U.S. patent application number 10/539412 was filed with the patent office on 2006-03-16 for process for manufacturing ethylene oxide.
Invention is credited to Mathias Mauvezin, Christine Poulain, Mehdi Rghioui, Hassan Taheri.
Application Number | 20060054314 10/539412 |
Document ID | / |
Family ID | 32406186 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060054314 |
Kind Code |
A1 |
Mauvezin; Mathias ; et
al. |
March 16, 2006 |
Process for manufacturing ethylene oxide
Abstract
The present invention relates to a process for manufacturing
ethylene oxide by the catalytic oxidation reaction of ethylene by
molecular oxygen in a tube reactor. The reactor comprises a bundle
of reaction tubes (5) which are immersed in a heat exchange fluid
and filled with a solid silver-based catalyst (8) and which are
traversed by a reactive gas current containing ethylene and
molecular oxygen, which in contact with the catalyst forms the
ethylene oxide. The area of the internal cross-section of the
reaction tubes (5) decreases between the inlet (1) and the outlet
(3) of the tubes over at least a portion of the length of the tubes
and remains constant over any remaining portion. The process makes
it possible to increase the selectivity of the reaction to ethylene
oxide for a given production of ethylene oxide. It also makes it
possible to use a maximum charge of active catalyst per unit of
internal tube volume available in the reactor, owing in particular
to an optimum heat exchange capable more particularly of supplying
a relatively stable reaction temperature profile over the whole
length of the reaction tubes and preventing in particular reaction
runaways.
Inventors: |
Mauvezin; Mathias;
(Martigues, FR) ; Poulain; Christine; (Carry le
Rouet, FR) ; Rghioui; Mehdi; (Martigues, FR) ;
Taheri; Hassan; (Naperville, IL) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Family ID: |
32406186 |
Appl. No.: |
10/539412 |
Filed: |
December 3, 2003 |
PCT Filed: |
December 3, 2003 |
PCT NO: |
PCT/GB03/05203 |
371 Date: |
June 17, 2005 |
Current U.S.
Class: |
165/216 |
Current CPC
Class: |
B01J 8/067 20130101;
B01J 2208/00212 20130101; F28D 7/16 20130101; F28F 13/08 20130101;
B01J 8/008 20130101 |
Class at
Publication: |
165/216 |
International
Class: |
F24F 3/00 20060101
F24F003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2002 |
FR |
0216145 |
Claims
1. Process for manufacturing ethylene oxide by the catalytic
oxidation reaction of ethylene by molecular oxygen in a tube
reactor comprising three successive and adjacent chambers traversed
by a reactive gas current containing ethylene and molecular oxygen,
an inlet chamber of the reactive gas current, then a central
chamber forming a gas current resulting from the reacting and
comprising the ethylene oxide, and an outlet chamber of the
resulting gas current, the central chamber comprising a bundle of
reaction tubes immersed in a heat exchange fluid and filled with a
solid silver-based catalyst in contact with which the reactive gas
current forms the ethylene oxide, each reaction tube possessing an
inlet issuing into the inlet chamber and an outlet issuing into the
outlet chamber, the process being characterised in that the area of
the internal cross-section of the reaction tubes decreases between
the inlet and the outlet of the tubes over at least a portion of
the length of the tubes and remains constant over any remaining
portion.
2. Process according to claim 1, characterised in that the area of
the internal cross-section of the reaction tubes decreases
continuously.
3. Process according to claim 1, characterised in that the area of
the internal cross-section of the reaction tubes decreases
discontinuously, preferably by stages.
4. Process according to claim 1, characterised in that the area of
the internal cross-section (A1) at the inlet of the reaction tubes
is from 1.5 to 12 times, preferably from 2 to 10 times, more
particularly from 3 to 9 times greater than the area of the
internal cross-section (A2) at the outlet of said tubes.
5. Process according to claim 1, characterised in that the decrease
in the area of the internal cross-section of the reaction tubes is
effected once only over the length of the tubes, either
continuously over a portion of the length of the tubes, or
discontinuously, preferably by a stage, such a decrease being
effected at the latest before the last fifth of the length of the
tubes situated towards the outlet.
6. Process according to claim 1, characterised in that the decrease
in the area of the internal cross-section of the reaction tubes is
effected two or more successive times over the length of the tubes,
either continuously over two or more portions of the length of the
tubes, or discontinuously, preferably by two or more successive
stages, such a decrease being effected for the first time at the
latest before the last fifth of the length of the tubes situated
towards the outlet.
7. Process according to claim 1, characterised in that the reaction
tubes have a length (L) of from 6 to 20 m, preferably from 8 to 15
m, an area of the internal cross-section (A1) at the inlet of the
tubes from 12 to 80 cm.sup.2, preferably from 16 to 63 cm.sup.2,
and an area of the internal cross-section (A2) at the outlet of the
tubes of less than A1 and ranging from 1.2 to 16 cm.sup.2,
preferably from 1.8 to 12 cm.sup.2.
8. Process according to claim 1, characterised in that the reaction
tubes have a cylindrical shape and exhibit a circular internal
cross-section whose internal diameter (Di) decreases between the
inlet and the outlet of the tubes over at least a portion of the
length of the tubes and remains constant over any remaining
portion.
9. Process according to claim 8, characterised in that the internal
diameter (D1i) at the inlet of the reaction tubes is from 1.2 to
3.5 times, preferably from 1.4 to 3.1 times, more particularly from
1.7 to 3 times higher than the internal diameter (D2i) at the
outlet of said tubes.
10. Process according to claim 8, characterised in that the
reaction tubes have a length (L) of from 6 to 20 m, preferably from
8 to 15 m, an internal diameter (D1i) at the inlet of the tubes of
from 38 to 100 mm, preferably from 45 to 90 mm, and an internal
diameter (D2i) at the outlet of the tubes of less than D1i and
ranging from 12 to 45 mm, preferably from 15 to 40 mm.
11. Process according to claim 1, characterised in that the
reaction tubes have a wall whose thickness is constant from the
inlet up to the outlet of the tubes.
12. Process according to claim 1, characterised in that the
reaction tubes have a wall whose thickness varies from the inlet up
to the outlet of the tubes.
13. Process according to claim 8, characterised in that the
reaction tubes have an external diameter which is constant between
the inlet and the outlet of the tubes and preferably equal to the
external diameter at the inlet of said tubes.
14. Process according to claim 1, characterised in that the heat
exchange fluid immersing the bundle of reaction tubes is chosen
from among water superheated under pressure and organic heat
carrying fluids, preferably mixtures of oils or hydrocarbons.
15. Process according to claim 14, characterised in that the
organic heat carrying fluid is used at a relative pressure of from
100 to 1500 kPa, preferably from 200 to 800 kPa, more particularly
from 200 to 600 kPa.
16. Process according to claim 14, characterised in that the
superheated water is used at a relative pressure of from 1500 to
1800 kPa.
17. Process according to claim 1, characterised in that the
temperature of the reactive gas current in the reaction tubes is
chosen in a range of from 140 to 350.degree. C., preferably from
180 to 300.degree. C., more particularly from 190 to 280.degree.
C.
18. Process according to claim 1, characterised in that the
reactive gas current is pre-heated to a temperature of from 100 to
200.degree. C., preferably from 140 to 190.degree. C.
19. Process according to claim 1, characterised in that the
temperature of the gas current resulting from the reaction at the
outlet of the reaction tubes remains at a maximum temperature
attained by the reactive gas current in the reaction tubes or
preferably decreases to a temperature equal to or less than
250.degree. C., preferably 240.degree. C., more particularly
230.degree. C., in particular a temperature chosen in a range of
from 180 to 250.degree. C., preferably from 190 to 240.degree. C.,
more particularly from 200 to 230.degree. C.
Description
[0001] The present invention relates to a process for manufacturing
ethylene oxide by the catalytic oxidation reaction of ethylene.
[0002] The catalytic oxidation reaction of ethylene by molecular
oxygen leading to the formation of ethylene oxide is known to be
strongly exothermic. It is often carried out in a tube reactor, in
particular a vertical multitubular shell exchanger type reactor or
a vertical shell-and-tube exchanger type reactor. In general, the
tube reactor comprises three successive and adjacent chambers
traversed by a reactive gas current comprising ethylene and
molecular oxygen: an inlet chamber of the reactive gas current,
then a central chamber where the ethylene oxide is formed in a gas
current resulting from the catalytic oxidation reaction and an
outlet chamber of the resulting gas current. The central chamber
comprises generally a bundle of reaction tubes immersed in a heat
exchange fluid and filled with a solid silver-based catalyst. The
reactive gas current passes to the interior of the reaction tubes
and, by contact with the catalyst, leads to the formation of
ethylene oxide in the gas current resulting from the reaction. Each
reaction tube comprises an inlet issuing into the inlet chamber and
an outlet issuing into the outlet chamber. In each of the reaction
tubes, three successive zones from the inlet to the outlet of the
tubes are generally found, that is to say in the flow direction of
the gas current, namely a pre-heating zone situated towards the
inlet of the tubes, then a reaction zone and a quenching or cooling
zone situated towards the outlet of the tubes.
[0003] The desired product of the catalytic oxidation reaction of
ethylene is ethylene oxide. However, non-desired secondary
reactions may take place, such as complete oxidation of the
ethylene and ethylene oxide into carbon dioxide and water,
isomerisation of the ethylene oxide into acetaldehyde and the
secondary oxidation of ethylene into formaldehyde. Said secondary
reactions contribute to lowering the selectivity of the catalytic
oxidation reaction of the ethylene to ethylene oxide.
[0004] Several problems arise simultaneously in the manufacture of
ethylene oxide. The most serious problems are linked to the
strongly exothermic character of the catalytic oxidation reaction
of ethylene to ethylene oxide and to the control of the temperature
of the reaction, in particular the whole length of the reaction
tubes, from the entry of the reactive gas mixture into the tube
reactor up to the exit of the gaseous mixture resulting from the
reaction. One of the major risks of the process is the formation of
hot spots leading to reaction runaways, known generally by the term
"post-combustion", and to the formation of carbon dioxide, carbon
monoxide and aldehydes such as formaldehyde and acetaldehyde, some
of said secondary products being particularly difficult to separate
subsequently from the ethylene oxide. An irregular reaction
temperature profile, poorly controlled and in particular increasing
along the whole length of the reaction tubes, may lead not only to
hot spots, but also to an excessive final temperature. The hot
spots and an excessive final temperature affect the selectivity of
the reaction to ethylene oxide. In addition, a locally high
temperature and an excessive final temperature may be such that
they attain a value corresponding to the maximum flammability
temperature of the gaseous mixture, and thus cause an
explosion.
[0005] Solutions have been proposed for partially resolving some of
said problems through methods of various degrees of complexity.
There is proposed in Australian patent AU 211 242 a process for
manufacturing ethylene oxide in a tube reactor consisting of
conventional reaction tubes which comprise an inlet zone filled
with inert particles such as spheres of alumina and an empty outlet
zone. Between said two zones, the reaction tubes comprise a
reaction zone filled with a silver-based supported catalyst the
concentration of which rises between the inlet and the outlet of
said zone. As a result, the catalytic activity increases along the
reaction tubes, from the inlet up to the outlet of the tubes, in
the flow direction of the reactive gas current.
[0006] There is proposed in American patent U.S. Pat. No. 5,292,904
a process for manufacturing ethylene oxide in a tube reactor
consisting of conventional reaction tubes which comprise a
pre-heating zone situated towards the inlet of the tubes and a
cooling zone situated towards the outlet of the tubes, said two
zones being filled with an inert refractory product such as a
refractory alumina.
[0007] There is proposed in International patent application WO
02/26370 a catalytic reaction process in a tube reactor consisting
of conventional reaction tubes which comprise an upstream portion
and/or a downstream portion situated respectively towards the inlet
and the outlet of the tubes, said portions containing a heat
exchange insert mainly in the form of rods and having a length
equal to 1 to 20% of the total length of the reaction tube. When
the process is used for the manufacture of ethylene oxide, it is
stated that the upstream and downstream portions of the reaction
tubes contain the insert, and that the insert contained in the
upstream portion may have a length equal to 1 to 10% of the total
length of the reaction tube, while the insert contained in the
downstream portion may have a length twice that contained in the
upstream portion. However, it is noticed that in all cases the
catalyst occupies solely the central portion of the reaction tubes
and that a not inconsiderable portion of the tubes is thus filled
with inert solid materials intended to promote solely the heat
exchanges. Thus, a relatively great portion of the conventional
reaction tubes is not reserved for the production of ethylene oxide
and as a result affects the production of ethylene oxide per unit
of internal tube volume available in the reactor.
[0008] International patent application WO 03/01149 describes a
tubular reactor used for exothermic chemical conversions of organic
compounds. The tubular reactor comprises reaction tubes filled with
a catalyst and through which a reactive gas current flows. Each
reaction tube comprises a sequence of zones such that each
downstream zone has a smaller or preferably larger cross-section
than the contiguous upstream zone. However, as illustrated in the
Figures, the cross-section of the reaction tubes only increases
from the prior upstream zone in tubular reactors which are
particularly used for manufacturing maleic anhydride and also used
for manufacturing other organic compounds such as phthalic
anhydride, ethylene oxide, acrylic acid, vinyl acetate or ethylene
dichloride.
[0009] German patent application DE 29 29 300 describes a catalytic
reactor, for use in carrying out endothermic or exothermic
reactions, through which a reactant fluid is flowed, and comprising
reaction tubes filled with catalyst material, which are in thermal
contact with a heat-emitting or heat-absorbing fluid, and
characterized in that the cross-section surface area of the
reaction tubes is varied, along with the direction of flow of the
reacting fluid, depending upon the quantity of heat required for
completion of a given reaction, or the quantity of heat released on
the course of a reaction. However, as illustrated in FIGS. 1 and 4,
the cross-section surface area of the reaction tubes firstly
decreases and then increases along with the direction of flow of
the reacting fluid, while in FIG. 2 the cross-section surface area
firstly increases and then decreases, in FIG. 3 the cross-section
surface area increases for some reaction tubes and decreases for
the other reaction tubes in the reactor, and in FIG. 5 the
cross-section surface area decreases. The reactors described by the
German patent application are proposed to be used in methanol or
ammonia synthesis. The reactor shown in FIG. 2 is specifically used
for methanol synthesis which is an exothermic reaction.
[0010] The process of the present invention is intended to resolve
the technical problems described above. It is intended in
particular to increase the selectivity of the catalytic oxidation
reaction of ethylene to ethylene oxide and the production of
ethylene oxide per unit of internal tube volume available in the
reactor, and simultaneously to improve the safety of the process in
particular as regards the risks of reaction runaway and explosion,
by controlling in particular the profile of the temperature of the
reaction the whole length of the reaction tubes.
[0011] The present invention relates to a process for manufacturing
ethylene oxide by the catalytic oxidation reaction of ethylene by
molecular oxygen in a tube reactor comprising three successive and
adjacent chambers traversed by a reactive gas current comprising
ethylene and molecular oxygen, an inlet chamber of the reactive gas
current, then a central chamber forming a gas current resulting
from the reaction and comprising the ethylene oxide, and an outlet
chamber of the resulting gas current, the central chamber
comprising a bundle of reaction tubes immersed in a heat exchange
fluid and filled with a solid silver-based catalyst in contact with
which the reactive gas current forms the ethylene oxide, each
reaction tube possessing an inlet issuing into the inlet chamber
and an outlet issuing into the outlet chamber, the process being
characterised in that the area of the internal cross-section of the
reaction tubes decreases between the inlet and the outlet of the
tubes over at least a portion of the length of the tubes and
remains constant over any remaining portion.
[0012] FIG. 1 represents diagrammatically a tube reactor comprising
reaction tubes as used in the process of the invention.
[0013] FIGS. 2a, 2b, 3, 4a and 4b represent diagrammatically
various reaction tubes as used in the process of the invention.
[0014] FIG. 5 represents a graph linking, on the ordinate, the
temperature of the reactive gas current (measured in degrees
Celsius) with, on the abscissa, the length of the reaction tube
(measured in metres) from the inlet of the tube, said graph being
drawn according to the conditions of Example 1.
[0015] FIG. 6 represents a graph linking, on the ordinate, the
selectivity (S) of the reaction to ethylene oxide (expressed in %)
to, on the abscissa, the production (P) of ethylene oxide
(expressed in tonnes of ethylene oxide per day) in the conditions
of Examples 1 and 2 and of Comparative Example 3.
[0016] According to the invention, it was found that it is possible
to obtain a relatively stable reaction temperature profile the
whole length of the reaction tubes, to avoid reaction runaways and
to reduce significantly the final temperature of the reaction,
while at the same time improving the selectivity and the output of
the reacting to ethylene oxide, in particular when from the inlet
up to the outlet of the reaction tubes (i.e. in the flow direction
of the reactive gas current) the area of the internal cross-section
of the tubes decreases over the whole length of the tubes, or
decreases over at least a portion of the length of the tubes and
remains constant over the remaining portion. In particular, the
reaction tubes have a shape so that the area of the internal
cross-section of the tubes do not increase over any portion of the
tubes in the flow direction of the reactive gas current. The area
may decrease continuously or, preferably, discontinuously, in
particular by stages. Furthermore, all the reaction tubes present
in the tube reactor preferably have an internal cross-section as
previously described according to the present invention.
[0017] The effects sought by the present invention are particularly
attractive when the area of the internal cross-section (A1) at the
inlet of the reaction tubes is from 1.5 to 12 times, preferably
from 2 to 10 times, in particular from 3 to 9 times greater than
the area of the internal cross-section (A2) at the outlet of said
tubes.
[0018] The effects sought may, in addition, be particularly
remarkable in the following conditions. When the decrease in the
area of the internal cross-section of the reaction tubes is
effected once only over the length of the tubes, either
continuously over a portion of the length of the tubes, or
discontinuously, more particularly by a stage, it may be effected
at the latest (in the flow direction of the reactive gas current)
before the last fifth of the length of the tubes (situated towards
the outlet), preferably before the last quarter, in particular
before the last third, more particularly before the last half of
the length of the tubes (situated towards the outlet), or else at
the earliest not before the first third of the length of the tubes
(situated towards the inlet). When the decrease in the area of the
internal cross-section of the reaction tubes is effected two or
more successive times over the length of the tubes, either
continuously over two or more portions of the length of the tubes,
or discontinuously, more particularly in two or more successive
stages, it may be effected for the first time at the latest (in the
flow direction of the reactive gas current) before the last fifth
of the length of the tubes (situated towards the outlet),
preferably before the last quarter, in particular before the last
third, more particularly before the last half of the length of the
tubes (situated towards the outlet), or else at the earliest not
before the first third of the length of the tubes (situated towards
the inlet), e.g. not before the first 5/12 of the length of the
tubes (situated towards the inlet).
[0019] For example, the reaction tubes may have a length (L) of
from 6 to 20 m, preferably from 8 to 15 m, an area of the internal
cross-section (A1) at the inlet of the tubes of from 12 to 80
cm.sup.2, preferably from 16 to 63 cm.sup.2, and an area of the
internal cross-section (A2) at the outlet of the tubes of less than
A1 and ranging from 1.2 to 16 cm.sup.2, preferably from 1.8 to 12
cm.sup.2.
[0020] The tube reactor is generally of the vertical shell-and-tube
exchanger type, that is to say comprising a vertical bundle of
reaction tubes. By bundle of reaction tubes is meant generally an
assembly of mutually identical and parallel tubes. According to a
practical form of the invention, the reaction tubes may have a
cylindrical shape and exhibit a circular internal cross-section
whose internal diameter (Di) decreases between the inlet and the
outlet of the tubes over at least a portion of the length of the
tubes and remains constant over any remaining portion. Thus, it was
found that from the inlet up to the outlet of the reaction tubes
the internal diameter (Di) of the tubes may decrease over the whole
length of the tubes, or may decrease over at least a portion of the
length of the tubes and remain constant over the remaining portion.
The internal diameter (Di) may decrease continuously or
discontinuously, in particular by stages, from the inlet up to the
outlet of the tubes. Good results are obtained in particular when
the internal diameter (D1i) at the inlet of the reaction tubes is
from 1.2 to 3.5 times, preferably from 1.4 to 3.1 times, more
particularly from 1.7 to 3 times higher than the internal diameter
(D2i) at the outlet of said tubes.
[0021] Remarkable results may also be obtained in the following
circumstances. When the internal diameter (Di) of the reaction
tubes decreases once only over the length of the tubes, either
continuously over a portion of the length of the tubes or
discontinuously, in particular by a stage, the decrease of Di may
be effected at the latest (in the flow direction of the reactive
gas current) before the last fifth of the length of the tubes
(situated towards the outlet), preferably before the last quarter,
in particular before the last third, more particularly before the
last half of the length of the tubes (situated towards the outlet),
or else at the earliest not before the first third of the length of
the tubes (situated towards the inlet). When the internal diameter
(Di) of the reaction tubes decreases two or more successive times
over the length of the tubes, either continuously over two or more
portions of the length of the tubes or discontinuously, in
particular by two or more stages, the decrease of Di may be
effected for the first time at the latest (in the flow direction of
the reactive gas current) before the last fifth of the length of
the tubes (situated towards the outlet), preferably before the last
quarter, in particular before the last third, more particularly
before the last half of the length of the tubes (situated towards
the outlet), or else at the earliest not before the first third of
the length of the tubes (situated towards the inlet), e.g. not
before the first 5/12 of the length of the tubes (situated towards
the inlet).
[0022] For example, the reaction tubes of cylindrical shape may
have a length (L) of from 6 to 20 m, preferably from 8 to 15 m, an
internal diameter (Di) which, according to the invention, decreases
between the inlet and the outlet of the tubes and which may be
chosen in a range of from 12 to 100 mm, preferably from 15 to 90
mm. In addition, the reaction tubes may have an internal diameter
(D1i) at the inlet of the tubes which may be chosen in a range of
from 38 to 100 mm, preferably from 45 to 90 mm, and an internal
diameter (D2i) at the outlet of the tubes which is less than D1i
and which may be chosen in a range of from 12 to 45 mm, preferably
from 15 to 40 mm.
[0023] According to the invention, the reaction tubes have an
internal cross-section whose area decreases between the inlet and
the outlet of the tubes. They may, in addition, have a wall whose
thickness is constant, or on the contrary varies, for example
decreases or increases from the inlet up to the outlet of the tubes
(in the flow direction of the reactive gas current). It is possible
in particular to use reaction tubes of cylindrical shape which have
an internal diameter (Di) which decreases from the inlet up to the
outlet of the tubes, for example continuously or discontinuously,
in particular by stages, as described previously according to the
invention, and which may, in addition, have an external diameter
(De) which is constant between the inlet and the outlet of the
tubes and equal in particular to the external diameter (D1e) at the
inlet of said tubes. In this case, it was found in a remarkable
manner that the resulting enlargement of the wall of the reaction
tubes from the inlet up to the outlet of the tubes does not affect,
or only in an insignificant manner, the effects sought by the
process of the invention.
[0024] The solid silver-based catalyst used in the present
invention may be chosen from among the silver-based supported
catalysts capable of catalysing the oxidation of ethylene to
ethylene oxide with the aid of molecular oxygen. The catalyst may
be chosen from among catalysts comprising mainly of metallic silver
deposited on a porous refractory solid support. The support may be
chosen from among refractory products of natural, artificial or
synthetic origin, preferably from among those having a macro-porous
structure, more particularly having a specific surface area
(B.E.T.) of less than 20 m.sup.2/g, in particular of from 0.01 to
10 m.sup.2/g, and an apparent porosity of more than 20% by volume,
more particularly of from 30 to 70% by volume. The most appropriate
supports may be those which comprise of siliceous and/or aluminous
products (based on silica and/or alumina respectively). For
example, the support may be chosen from among oxides of aluminium
(in particular those known under the trade reference
"Alundum".RTM.), charcoal, pumice stone, magnesia, zirconium,
kieselguhr, fuller's earth, silicon carbide, porous agglomerates
containing silicon and/or silicon carbide, clays, natural,
artificial or synthetic zeolites, metal oxide gel-based materials
containing oxides of heavy metals such as molybdenum or tungsten,
and ceramic products. Aluminous products are preferred, in
particular those containing alumina of the alpha type, having in
particular a specific surface area (B.E.T.) of from 0.15 to 0.6
m.sup.2/g and an apparent porosity of from 46 to 52% by volume. The
B.E.T. method used to determine the specific surface area is
described in J. Am. Chem. Soc., 60, 309-16 (1938).
[0025] The catalyst may contain from 1 to 20%, preferably from 2 to
16% by weight of silver. It may in addition contain at least one
metallic promoter agent, in particular chosen from among the
alkaline metals, alkaline-earth metals such as calcium or barium,
and other metals such as thallium, antimony, tin or rhenium. The
catalyst may come in the form of particles having in particular a
mean diameter at least equal to 1 or 2 mm and at most equal to half
of the narrowest internal diameter of the reaction tubes employed,
in particular a mean diameter chosen from a range of from 1.5 to 15
mm, preferably from 4 to 8 mm, for example in the form of spherical
or hemispherical particles, rings, pellets or granules. The
catalyst may be prepared according to various processes such as
those described in the American patents U.S. Pat. No. 3,043,854,
U.S. Pat. No. 3,207,700, U.S. Pat. No. 3,575,888, U.S. Pat. No.
3,702,259 and U.S. Pat. No. 3,725,307, or in the European patent EP
0 266 015.
[0026] One of the advantages of the present invention is being able
to use reaction tubes containing the catalyst over the whole or at
least over almost the whole (that is to say more than 95%) of the
length of the tubes, from the inlet up to the outlet of the tubes,
and more particularly in the zone situated towards the outlet. Only
one portion, generally at most equal to 5% of the length, situated
towards the outlet, may be occupied by a device for supporting the
catalyst charge, such as a grille or spring). Hence, thanks to the
particular configuration of the reaction tubes according to the
present invention, a maximum catalyst charge may be employed for
the internal tube volume available in the reactor, and said charge
is capable of being, in addition, active for the production of
ethylene oxide. Said advantageous results are, in addition,
obtained while at the same time maintaining a high selectivity of
the reaction to ethylene oxide and supplying in particular a
relatively stable reaction temperature profile over the whole
length of the tubes. It may be possible, however, if it is so
desired, to insert into the reaction tubes inert solid materials,
or preferably, where applicable, to mix the catalyst with said
materials. The inert solid materials may be optionally chosen from
among inert particles or solid and in particular hollow inserts,
for example of metal or of metal alloy, or of inert refractory
product used in particular as a solid inert filling product, for
example in the form of powdery, spherical or hemispherical
particles, rings, pellets or granules. The inert refractory
products optionally used may be of an identical or different nature
to those of the supports present in the catalyst. They may be
chosen from among the catalyst supports, in particular those
mentioned previously, and from among refractory products having in
particular a small B.E.T. specific surface area, preferably of less
than 0.1, more particularly less than 0.05, in particular less than
0.01 m.sup.2/g. The refractory products with a small B.E.T.
specific surface area may be chosen from among silica, alumina,
silicon carbide, alumina and silica mixtures optionally modified by
alkaline or alkaline-earth metals, ceramic products, glass-type
materials such as sodium polysilicates containing more particularly
a stoichiometric excess of silica.
[0027] The process for manufacturing ethylene oxide employs
molecular oxygen, which may be used in the form of pure molecular
oxygen, for example with an oxygen purity equal to or more than 95%
by volume, or in the form of air. The reactive gas current which
traverses the tube reactor may consist of a gaseous mixture of
ethylene, molecular oxygen and optionally one or more other gases
chosen from among carbon dioxide, nitrogen, argon, methane, ethane
and at least one reaction inhibitor or moderator chosen in
particular from among halogenated hydrocarbons such as ethyl
chloride, vinyl chloride or 1,2-dichloroethane. In the reactive gas
current, the concentration of ethylene is generally as high as
possible, more particularly equal to or less than 40% by volume,
and it is in particular chosen from a range of from 15 to 35% by
volume. The concentration of molecular oxygen in the reactive gas
current may be chosen from a range of 3 to 20%, preferably of 4 to
10% by volume. The concentration of carbon dioxide in the reactive
gas current is generally less than or equal to 10% by volume, and
may be chosen from a range of from 4 to 8% by volume. Methane
and/or nitrogen may be used as diluents in the reactive gas current
in order more particularly to reduce the flammability range of the
gaseous mixture and to remove it into a zone not used. Thus methane
and/or nitrogen may be present in the reactive gas current in a
concentration as high as possible. For example, the reactive gas
current may contain by volume from 1 to 40% of ethylene, from 3 to
12% of molecular oxygen, from 0 to 10% of carbon dioxide, from 0 to
3% of ethane, from 0.3 to 50 parts by volume per million (vpm) of a
reaction inhibitor or moderator of the halogenated hydrocarbon
type, the remainder being argon and/or nitrogen and/or methane. The
absolute pressure of the reactive gas current in the tube reactor
may be chosen in a range of from 0.1 to 4 MPa, preferably from 1 to
3 MPa. The volume space hour velocity (VSHV) of the reactive gas
current in the reaction tubes may be chosen in a range of from 1000
to 10 000 h.sup.-1 (m.sup.3 per m.sup.3.h of catalyst), preferably
from 2000 to 8000 h.sup.-1, measured in standard temperature and
pressure conditions.
[0028] The reactive gas current may with advantage be pre-heated to
a temperature of from 100 to 200.degree. C., preferably from 140 to
190.degree. C. The temperature of the reactive gas current in the
reaction tubes may be chosen in a range of from 140 to 350.degree.
C., preferably from 180 to 300.degree. C., more particularly from
190 to 280.degree. C. Owing to the process of the invention, the
temperature of the reactive gas current at the inlet of the
reaction tubes may rise very rapidly or as it were instantaneously
to a temperature equal to or more than 210.degree. C. It may then
continue to increase, but far more moderately, and attain a maximum
temperature of at most equal to 270.degree. C., preferably at most
equal to 265.degree. C., more particularly at most equal to
260.degree. C., in particular over a portion of the length of the
tubes capable of extending from the first quarter to the fourth
fifth, preferably from the first half to the third quarter of the
length of the tubes in the flow direction of the reactive gas
current. At the outlet of the reaction tubes, the temperature of
the gas current resulting from the reaction may remain at said
maximum temperature or, preferably, may decrease to a temperature
equal to or less than 250.degree. C., preferably equal to or less
than 240.degree. C., more particularly equal to or less than
230.degree. C., for example in a range of from 180 to 250.degree.
C., preferably from 190 to 240.degree. C., more particularly from
200 to 230.degree. C.
[0029] It is particularly advantageous to note that, owing to the
process of the invention, the exchange of heat along the reaction
tubes makes it possible to combine a relatively stable reaction
temperature profile and a maximum quantity of catalyst used in
optimum activity conditions (the whole length of the tubes and more
particularly in the zone situated towards the outlet of the tubes)
per unit of internal tube volume available in the reactor. Said
combination makes it possible to prevent a relatively great portion
of the reaction tubes being sacrificed to something other than the
production of ethylene oxide and the maintenance of the catalyst
charge in the tubes, more particularly by an absence of the
catalyst, namely with the sole aim of controlling the heat
exchanges and preventing hot spots. One of the major advantages of
the process of the invention may further come from the fact that
the temperature of the gas current resulting from the reacting at
the outlet of the reaction tubes may be substantially reduced by at
least 5.degree. C., for example by at least 10.degree. C., compared
with the conventional processes. The result of said substantial
reduction in the temperature is that for any other furthermore
equal condition, such as an identical concentration of molecular
oxygen in the reactive gas current, the limits of flammability of
said current may be distanced accordingly and may thus permit a far
safer process to be provided without in so doing sacrificing the
yield and the selectivity of the reaction to ethylene oxide.
[0030] The bundle of reaction tubes is immersed in a heat exchange
fluid which may be chosen in particular from among organic beat
carrying fluids and water superheated under pressure (that is to
say water at saturation temperature). The organic heat carrying
fluids may be mixtures of oils or hydrocarbons such as linear or
branched alkanes having in particular a boiling point higher than
the maximum reaction temperature. It is possible to use the organic
heat carrying fluids at a relative pressure of from 100 to 1500
kPa, preferably from 200 to 800 kPa, more particularly from 200 to
600 kPa. The organic heat carrying fluids may be chosen in
particular from "Isopar".RTM. of Exxon, "Therminol".RTM. of
Monsanto and "Dowtherm".RTM. of Dow Chemicals. They may be used
according to a process and a heat exchange apparatus as described
in European patent application EP 0 821 678, in particular in FIG.
1 or 2, or else in American patent U.S. Pat. No. 4,759,313. The
heat exchange fluid may also be water superheated under pressure,
in particular used at a relative pressure of from 1500 to 8000 kPa.
In this case, the superheated water may be used according to a
process and a heat exchange apparatus as described in American
patent U.S. Pat. No. 5,292,904. The temperature of the heat
exchange fluid at the outlet of the tube reactor generally lies
between 210 and 300.degree. C., preferably between 220 and
280.degree. C., more particularly between 210 and 280.degree. C.
The temperature of the heat exchange fluid at the inlet of the tube
reactor generally lies between 120 and 250.degree. C., preferably
between 130 and 240.degree. C., more particularly between 130 and
230.degree. C.
[0031] The process of the invention may with advantage be carried
out continuously, more particularly by utilising continuously the
reactive gas current which traverses successively and continuously
the three chambers of the tube reactor and by recovering
continuously at the outlet of the reactor the gas current resulting
from the reaction and containing the ethylene oxide.
[0032] FIG. 1 is a diagrammatic representation of a tube reactor as
used in the process of the invention. The tube reactor is of the
vertical shell-and-tube exchanger type. The reactor contains three
successive and adjacent chambers: an inlet chamber (1), then a
central chamber (2) and an outlet chamber (3). There issues into
the inlet chamber (1) a pipe (4) for the feeding of a reactive gas
current containing ethylene and molecular oxygen. The central
chamber (2) comprises a bundle of reaction tubes (5) parallel and
identical to one another, and preferably cylindrical, each tube (5)
containing in inlet (6) issuing into the inlet chamber (1) and an
outlet (7) issuing into the outlet chamber (3). The reaction tubes
(5) are filled with a solid silver-based catalyst (8) (shown tinted
grey) over the whole or almost the whole of the length of the tubes
(with the exception of a device for supporting the catalyst charge
in the tube, such as a grille or a spring, not shown in FIG. 1).
The area of the internal cross-section of each reaction tube (5)
decreases discontinuously between the inlet (6) and the outlet (7)
of the tubes, by three successive stages (9), so that each reaction
tube (5) is composed of four successive and contiguous tubular
sections (10), each having an increasingly reduced internal
cross-sectional area from the inlet (6) to the outlet (7). The
reaction tubes (5) are immersed in a heat exchange fluid (11) which
is introduced into the central chamber (2) through a pipe (12) for
the feeding of fluid and which is drawn off from the central
chamber (2) through a discharge pipe (13). The outlet chamber (3)
is provided with a pipe (14) for discharge of the gaseous current
resulting from the reaction and containing the ethylene oxide.
[0033] FIGS. 2a and 2b are diagrammatic representations of the
reaction tubes (5) capable of being used in the tube reactor shown
in FIG. 1 and enabling the process of the invention to be carried
out. The elements of FIGS. 2a and 2b identical to those shown in
FIG. 1 are marked with the same numerical references. FIG. 2a
represents diagrammatically a reaction tube (5) which is provided
with an inlet (6) and an outlet (7), and which has an internal
cross-sectional area which decreases continuously from the inlet
(6) to the outlet (7). FIG. 2b represents diagrammatically a
reaction tube (5) provided with an inlet (6) and an outlet (7). The
area of the internal cross-section of the reaction tube (5)
decreases continuously over a portion (15) of the length of the
tube, and remains constant over the remaining upstream portion (16)
situated towards the inlet (6) and over the remaining downstream
portion (17) situated towards the outlet (7). The reaction tubes
(5) as represented in FIGS. 2a and 2b are shown empty and without
the catalyst (8) as represented in FIG. 1.
[0034] FIG. 3 is a diagrammatic representation of a reaction tube
(5) capable of being used in the tube reactor shown in FIG. 1
according to the process of the invention. The elements of FIG. 3
identical to those shown in FIG. 1 are marked with the same
numerical references. The reaction tube (5) is provided with an
inlet (6) and an outlet (7). The area of the internal cross-section
of the reaction tube (5) decreases discontinuously between the
inlet (6) and the outlet (7), by two successive stages (9), so that
the reaction tube (5) is composed of three successive and
contiguous tubular sections (10), each having an increasingly
reduced internal cross-sectional area from the inlet (6) to the
outlet (7). The reaction tube (5) as shown in FIG. 3 is shown empty
and without the catalyst (8) as represented in FIG. 1.
[0035] FIGS. 4a and 4b are diagrammatic representations of the
reaction tubes (5) capable of being used in the tube reactor shown
in FIG. 1 and enabling the process of the invention to be carried
out. The elements of FIGS. 4a and 4b identical to those shown in
FIG. 1 are marked with the same numerical references. FIG. 4a
represents diagrammatically a reaction tube (5) of cylindrical
shape which is provided with an inlet (6) and an outlet (7). The
area of the circular internal cross-section of the reaction tube
decreases discontinuously between the inlet (6) and the outlet (7),
by two successive stages (9), so that the reaction tube (5) is
composed of three successive and contiguous cylindrical tubular
sections (10), each having an increasingly reduced internal
diameter (Di) from the inlet (6) to the outlet (7). The reaction
tube (5) possesses an external diameter (De) which remains constant
between the inlet (6) and the outlet (7). The reaction tube (5) may
be in practice composed of three cylindrical and coaxial tubes
(10.sub.A, 10.sub.B and 10.sub.C) inserted into one another, so
that in particular the external surface of the tube 10.sub.B is
contiguous with the internal surface of the tube 10.sub.A, and that
the external surface of the tube 10.sub.C is contiguous with the
internal surface of the tube 10.sub.B. FIG. 4b represents
diagrammatically a reaction tube (5) of cylindrical shape which is
provided with an inlet (6) and an outlet (7). The reaction tube (5)
possesses an internal diameter (Di) which decreases continuously
over a portion (15) of the length of the tube, and which remains
constant over the remaining upstream portion (16) situated towards
the inlet (6) and over the remaining downstream portion (17)
situated towards the outlet (7). The reaction tube (5) possesses an
external diameter (De) which remains constant between the inlet (6)
and the outlet (7). The reaction tube (5) may be in practice
composed of two cylindrical and coaxial tubes (16.sub.A and
17.sub.A) inserted into one another, so that in particular the
external surface of the tube (17.sub.A) is contiguous with the
internal surface of the tube (16.sub.A). The tube (17.sub.A) is
prolonged and contiguous with a tube (15.sub.A) coaxial with the
two tubes (16.sub.A and 17.sub.A). The tube (15.sub.A) has a
cylindrical external wall whose surface is contiguous with the
internal surface of the tube (16.sub.A), and a revolving truncated
internal wall whose large base contiguous with the tube (17.sub.A)
has a diameter identical to the internal diameter of the tube
(17.sub.A) and whose small base has a diameter identical to the
internal diameter (Di) of the tube (16.sub.A). The reaction tubes
(5) as shown in FIGS. 4a and 4b are shown empty and without the
catalyst (8) as represented in FIG. 1.
[0036] The process of the present invention offers in particular
the following advantages: [0037] a substantially increased
selectivity of the reaction to ethylene oxide for one and the same
level of production of ethylene oxide, for example of at least 3
points (expressed in %); [0038] a clearly increased production of
ethylene oxide by unit of internal tube volume available in a tube
reactor; [0039] a maximum charge of active catalyst in the
production of ethylene oxide per unit of internal tube volume
available in a tube reactor; [0040] a relatively stable reaction
temperature profile the whole length of the reaction tubes; [0041]
a substantially reduced temperature at the outlet of the reaction
tubes compared with that of the conventional processes; [0042] a
safer process for manufacturing ethylene oxide by virtue of
operating conditions which are more removed from the flammability
conditions of the gas current; [0043] a substantial decrease in the
quantity of carbon dioxide produced compared with that of ethylene
oxide, and a marked reduction in the discharges of carbon dioxide
into the environment.
[0044] The selectivity of the reaction to ethylene oxide (expressed
in %) may be calculated according to the following equation:
Selectivity=100.times.(molar production of ethylene oxide)/(molar
consumption of ethylene) (1)
[0045] The following examples illustrate the present invention.
EXAMPLE 1
[0046] The manufacture of ethylene oxide was carried out
continuously in a tube reactor as shown in FIG. 1, comprising an
inlet chamber (1), a central chamber (2) and an outlet chamber (3).
The central chamber (2) comprised a bundle of 3709 cylindrical
reaction tubes, identical and parallel to one another. Each
reaction tube (5), as shown diagrammatically in FIG. 3, comprised
two successive stages (9), such that the tube (5) was composed of
three successive and contiguous cylindrical tubular sections (10),
each having a length (L) and an internal diameter (Di) decreasing
between the inlet (6) and the outlet (7). The length (L) and the
internal diameter (Di) of the three sections (10) had successively
between the inlet (6) and the outlet (7) of the tubes the following
values: L=5 m and Di=51.2 mm; L=5 m and Di=38.4 mm; L=2 m and
Di=25.6 mm. The reaction tubes (5) were filled with a silver-based
supported catalyst, in an equal manner between one another and over
almost the whole (96%) of their length (only a last portion 0.5 m
in length situated just before the outlet (7) being occupied by a
spring for supporting the catalyst in the tube). The catalyst was a
catalyst containing 14.7% by weight of silver supported on alumina.
The total volume of the catalyst introduced into the reaction tubes
of the reactor is about 62.5 m.sup.3.
[0047] There was introduced continuously into the tube reactor a
reactive gas current containing by volume 28.2% of ethylene, 6.5%
of molecular oxygen, 5% of carbon dioxide, 4.7% of nitrogen, 5.5%
of argon, 0.3% of ethane, 4.8 vpm of ethyl chloride, the remainder
being methane, at a flow rate of 270.8 tonnes/hour, at an absolute
pressure of 2.06 MPa, the reactive gas current being pre-heated to
about 150.degree. C. Replenishments with fresh constituents of the
reactive gas current, more particularly with fresh ethylene and
oxygen, were carried out continuously to enable the composition of
said current to be kept constant during the production. The bundle
of reaction tubes was immersed in water superheated to 210.degree.
C. (at saturation temperature). The temperature of the reactive gas
current was measured along the reaction tubes, which made it
possible, according to the graph shown in FIG. 5, to draw a curve
(1) plotting the temperature of the gas current as a function of
the length of the tube (5) starting from the inlet (6).
[0048] Five tests were conducted in said conditions, the rates of
introduction of fresh constituents of the reactive gas current,
more particularly of fresh ethylene and oxygen, being changed for
each of them in order to obtain for each test a production (P) of
ethylene oxide (expressed in tonnes of ethylene oxide per day) and
for each production (P) thus obtained the selectivity (S) of the
reaction to ethylene oxide (expressed in %) was calculated
according to equation (1) mentioned above. The results of said
tests were listed in Table 1 and enabled a curve (1) to be drawn
according to the graph shown in FIG. 6 linking the selectivity (S)
to the production (P) of ethylene oxide. TABLE-US-00001 TABLE 1
Selectivity (S) as a function of the production (P) of ethylene
oxide Selectivity (S) Production (P) Example 1 Test (%) (t/d) 1
83.2 256 2 82.1 275 3 81.0 290 4 79.8 302 5 78.5 314
EXAMPLE 2
[0049] Exactly the same procedure was adopted as in Example 1,
except that the tube reactor comprised a bundle of 2760 cylindrical
reaction tubes (5), identical and parallel to one another, and that
each tube (5) as shown in FIG. 3 comprised two successive stages
(9), so that the tube was composed of three successive and
contiguous cylindrical tubular sections (10), each having a length
(L) and an internal diameter (Di) decreasing between the inlet (6)
and the outlet (7). The length (L) and the internal diameter (Di)
of the three sections (10) had successively between the inlet (6)
and the outlet (7) of the tubes the following values: L=5 m and
Di=64.0 mm; L=5 m and Di=38.4 mm; L=2 m and Di=25.6 mm. The
reaction tubes were filled with the silver-based catalyst, as in
Example 1, in an equal manner between one another and over almost
the whole (96%) of their length. The total volume of the catalyst
introduced into the reaction tubes of the reactor was substantially
identical to that of Example 1.
[0050] Three tests were conducted in said conditions, the rates of
introduction of fresh constituents of the reactive gas current,
more particularly of fresh ethylene and oxygen, being changed for
each of them in order to obtain for each test a production (P) of
ethylene oxide (expressed in tonnes of ethylene oxide per day) and
for each production (P) thus obtained the selectivity (S) of the
reaction to ethylene oxide (expressed in %) was calculated
according to equation (1) mentioned above. The results of said
tests were listed in Table 2 and enabled a curve (2) to be drawn
according to the graph shown in FIG. 6 linking the selectivity (S)
to the production (P) of ethylene oxide. TABLE-US-00002 TABLE 2
Selectivity (S) as a function of the production (P) of ethylene
oxide Selectivity (S) Production (P) Example 2 Test (%) (t/d) 1
81.7 277 2 80.4 299 3 78.9 315
EXAMPLE 3 (Comparative)
[0051] Exactly the same procedure was adopted as in Example 1,
except that the tube reactor comprised a bundle of 4750 cylindrical
reaction tubes (5), identical and parallel to one another, and that
each tube (5) had a conventional shape and possesses in particular
an internal diameter (Di) which was constant between the inlet (6)
and the outlet (7) of the tubes and which was equal to 38.7 mm, and
a length (L) of 12 m. The reaction tubes were filled with the
silver-based catalyst, as in Example 1, in an equal manner between
them and over almost the whole (96%) of their length. The total
volume of catalyst introduced into the reaction tubes of the
reactor was substantially identical to that of Example 1.
[0052] The temperature of the reactive gas current was measured
along the reaction tubes, which enabled a curve (2) to be drawn
according to the graph shown in FIG. 5 plotting the temperature of
the gas current as a function of the length of the tube (5)
starting from the inlet (6).
[0053] Five comparative tests were conducted in said conditions,
the rates of introduction of fresh constituents of the reactive gas
current, more particularly of fresh ethylene and oxygen, being
changed for each of them in order to obtain for each test a
production (P) of ethylene oxide (expressed in tonnes of ethylene
oxide per day) and for each production (P) thus obtained the
selectivity (S) of the reacting to ethylene oxide (expressed in %)
was calculated according to equation (1) mentioned above. The
results of said tests were listed in Table 3 and enabled a curve
(3) to be drawn according to the graph shown in FIG. 6 linking the
selectivity (S) to the production (P) of ethylene oxide.
TABLE-US-00003 TABLE 3 Selectivity (S) as a function of the
production (P) of ethylene oxide Example 3 Selectivity (S)
Production (P) (comparative) Test (%) (t/d) 1 83.8 235 2 82.8 248 3
81.8 257 4 80.8 266 5 79.7 275
[0054] An analysis of the results given in Tables 1, 2 and 3 and in
the graphs of FIGS. 5 and 6 shows that: [0055] (a) according to the
process of the invention, the reaction temperature profile along
the tubes was relatively stable between the inlet and the outlet of
the tubes (curve (1) of FIG. 5), compared with the temperature
profile obtained with conventional reaction tubes (curve (2) of
FIG. 5); thus according to the invention, in the inlet zone of the
tubes the temperature rose far quicker and attained very rapidly
the temperature at which the catalytic reaction for the formation
of ethylene oxide started; thereafter the temperature continued to
increase progressively and attained a maximum value of close to
250.degree. C. and then decreased slightly to about 215.degree. C.,
in particular in the outlet zone of the tubes, which thus made it
possible to distance the operating conditions from the maximum
flammability zone of the gaseous mixture, and nevertheless gave the
catalyst an opportunity to continue to produce ethylene oxide with
a good selectivity; [0056] (b) the selectivity (S) of the reaction
to ethylene oxide for a given production (P) of ethylene oxide was,
thanks to the process of the invention, higher (curves (1) and (2)
of FIG. 6) than the selectivity (S) obtained according to a
conventional process, all things being equal (curve (3) of FIG.
6).
* * * * *