United States Patent ll.

" P 1C6 3,585,217

1 2
jects and advantages are achieved in an improved process
3,585,217 for the production of ethylene oxide by reacting ethylene
PRODUCTIIGN 0F ETHYLENE OXIDE with oxygen or gases containing oxygen at temperatures
Eckart Titzenthaler, Oberhausen, Germany, assignor to of 150° to 400° C. and pressures between atmospheric
Badischc Anilin- dz Soda-Fabrik Alrtiengesellschaft, C21 pressure and 30 atmospheres in the presence of catalysts
Ludwigshafen (Rhine), Germany containing silver, wherein the improvements comprises
N0 Drawing. Filed Get. 4, 1967, Ser. No. 672,695 using as catalyst silver silicate having a silver content
Claims priority, application Germany, Oct. 6, 1966,
P 12 79 007.142 of 30 to 90% by weight based on silver silicate.
lint. ill. (307d 1/14 The new process has the advantage that in addition to a
U.S. Cl. 260—3485 9 Claims 10 long life, a much higher speci?c yield of ethylene oxide is
obtained than hitherto. Moreover the new catalyst has a
high abrasion resistance and only a slight tendency to
ABSTRACT OF THE DISCLOSURE agglomerate and this is an advantage particularly when
using a ?uidized bed. Furthermore the catalyst is easy to
Production of ethylene oxide by reaction of ethylene prepare.
with oxygen or gases containing oxygen at temperatures Ethylene is used as the starting material. It is also pos
of 150° to 400° C. in the presence of silver silicate as sible to use gases containing ethylene. The gas advanta
catalyst. Glycol and polyethylene oxides may be prepared geously contains more than 0.5% by volume of ethylene.
from ethylene oxide. lnert gases, for example carbon dioxide, nitrogen, water
20 vapor or small amounts of saturated hydrocarbons may be
contained in the gas in addition to ethylene. To suppress
This invention relates to an improved process for the the formation of carbon dioxide, the reaction may be
production of ethylene oxide. carried out in known manner in the presence of for exam
In a commercial process for the production of ethylene ple 0.01 to 10 ppm. of compounds containing halogen,
ethylene is oxidized with gases containing oxygen in the 25 for example in the presence of chlorohydrocarbons, such
presence of silver as a catalyst. It is known from U.S. as ethylene chloride, or chlorinated phenols. The com
patent speci?cation No. 2,562,857 and from U.S. patent pounds containing halogen may be supplied for example
speci?cations Nos. 2,837,424 and 2,837,486 that suitable by means of inert gases.
catalysts are obtained by removing alkaline earth metals The reaction is carried out with oxygen or a gas con
from alloys of silver with alkaline earth metals, leaving taining oxygen. When oxygen-containing gases are used,
only a small residue of the alkaline earth metals. Catalysts these generally contain 10 to 30% by volume of oxygen,
prepared by this method do not have very good activity or preferably 15 to 25% by volume of oxygen. It is preferred
selectivity. Silver catalysts having improved activity are to use air. It is also possible however to use gases having
obtained by applying reduced silver compounds to inert a higher oxygen content.
carrier materials followed by reduction. Carrier materials Ethylene and oxygen (or ethylene and oxygen-contain
include clay, alumina, mullite, silicon carbide or beryllium ing gas) are in general used so that the mixture is outside
porcelains (U. K. patent speci?cation No. 711,601), spinels the explosive limits. The explosive limits may be deter
(U.S. patent speci?cations Nos. 2,713,586, 2,593,100 and mined by known methods for each gas mixture. It is ad
2,593,097), magnetite (U.S. patent speci?cation No. 40 vantageous to use oxygen in excess, for example up to
2,593,156), graphite (U.S. patent speci?cation No. 2,615, 50 mole percent, with reference to ethylene. The reac
899) or silicon dioxide (U.S. patent speci?cation No. tion is carried out in the gas phase in general at temper
2,430,443). Finely divided silver has only poor adhesion atures of 150° to 400° C., preferably 170° to 350° C.
to the carrier, however, and this is a disadvantage espe The reaction may be carried out at atmospheric pres
cially when the catalysts are used in a ?uidized bed. More sure, slightly subatmospheric pressure or slightly super
over these catalysts tend to agglomerate during the reac atmospheric pressure, for example up to 2 atmospheres.
tion. The activity of the catalysts can be increased by In commercial operation it is preferred to use pressures
additives. The following have been described as suitable of up to 30 atmospheres.
additives: alkaline earth metal oxides, alkaline earth metal The silver catalysts advantageously contain 30 to 90%
carbonates or salts of alkaline earth metals with lower by weight, preferably 45 to 85% by weight, of silver. The
fatty acids (U.S. patent speci?cations Nos. 2,628,965 and silver catalysts may also contain prior art activators, such
2,593,099), and metal halides (U.S. patent speci?cations as compounds of Group I, II or III of the Periodic System,
Nos. 2,615,900 and 2,799,687). The catalysts provided for example oxides, carbonates, hydroxides or salts with
with the said additives also tend to agglomerate in a ?uid lower fatty acids. Halogen compounds, such as alkali
ized bed. metal chlorides, which are known to counteract the forma
Furthermore it has been stated in Japanese patent speci 55 tion of carbon dioxide, may be incorporated into the cata
?cation No. 18,662/ 63 that silver silicate, silver ?uosilicate lysts. The silver silicates may be used unsupported (Le.
or silver heteropolysilicates are suitable catalysts. They are without carrier). In this case the silver silicate is advanta
however only used in combination with other catalysts, geously prepared by reaction of an alkali metal silicate
such as silver titanate in the liquid phase with the use of solution, for example waterglass, with solutions of silver
a solvent. The production of the mixed catalysts and oper 60 salts, such as silver nitrate, followed by drying of the
ation in the liquid phase is expensive. precipitate at 100° to 120° C.
With all the abovementioned catalysts, speci?c yields of ‘It is preferred to use silver polysilicates in which there
less than 1000 g. of ethylene oxide per kilogram of silver are about three silicon atoms to two silver atoms. It is
per hour are obtained. also possible however to use silver orthosilicate which may
It is an object of the present invention to provide a 65 be obtained for example by a process described in Zeit
process ‘which gives high speci?c yields of ethylene oxide. schrift fiir anorganische und allgemeine Chemie, 318, 72
Another object of the invention is to provide a process to 88 (1962), by reaction of silver oxide with pure precipi
for the production of ethylene oxide in which the cata tated silicic acid in equivalent proportions followed by
lyst used has high resistance to abrasion and a low tend treatment with a silver nitrate melt at 280° C.
ency to agglomerate. 70 It is also possible to apply the silver silicates in a moist
In accordance with this invention these and other ob condition to the carrier, such as fuller’s earth, pelleted
 3,585,217
silicic acid, aluminum oxide or silicates and to heat the perature of 290° C. has been exceeded, 10,000 parts by
product for example at 100° to 110° C. volume (S.T.P.) of nitrogen which contains 200 p.p.m.
The ?nished supported catalysts in general contain 5 of ethylene chloride is added per hour to the gas mixture.
to 20% by weight of silver. In a suitable particle size, When a temperature of 290° to 298° C. is used, the ef
silver silicates are suitable for reaction in a ?uidized bed, ?uent gas contains 0.98% by volume of ethylene oxide.
preferably wthout a carrier. The catalyst may be rapidly The yield is 432 g. per hour of ethylene oxide per liter of
brought into its active form by treatment with hydrogen catalyst or 1650 g. of ethylene oxide per kilogram of
prior to the reaction. silver used per hour.
The process according to the invention may be carried When the experiment is carried out at 300° to 308° C.,
out for example by arranging silver silicate having the the e?luent gas contains 1.10% by volume of ethylene ox
said composition (which may have been applied to a ide and the hourly yield is 475 g. of ethylene oxide per
carrier) stationarily in a tube and passing ethylene and liter of catalyst or 1400 g. of ethylene oxide per kilogram
oxygen in the stated proportions or a gas containing eth of silver used.
ylene and oxygen through the tube at the stated tempera EXAMPLE 3
tures and pressures. The ethylene and the oxygen or oxy
gen-containing gas may be metered separately into the A boiling solution of 304 parts of potassium water
reaction chamber or may be previously mixed. In another glass (28° to 29° Bé., consisting of 8.19% by weight of
preferred embodiment ethylene and oxygen or a gas mix potassium oxide and 21.02% by weight of silicon dioxide)
ture containing ethylene and oxygen are passed at the and 1000 parts by volume of water is allowed to ?ow into
said temperatures through a ?uidized bed of silver silicate ~ a boiling solution of 100 parts of silver nitrate and 1000
particles. Undesirable formation of carbon dioxide may parts by volume of water while stirring. The precipitate
be lessened by adding inert gases which may contain halo is isolated by ?ltration and washed with hot water until
gen compounds. The ethylene oxide is separated from the it is free from nitrate ions. The ?lter cake is then dried
gas mixture obtained, for example by washing with water. at 125 ° C. until it has a constant weight and then an
After the ethylene oxide has accumulated in Water it is nealed for three hours at 400° C. The silver silicate has
isolated by distillation. The residual gas may be recycled a silver content of 46.0% by weight. It is broken up and
to the reaction after it has been enriched with ethylene a fraction from 0.2 to 0.3 mm. in diameter is screened
and oxygen. out.
The invention is illustrated further by the following A vertical tube having a capacity of 2400 parts by vol
examples in which the parts speci?ed are parts by weight 30 ume and closed at the bottom by a porous gas-permeable
unless stated otherwise. Parts by weight bear the same plate is charged with 78 parts of the silver silicate par
relation to parts by volume as the kilogram to the liter. ticles. 6,380,000 parts by volume (S.T.P.) of a gas mix
ture consisting of 5.6% by volume of ethylene, 0.01% by
EXAMPLE 1 volume of ethane, 6.9% by volume of carbon dioxide,
A boiling solution of 170 parts of 35% by weight water 35 6.4% by volume of oxygen, 0.1 p.p.m. of ethylene chlo
glass (Deutsches Arzneibuch (DAB) 6) and 1000 parts ride and the remainder nitrogen is passed in per hour
by volume of water is allowed to ?ow into a boiling so through the porous plate. Part of the gas mixture is pre
lution of 100 parts of silver nitrate and 1000 parts by heated to 270° to 300° C. to keep the catalyst layer at
volume of water while stirring. The precipitate is iso a temperature of 180° C. The ?uidized layer of silver
lated by ?ltration and washed with hot Water until it is 40 silicate is heated to 260° C. in the course of several days
free from nitrate ions. The ?lter cake is then dried at and kept at this temperature. A pressure of 6 atmospheres
110° C. until its weight is constant. The silver content is maintained in the reaction tube. The pressure is re
is about 48% by weight. The silver silicate obtained is leased and the product cooled. The e?°luent gas contains
then broken up and a fracton having a particle size of 0.65% by volume of ethylene oxide. This is equivalent
0.15 to 0.3 mm. is screened out. This screen fraction is to a yield of 679 g. of ethylene oxide per liter of cata
heated for three hours at 400° C. prior to use. lyst or 2270 g. of ethylene oxide per kg. of silver used.
A vertical tube having a capacity of 1900 parts by vol I claim:
ume, closed ‘at the bottom by a porous gas-permeable 1. A process for the production of ethylene oxide by
plate, is charged with 57 parts of the silver silicate par reaction of ethylene with oxygen or gases containing oxy
ticles, and 2,200,000 parts by volume (S.T.P.) of a pre gen at temperatures of from 150° to 400° C. and at
heated gas mixture consisting of 5.5% by volume of eth pressures of from atmospheric pressure to 30 atmospheres
ylene, 0.015% by volume of ethane, 7% by volume of in the presence of catalysts containing silver in the gas
carbon dioxide, 6.3% by volume of oxygen, 0.1 p.p.m. phase wherein the improvement comprises using a silver
of ethylene chloride and the remainder nitrogen is intro polysilicate having about three silicon atoms to two silver
duced per hour into the bottom of the tube through the atoms as the catalyst.
porous plate. The ?uidized silver silicate bed is heated up 2. A process as claimed in claim 1 wherein the gas
to 300° C. in the course of several days and kept at this used contains more than 0.5% by volume of ethylene.
temperature. The e?°luent gas contains 0.75% by volume 3. A process as claimed in claim 1 wherein a com
of ethylene oxide. This is equivalent to a yield per hour pound containing halogen is used as an inhibitor.
of 330 g. of ethylene oxide per liter of catalyst or 1190 4. A process as claimed in claim 1 wherein an oxygen
g. of ethylene oxide per kilogram of silver. 00 containing gas is used which contains 10 to 30% by
volume of oxygen.
EXAMPLE 2 5. A process as claimed in claim 1 in which air is
Silver silicate is prepared as described in Example 1 used as the oxygen-containing gas.
and mixed While in the moist condition with 0.143 part of 6. A process as claimed in claim 1 in which oxygen
boric acid and which is dissolved in 50 parts by volume of is present in an excess of up to 50 mole percent with ref
water. The catalyst composition is then dried for one day erence to ethylene.
at 125° C. The dried catalyst is broken up and the screen 7. A process as claimed in claim 1 carried out at from
fraction from 0.15 to 0.3 mm. is activated at 400° C. 170° to 350° C.
The catalyst contains 49.1% by weight of silver and 0.02% 70 8. A process as claimed in claim 1 wherein the catalyst
by weight of boron. used is a silver silicate having a silver content of 40 to
55 parts of the catalyst is placed in the apparatus de 85% by weight.
scribed in Example 1 and 2,200,000 parts by volume 9. A process as claimed in claim 1 carried out in a
(S.T.P.) per hour of the gas mixture described in Ex ?uidized bed.
ample 1 is introduced at the bottom. As soon as the tem 75 (References on following page)
 3,585,217
6
References Cited 892,381 3/1962 Great Britain ____ __ 260—348.5
FOREIGN PATENTS 527,261 7/1956 Canada _________ __ 260-3485

38/18,662 9/1963 Japan __________ _- 260-3485 NORMA S. MILESTONE, Primary Examiner