wherein the ethylene glycol-containing water purge stream contains from about

0.2 to about 3 percent ethylene glycol and the purge

stream is contacted with adsorbent at from about 80 to
about 140 F.

3. The process of claim 1 wherein the ethylene glycol

reaction system contains a glycol reactor wherein eth
60

ylene oxide is hydrolyzed with water to ethylene glycols

and an evaporator system wherein water is separated

system shown. Glycol was produced in vessel 16 by

from the ethylene glycols, and wherein the ethylene

reacting ethylene oxide and water at a temperature of

about 100 to about 120C. and at a pressure of about

glycol-containing water purge stream of improved ul

traviolet light transmittance is forwarded to the glycol

8.3 atmospheres. The glycol was evaporated in unit 19

reactor, or to the evaporator system as re?ux, or to

and monoethylene glycol was distilled in column 23 at 65 both of said glycol reactor and evaporator system.
4. The process of claim 3 wherein the adsorbent is
atmospheric pressure with a bottoms temperature of
activated carbon.
about 246C. and an overhead temperature of about

198C. The monoethylene glycol product from the still

a: