PROCESS FOR PREPARING ETHENE
The present invention relates to a process for producing ethene by the vapour phase
dehydration of ethanol using a heteropolyacid catalyst.
Ethene is an important commodity chemical and monomer which has traditionally
been produced industrially by the steam or catalytic cracking of hydrocarbons derived from
crude oil. However there remains an increasing need to find alternative economically
viable methods of making this product. By virtue of its ready availability from the
fermentation of biomass and synthesis gas based technologies, ethanol is emerging as an
important potential feedstock from which ethene can be made in the future.
The production of ethene by the vapour phase chemical dehydration of ethanol is a
well-known chemical reaction which has been operated industrially for many years (see for
example Kirk Othmer Encyclopaedia of Chemical Technology (third edition), Volume 9,
pages 4 11 to 413). Traditionally this reaction has been carried out in the presence of an
acid catalyst such as activated alumina or supported phosphoric acid.
In recent years attention has turned to finding alternative catalysts having improved
performance. This has led to the use of supported heteropolyacid catalysts, such as those
disclosed in EP1925363, which have the benefit of improved selectivity, productivity and
reduced ethane formation following the dehydration of a feedstock comprising ethanol and
ethoxyethane for the production of ethene. This is desirable because firstly ethane is an
undesirable by-product and secondly its separation from ethene on a large scale is both
difficult and energy intensive. Related documents WO 2007/063281 and WO
2007/003899 also disclose modes of carrying out dehydration of oxygenate feedstocks
with supported heteropolyacid catalysts.
In the dehydration process, a feed typically comprising ethanol, optionally water and
other components (e.g. ethoxyethane) is continuously fed to a reactor containing a bed of
heteropolyacid catalyst and the products continuously removed. Under steady state
conditions, the feed entering the reactor is rapidly converted near the inlet into an
equilibrium mixture of water, ethanol and ethoxyethane (the product of a rapid first stage
dehydration of the ethanol). Such processes are typically conducted at elevated
temperature and pressure. In exemplified dehydration processes employing heteropolyacid
catalysts disclosed in the prior art, the temperature of the reaction does not exceed 240 °C,
whilst the sum of the partial pressures of the reactants is typically 2 MPa (i.e. excluding
partial pressures of inert diluents, such as nitrogen).
It has been found that productivity in a process for producing ethene by the vapour
phase dehydration of ethanol using a heteropolyacid catalyst is improved by operating at
high temperature; in particular at temperatures higher than those exemplified in the prior
art. Although it has now become desirable to operate at the highest possible temperatures
to increase ethene productivity, whilst maintaining appropriate selectivity, one problem
that has hitherto not been acknowledged relates to catalyst deactivation. It has been found
that when operating the dehydration process at high temperature, deactivation of the
heteropolyacid catalyst is exacerbated. Without being bound by any particular theory, this
is believed to occur as a result of undesirable side reactions with high activation energies,
which contribute to deactivation, becoming more prevalent as a result of the higher
temperatures being used.
It is known that oxygenate dehydration can lead to carbon build-up on acidic
catalysts, such as silicotungstic-Si0 , which leads to catalyst deactivation. Carbon laydown
leading to catalyst deactivation is, for instance, mentioned in WO 2008/138775. That
document reports such deactivation in a heteropolyacid catalysed oxygenate dehydration
conducted at atmospheric pressure and comprising use of a sequence of vapour phase
feeds, including ethanol in helium and diethyl ether in helium. Deactivation results
obtained in respect of an equivalent operation conducted at an elevated pressure of 2.1
MPa (21 bara), that is, the sum of the partial pressures of the reactants excluding inert
diluents/components, were reported as being consistent with those observed at atmospheric
pressure. This suggests that carbon lay-down is unaffected by the pressure of the
operation.
Replacement of the catalyst in a dehydration system is labour intensive, has
significant materials costs and involves temporarily shutting down what is likely to be a
continuous process, which has detrimental impact on product output. Consequently, there
is likely to be a greater motivation to accept more moderate productivity by operating at
lower temperature in order to benefit from longer catalyst lifetime.
It has now surprisingly been found that catalyst lifetime during operation at high
temperatures can be extended by performing the dehydration process at lower pressures
than exemplified in the prior art. Contrary to what is suggested in the prior art, by
performing the dehydration reaction at certain intermediate pressures, the temperature of
the reaction may be increased to enhance ethene productivity, without exacerbating
catalyst deactivation. Consequently, the particular combination of process features
according to the present invention has the benefit of maximising productivity in a
dehydration process over an extended catalyst lifetime.
According to the present invention, there is provided a process for the preparation of
ethene by vapour phase chemical dehydration of a feed comprising ethanol (and preferably
water and/or ethoxyethane), said process comprising contacting the feed with a supported
heteropolyacid catalyst in a reactor, wherein the feed temperature is at least about 250 °C
and the pressure inside the reactor is at least about 0.80 MPa but less than about 1.80 MPa.
Reference herein to the pressure inside the reactor corresponds to the sum of the
partial pressures of the reactants, namely those of ethanol and (if present) water and
ethoxyethane, as well as the partial pressure of the ethylene product. Unless otherwise
indicated herein, partial pressures of inert diluents, such as helium and nitrogen, or other
inert components are excluded from the total stated pressure. Thus, reference to reactor
pressure herein is in accordance with the formula: Prea ctor = Pwater + Pethanoi + Pethoxyethane +
Pethylene-
As will be appreciated by the skilled person, there is often a pressure drop that occurs
in a dehydration reactor between the point where the feed stream enters the reactor and that
where the effluent stream emerges from the reactor. For example, the feed stream pressure
may be at about 1.4 MPa whilst the effluent stream may be at a pressure of about 1.0 MPa;
corresponding to a pressure drop of about 0.4 MPa. As a consequence, there is, to a
varying extent, an internal pressure gradient which exists inside the reactor itself. It is
therefore to be understood that reference herein to the "pressure inside the reactor", or the
"internal pressure of the reactor", means any pressure falling within the pressure range
defined by the above-mentioned internal pressure gradient. The pressure inside the reactor
itself therefore lies between the feed stream pressure and the effluent stream pressure.
It has been surprisingly found that the combination of operating conditions according
to the present invention maximises ethene productivity whilst significantly reducing the
level of heteropolyacid catalyst deactivation which would otherwise result from conducting
the reaction at higher temperature than is conventional for this type of reaction.
Mechanisms by which the supported heteropolyacids are believed to undergo deactivation
include: i) neutralisation by inorganic cations, such as ammonia / ammonium cations, and
organic nitrogen-containing compounds; ii) carbon deposition; and iii) decomposition of
the heteropolyacid to its constituent oxides.
Deactivation as a result of neutralisation by inorganic cations and organic nitrogencontaining
compounds may be mitigated by committing the ethanol based raw materials to
a clean-up procedure to remove the neutralising species. Without wishing to be bound by
any particular theory, it is believed that the operating conditions according to the process
of the present invention largely eliminate any deactivation of the heteropolyacid catalyst as
a result of carbon deposition and decomposition. A lower pressure of operation is believed
to reduce the amount of adsorbed species on the surface of the catalyst, which may lead to
deactivation. Meanwhile, operating at pressures above atmospheric, for instance at
pressures of at least about 0.80 MPa inside the reactor, is believed to help reduce carbon
deposition. As a consequence, the catalyst lifetime is significantly extended, which has
clear economic benefits relating to re-use and replacement of the catalyst, as well as the
reduction of waste. The operating conditions of the present invention thus correspond to a
narrow window within which significant catalyst deactivation is avoided, whilst ethylene
productivity is promoted.
The dehydration of the feedstock according to the present invention is believed
(Chem. Eng Comm. 1990, 95, 27 to 39) to proceed by either the direct dehydration to
olefin(s) and water (Equation 1); or via an ether intermediate (Equations 2 and 3).
(1) EtOH = + H20
(2) EtOH Et20 + H20
(3) Et20 = + EtOH
The direct conversion of the ether to two moles of olefin and water has also been
reported (Chem. Eng. Res. and Design 1984, 62, 8 1 to 91). All of the reactions shown
above are typically catalysed by Lewis and/or Bronsted acids. Equation 1 shows the
endothermic direct elimination of ethanol to ethene and water; competing with Equation 1
are Equations 2 and 3 i.e. the exothermic etherification reaction (Equation 2), and the
endothermic elimination of ethoxyethane to produce ethene and ethanol (Equation 3).
However, the dehydration reaction of ethanol to ethene is overall said to be endothermic.
The present invention provides a process for the preparation of ethene by vapour
phase chemical dehydration of a feed comprising ethanol, (and preferably further
comprising water and/or ethoxyethane), said process comprising contacting the feed with a
supported heteropolyacid catalyst in a reactor, wherein the feed temperature is at least
about 250 °C and the pressure inside the reactor is at least about 0.80 MPa but less than
about 1.80 MPa.
Preferably, the amount of water in the feed of the process of the present invention is
at most about 50 wt.%, more preferably at most about 20 wt.%, most preferably at most
about 10 wt.%, or even at most about 7 wt.%, based on the total weight of water, ethanol
and ethoxyethane in the reactant feed stream. Preferably, the amount of water in the
reactant feed stream is at least about 0.1 wt.%, more preferably at least about 0.5 wt.% and
most preferably at least about 1 wt.%, based on the total weight of water, ethanol and
ethoxyethane in the reactant feed stream.
The liquid product stream following olefin removal comprises mostly unreacted
ethanol, diethyl ether and water. The applicants have found that it is particularly preferable
to recycle the major portion of the alcohols and ethers back to the vapour phase
dehydration reactor after water by-product removal.
In some embodiments of the invention, the feed comprises an inert, non-condensable
diluent. In other embodiments, an inert, non-condensable diluent is added down the
catalyst bed, or between multple catalyst beds arranged in series or in parallel, if used.
Preferred diluents comprise nitrogen, helium, ethene and/or saturated hydrocarbons, for
example hexanes, 2-methylpropane or n-butane. More preferably, the feed diluent is
selected from nitrogen and/or helium.
As regards further preferred operating conditions of the process of the present
invention, the feed temperature for the dehydration reaction is preferably at least about 252
°C, more preferably the feed temperature for the reaction is at least about 255 °C, even
more preferably the feed temperature for the reaction is at least about 260 °C, even more
preferably still the feed temperature for the reaction is at least about 280 °C. Most
preferably, the feed temperature for the reaction is at least about 300 °C. The upper limit
of the feed temperature is below the temperature at which selectivity for ethene is
negatively impacted and/or one which is overly energy intensive. Preferably, the upper
limit of the feed temperature is about 350 °C, more preferably about 325 °C. Thus,
preferred feed temperature ranges for the dehydration reaction include: a) at least about
252 °C to about 350°C; b) at least about 252 °C to about 325 °C; c) at least about 255 °C to
about 350 °C; d) at least about 255 °C to about 325 °C; e) at least about 260 °C to about
350 °C; f at least about 260 °C to about 325 °C; g) at least about 280 °C to about 350 °C;
h) at least about 280 °C to about 325 °C; i) at least about 300 °C to about 350 °C; and j ) at
least about 300 °C to about 325 °C.
In a preferred embodiment, the reactor has an internal pressure of from about 0.90
MPa to about 1.60 MPa. More preferably, the reactor has an internal pressure of from
about 0.95 MPa to about 1.30 MPa. Most preferably, the reactor has an internal pressure
of from about 1.00 MPa to about 1.20 MPa.
Preferably, the feed stream pressure is from about 1.00 MPa to about 1.80 MPa, more
preferably the feed stream pressure is from about 1.20 MPa to about 1.60 MPa, and most
preferably the feed stream pressure is from about 1.30 MPa to about 1.50 MPa, for
example about 1.40 MPa. Preferably, the effluent stream pressure is from about 0.80 MPa
to about 1.40 MPa, more preferably the effluent stream pressure is from about 0.85 MPa to
about 1.20 MPa, and most preferably the effluent stream pressure is from about 0.90 MPa
to about 1.10 MPa, for example about 1.00 MPa.
In accordance with the present invention, any of the temperature ranges mentioned
above may be taken in combination with any of the pressure ranges described hereinbefore.
The term "heteropolyacid", as used herein and throughout the description of the
present invention, is deemed to include inter alia; alkali, alkali earth, ammonium, free
acids, bulky cation salts, and/or metal salts (where the salts may be either full or partial
salts) of heteropolyacids. Hence, the heteropolyacids suitable for the present invention
may be complex, high molecular weight anions comprising oxygen-linked polyvalent
metal atoms. Typically, each anion comprises about 12 to about 18, oxygen-linked
polyvalent metal atoms. The polyvalent metal atoms, known as peripheral atoms, surround
one or more central atoms in a symmetrical manner. The peripheral atoms may be one or
more of molybdenum, tungsten, vanadium, niobium, tantalum, or any other polyvalent
metal. The central atoms are preferably silicon or phosphorus, but may alternatively
comprise any one of a large variety of atoms from Groups I- VIII in the Periodic Table of
elements. These include copper, beryllium, zinc, cobalt, nickel, boron, aluminium,
gallium, iron, cerium, arsenic, antimony, bismuth, chromium, rhodium, silicon,
germanium, tin, titanium, zirconium, vanadium, sulphur, tellurium, manganese nickel,
platinum, thorium, hafnium, cerium, arsenic, vanadium, antimony ions, tellurium and
iodine. Suitable heteropolyacids include Keggin, Wells-Dawson and Anderson-Evans-
Perloff heteropolyacids. Specific examples of suitable heteropolyacids are as follows:
18-tungstophosphoric acid - H6[P2W18062] .xH20
12-tungstophosphoric acid - H3[PW12O40].xH2O
12-tungstosilicic acid - H4[SiW12O40].xH2O
Cesium hydrogen tungstosilicate - Cs3H[SiW12O40].xH2O
and the free acid or partial salts of the following heteropolyacids acids:
Monopotassium tungstophosphate - KH5[P2W18062].xH20
Monosodium 12-tungstosilicic acid - NaK3[SiW12O40].xH2O
Potassium tungstophosphate - K6[P2 18062] .xH20
Ammonium molybdodiphosphate - (NH4)6 [P2Mo18062] .xH20
Potassium molybdodivanado phosphate - K5[PMoV2O40].xH2O
In addition, mixtures of different heteropolyacids and salts can be employed. The
preferred heteropolyacids for use in the process described by the present invention is any
one or more heteropolyacid that is based on the Keggin or Wells-Dawson structures; more
preferably the chosen heteropolyacid for use in the process described by the present
invention is any one or more of the following: heteropolytungstic acid (such as
silicotungstic acid and phosphotungstic acid), silicomolybdic acid and phosphomolybdic
acid. Most preferably, the chosen heteropolyacid for use in the process described by the
present invention is any one or more silicotungstic acid, for example 12-tungstosilicic acid
(H4[SiWi2O40].xH2O).
Preferably, the heteropolyacids employed according to the present invention may
have molecular weights of more than about 700 and less than about 8500, preferably more
than about 2800 and less than about 6000. Such heteropolyacids also include dimeric
complexes.
The supported catalyst may be conveniently prepared by dissolving the chosen
heteropolyacid in a suitable solvent, where suitable solvents include polar solvents such as
water, ethers, alcohols, carboxylic acids, ketones and aldehydes; distilled water and/or
ethanol being the most preferable solvents. The resulting acidic solution has a
heteropolyacid concentration that is preferably comprised between about 10 to about 80
wt%, more preferably about 20 to about 70 wt% and most preferably about 30 to about 60
wt%. This said solution is then added to the chosen support (or alternatively the support is
immersed in the solution). The actual volume of acidic solution added to the support is not
restricted, and hence may be enough to achieve incipient wetness or wet impregnation,
where wet impregnation (i.e. preparation using an excess acidic solution volume relative to
pore volume of support), is the preferred method for the purposes of the present invention.
The resulting supported heteropolyacid may be modified, and various salts of
heteropolyacid may then be formed in the aqueous solution either prior to, or during,
impregnation of the acidic solution onto the support, by subjecting the supported
heteropolyacid to a prolonged contact with a solution of a suitable metallic salt or by
addition of phosphoric acid and/or other mineral acids.
When using a soluble metallic salt to modify the support, the salt is taken in the
desired concentration, with the heteropolyacid solution. The support is then left to soak in
the said acidic solution for a suitable duration (e.g. a few hours), optionally with periodic
agitation or circulation, after which time it is filtered, using suitable means, in order to
remove any excess acid.
When the salt is insoluble it is preferred to impregnate the catalyst with the HPA and
then titrate with the salt precursor. This method can improve the dispersion of the HPA
salt. Other techniques such as vacuum impregnation may also be employed.
The impregnated support may then be washed and dried. This may be achieved using
any conventional separation technique, including, for example, decantation and/or
filtration. Once recovered, the impregnated support may be dried, preferably by placing
the support in an oven at elevated temperature. Alternatively, or additionally, a desiccator
may be employed. On a commercial scale this drying stage is often achieved by a purge of
hot inert gas such as nitrogen, where a flammable solvent has been used for impregnation,
or air, where an aqueous solvent has been used for impregnation.
The amount of heteropolyacid impregnated on the resulting support is suitably in the
range of about 10 wt % to about 80 wt % and preferably about 20 wt % to about 50 wt %
based on the total weight of the heteropolyacid and the support. The weight of the catalyst
on drying and the weight of the support used, may be used to obtain the weight of the acid
on the support by deducting the latter from the former, giving the catalyst loading as 'g
heteropolyacid/kg catalyst'. The catalyst loading in 'g heteropolyacid /litre support' can
also be calculated by using the known or measured bulk density of the support. The
preferred catalytic loading of heteropolyacid is about 150 to about 600g heteropolyacid /
kg Catalyst.
According to a preferred embodiment of the present invention the average
heteropolyacid loading per surface area of the dried supported heteropolyacid catalyst is
more than about 0.1 micro moles/m2.
It should be noted that the polyvalent oxidation states and hydration states of the
heteropolyacids stated previously and as represented in the typical formulae of some
specific compounds only apply to the fresh acid before it is impregnated onto the support,
and especially before it is subjected to the dehydration process conditions. The degree of
hydration of the heteropolyacid may affect the acidity of the supported catalyst and hence
its activity and selectivity. Thus, either or both of these actions of impregnation and
dehydration process may change the hydration and oxidation state of the metals in the
heteropolyacids, i.e. the actual catalytic species used, under the process conditions given,
may not yield the hydration/oxidation states of the metals in the heteropolyacids used to
impregnate the support. Naturally therefore it is to be expected that such hydration and
oxidation states may also be different in the spent catalysts after reaction.
According to a preferred embodiment of the present invention, the amount of
chloride present in/on the said heteropolyacid supported catalyst is less than about 40 ppm,
preferably less than about 25 ppm and most preferably less than about 20 ppm.
The supported heteropolyacid catalyst used in the process of the present invention
may be a fresh catalyst or a previously used catalyst. Thus, in one embodiment, at least a
portion of the supported heteropolyacid catalyst has previously been employed in a process
for the preparation of an ethene from a feed comprising ethanol (and optionally water and
ethoxyethane). For example, at least a portion of the supported catalyst heteropolyacid may
derive from an extract of heteropolyacid from a previously used catalyst i.e. from a
partially deactivated material.
According to a further preferred embodiment of the present invention, the
heteropolyacid supported catalyst is a heteropolytungstic acid supported catalyst having the
following characteristic:
PV > 0.6 - 0.3 x [HPA loading/Surface Area of Catalyst]
wherein PV is the pore volume of the dried supported heteropolytungstic acid catalyst
(measured in ml/g catalyst); HPA loading is the amount of heteropolyacid present in the
dried supported heteropolyacid catalyst (measured in micro moles per gram of catalyst)
and Surface Area of Catalyst is the surface area of the dried supported heteropolytungstic
acid catalyst (measured in m2 per gram of catalyst).
Suitable catalyst supports may be in a powder form or alternatively may be in a
granular form, or in a pelletised form, a spherical form or as extrudates (including shaped
particles) and include, but are not limited to, clays, bentonite, diatomous earth, titania,
activated carbon, aluminosilicates e.g. montmorillonite, alumina, silica-alumina, silicatitania
cogels, silica-zirconia cogels, carbon coated alumina, zeolites, zinc oxide, flame
pyrolysed oxides. Supports can be mixed oxides, neutral or weakly basic oxides. Silica
supports are preferred, such as silica gel supports and supports produced by the flame
hydrolysis of SiCl4. Preferred supports are substantially free of extraneous metals or
elements which might adversely affect the catalytic activity of the system. Thus, suitable
silica supports are at least about 99% w/w pure. Impurities amount to less than about 1%
w/w, preferably less than about 0.60% w/w and most preferably less than about 0.30%
w/w. The pore volume of the support is preferably more than about 0.50ml/g and
preferably more than about 0.8 ml/g.
Suitable silica supports include, but are not limited to any of the following: Grace
Davison Davicat® Grade 57, Grace Davison Davicat® 1252, Grace Davison Davicat® SI
1254, Fuji Silysia CariAct® Q15, Fuji Silysia CariAct® Q10, Degussa Aerolyst® 3045
and Degussa Aerolyst® 3043. The average diameter of the support particles is about 2 to
about 10 mm, preferably about 3 to about 6 mm. However, these particles may be crushed
and sieved to smaller sizes of, for example, about 0.5 mm to about 2 mm, if desired.
The average pore radius (prior to impregnation with the heteropolyacid) of the
support is about 10 to about 500A, preferably about 30 to about 175A, more preferably
about 50 to about 150 A and most preferably about 60 to about 120A. The BET surface
area is preferably between about 50 and about 600 m /g and is most preferably between
about 150 and about 400 m2/g.
The BET surface area, pore volume, pore size distribution and average pore radius
were determined from the nitrogen adsorption isotherm determined at 77K using a
Micromeritics TRISTAR 3000 static volumetric adsorption analyser. The procedure used
was an application of British Standard methods BS4359:Part 1:1984 'Recommendations
for gas adsorption (BET) methods' and BS759 1:Part 2:1 992, 'Porosity and pore size
distribution of materials' - Method of evaluation by gas adsorption. The resulting data
were reduced using the BET method (over the pressure range 0.05-0.20 P/Po) and the
Barrett, Joyner & Halenda (BJH) method (for pore diameters of 20-1000 A) to yield the
surface area and pore size distribution respectively.
Suitable references for the above data reduction methods are Brunauer, S, Emmett, P
H, & Teller, E, J. Amer. Chem. Soc. 60, 309, (1938) and Barrett, E P, Joyner, LG &
Halenda P P, J. Am Chem. Soc. , 1951 73 373-380.
Samples of the supports and catalysts were out gassed for 16 hours at 120 °C under a
vacuum of 5x10-3 Torr prior to analysis.
The present invention also provides a use of a reactor having an internal pressure of
at least about 0.80 MPa but less than about 1.80 MPa, in a vapour phase chemical
dehydration of a feed comprising ethanol, (and preferably further comprising water and
ethoxyethane) and having a feed temperature of at least about 250 °C in the presence of a
supported heteropolyacid catalyst, for preventing or reducing deactivation of the supported
heteropolyacid catalyst. Preferred temperatures of the feed in this aspect of the invention
are the same as those described hereinbefore. Preferably, there is provided use of a
pressure of about 0.90 MPa to about 1.60 MPa inside the reactor. More preferably, there is
provided use of a pressure of about 0.95 MPa to about 1.30 MPa inside the reactor. Most
preferably, there is provided a use at a pressure of about 1.00 MPa to about 1.20 MPa
inside the reactor. Preferred feed and effluent stream pressures in this aspect of the
invention are the same as those described hereinbefore.
The present invention also provides a method for preventing or reducing deactivation
of a supported heteropolyacid catalyst when used in the preparation of ethene by vapour
phase chemical dehydration of a feed comprising ethanol, (and preferably further
comprising water and ethoxyethane) in a reactor, wherein the feed has a temperature of at
least about 250 °C, said method comprising maintaining or adjusting the pressure inside
the reactor to be at least about 0.80 MPa but less than about 1.80 MPa. Preferred
temperatures of the feed in this aspect of the invention are the same as those described
hereinbefore. Preferably, the pressure is maintained at, or adjusted to, a pressure of from
about 0.90 MPa to about 1.60 MPa inside the reactor. More preferably, the pressure is
maintained at, or adjusted to, a pressure of from about 0.95 MPa to about .30 MPa inside
the reactor. Most preferably, the pressure is maintained at, or adjusted to, a pressure of
from about 1.00 MPa to about 1.20 MPa inside the reactor. Preferred feed and effluent
stream pressures in this aspect of the invention are the same as those described
hereinbefore.
The present invention also provides products made by any of the processes described
herein, and particularly with respect to the appended claims.
The present invention will now be illustrated by way of the following examples and
with reference to the following figures:
FIGURE 1: Graphical representation of ethylene productivity against time of catalyst
exposure to a feed stream at 260 °C; and
FIGURE 2 : Graphical representation of temperature (and pressure) on ethylene
productivity.
Catalyst Preparation
A silicotungstic acid (STA) catalyst was used for conducting the dehydration
reactions according to the following examples.
A pure silica support with a surface area of 147m /g, pore volume of 0.84 ml/g and a
mean pore diameter of 230 Awas used for preparation of the STA catalyst. The catalyst
was prepared by adding silica (512 g) to a solution of silicotungstic acid (508 g) in water
(1249 g). Once the the silicotungstic acid solution had fully impregnated the pores of the
support the excess solution was drained, under gravity, from the support and this was then
dried and crushed to a particle size of 100 to 200mhi before being loaded into the reactor
tube.
The STA loading on the catalyst support as STA.6H20 , on a dry weight basis, was
estimated to be 24.5% w/w, based on the weight gained by the silica during the catalyst
preparation.
Vapour Phase Dehydration Reactions
A mass of STA catalyst (as indicated in Table 1 below) prepared in accordance with
the above method was loaded into a reactor tube having an isothermal bed and pressurised
to 0.501 MPa under inert gas (nitrogen and helium) flow. The catalyst was heated at 2
°C/min to 240 °C under a combined nitrogen (0.01500 mol/hr) and helium flow (0.00107
mol/hr) and held at this temperature for 8 hours before being cooled to 150 °C.
Ethanol (0.04084 mol/hr) was then added to the nitrogen / helium flow and the
temperature was increased at 2 °C/min to 225 °C. Once at 225 °C the feed pressure was
increased at a rate of 0.1 MPa/min such that the pressure inside the reactor was increased
to the value given in Table 1. Once at the desired pressure, the diethyl ether and water
reagents were added to the ethanol, helium and nitrogen flow. At this point the flows of
the feed components were adjusted to give ethanol (0.02677 mol/hr ), diethyl ether
(0.00776 mol/hr), water (0.00297 mol/hr ), helium (0.00106 mol/hr) and nitrogen (0.01479
mol/hr ) .
Once the catalyst performance had stabilised at 225 °C, typically after around lOOhrs,
the catalyst temperature, which is the same as the feed temperature in this particular
reactor, was increased to 260 °C and the ethylene productivity monitored versus time by
on-line GC analysis. The results of dehydration experiments at varying pressure are
presented in Table 1 below, showing the reactor ethylene productivity decreasing with time
on stream.
Table 1
Mass of Time on Ethylene Total
Example catalyst Stream Temperature Pressure Productivity
at 260°C (°C) (mol/kg
(mg) (MPa)
(hrs) catalyst/hr)
Example 1 13.6 1.68 260 1.430 867
Example 1 13.6 48.93 260 1.430 743
Example 1 13.6 82.65 260 1.430 708
Example 1 13.6 109.64 260 1.430 678
Example 1 13.6 184.07 260 1.430 553
Example 2 13.6 3.47 260 1.430 684
Example 2 13.6 43.87 260 1.430 643
Example 2 13.6 84.25 260 1.430 607
Example 2 13.6 111.17 260 1.430 596
Comparative Example 1 13.7 1.99 260 2.858 497
Comparative Example 1 13.7 49.69 260 2.858 339
Comparative Example 1 13.7 83.41 260 2.858 210
Comparative Example 1 13.7 110.3 260 2.858 114
Comparative Example 1 13.7 184.79 260 2.858 4
Comparative Example 2 13.7 1.57 260 2.858 501
Comparative Example 2 13.7 48.87 260 2.858 280
Comparative Example 2 13.7 82.67 260 2.858 183
Comparative Example 2 13.7 109.67 260 2.858 63
Comparative Example 2 13.7 183.83 260 2.858 7
Comparative Example 3 13.5 6.62 260 2.858 494
Comparative Example 3 13.5 46.95 260 2.858 342
Comparative Example 3 13.5 80.65 260 2.858 170
Comparative Example 3 13.5 114.26 260 2.858 83
Comparative Example 3 13.5 181.49 260 2.858 5
Comparative Example 4 13.6 2.82 260 2.858 388
Comparative Example 4 13.6 43.2 260 2.858 289
Comparative Example 4 13.6 83.59 260 2.858 102
Comparative Example 4 13.6 110.52 260 2.858 17
The results in Table 1, which are represented graphically in Figure 1, illustrate the
benefits of the process of the invention with regard to catalyst lifetime. It is clear from
Figure 1 that ethylene productivity remains high with Examples 1 and 2, which are
conducted at a pressure according to the present invention in a high-temperature (260 °C)
dehydration reaction, for a significantly longer period of time compared with Comparative
Examples 1 to 4, which are conducted at pressures not in accordance with the present
invention.
Notably, in a high-temperature dehydration (260 °C) process, ethylene productivity is
substantially diminished with Comparative Examples 1 to 4 after only 100 hours reaction
time at high temperature. This is indicative of substantial catalyst deactivation. Moreover,
as is clear from Figure 1, near complete catalyst deactivation is observed with Comparative
Examples 1 to 4 after 180 hours reaction time at high temperature.
In addition, the results in Table 1 also demonstrate that Examples 1 and 2 have
significantly higher maximum ethylene productivities (867 and 684 g/Kg catalyst/hr
respectively) compared with Comparative Examples 1 to 4 (497, 501, 494 and 388 g/Kg
catalyst/hr respectively). Thus, it is clear that the particular combination of temperature
and pressure of the dehydration process according to the present invention both increases
ethylene productivity and reduces catalyst deactivation.
In a further set of experiments, dehydration reactions were conducted with the same
STA catalyst in the same manner as described above, apart from after the stabilisation
period at 225 °C, the reaction temperature was modified to 220, 240, 260, 280 or 295 °C
and ethylene productivity was monitored versus time by on-line GC analysis. The results
of these additional dehydration experiments are presented in Table 2 below, also showing a
benefit to ethylene productivity when operating according to the present invention.
Table 2
Time on Ethylene
Mass of Total Stream at Temperature Productivity
Example Pressure
catalyst (mg) temperature (°C) (mol/kg
(MPa)
(hrs) catalyst/hr)
Example A 13.7 2 225 2.858 42
Example A 13.6 3.94 240 2.858 109
Example A 13.7 1.99 260 2.858 497
Example A 13.7 5.09 280 2.858 1058
Example A 13.6 7.41 295 2.858 1326
Example B 13.69 1.69 225 2.858 39
Example B 13.69 1.57 260 2.858 501
Example C 13.6 1.36 220 1.430 100
Example C 13.6 1.37 225 1.430 152
Example C 13.6 1.68 225 1.430 140
Example C 13.6 4.73 225 1.430 125
Example C 13.6 6.2 225 1.430 119
Example C 13.6 4.72 240 1.430 313
Example C 13.6 1.68 260 1.430 867
Example C 13.6 6.19 280 1.430 1463
Example D 13.5 6.62 225 2.858 28
Example D 13.5 6.62 260 2.858 494
Example E 13.6 1.36 220 2.144 46
Example E 13.6 1.37 225 2.144 85
Example E 13.7 2.56 225 2.144 67
Example E 13.6 4.66 225 2.144 64
Example E 13.6 6.65 225 2.144 65
Example E 13.6 4.2 240 2.144 208
Example E 13.7 2.1 260 2.144 695
Example E 13.6 6.2 280 2.144 1460
Example F 13.6 6 220 1.430 94
Example F 13.6 2.63 225 1.430 147
Example F 13.6 3.47 260 1.430 684
Example G 13.6 2.82 260 2.858 388
The results in Table 2, which are represented graphically in Figure 2, illustrate the
benefits of the process of the invention with regard to ethylene productivity. As is clear
from Figure 2, ethylene productivity is generally increased by increasing the temperature at
which the dehydration process is conducted, for all pressures tested. However, what is also
clear from Figure 2 is that conducting the dehydration reaction at a pressure in accordance
with the present invention (e.g. as in the case for Examples C and F) leads to superior
ethylene productivities compared with reactions conducted at high pressure (e.g. Examples
A and G).
The dimensions and values disclosed herein are not to be understood as being strictly
limited to the exact numerical values recited. Instead, unless otherwise specified, each such
dimension is intended to mean both the recited value and a functionally equivalent range
surrounding that value. For example, a dimension disclosed as "40 mm" is intended to
mean "about 40 mm."
Every document cited herein, including any cross referenced or related patent or
application, is hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise limited. The citation of any document is not an admission that it is
prior art with respect to any invention disclosed or claimed herein or that it alone, or in any
combination with any other reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of a term in this document
conflicts with any meaning or definition of the same term in a document incorporated by
reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and
described, it would be obvious to those skilled in the art that various other changes and
modifications can be made without departing from the spirit and scope of the invention. It
is therefore intended to cover in the appended claims all such changes and modifications
that are within the scope and spirit of this invention.

Claims
1. A process for the preparation of ethene by vapour phase chemical dehydration of a
feed comprising ethanol, said process comprising contacting a supported heteropolyacid
catalyst in a reactor with the feed, wherein the feed temperature is at least 250 °C and the
pressure inside the reactor is at least 0.80 MPa but less than 1.80 MPa.
2. A process according to Claim 1, wherein the process is conducted at a feed
temperature of at least 252 °C, preferably wherein the feed temperature is at least 255 °C,
more preferably wherein the feed temperature is at least 260 °C; even more preferably
wherein the feed temperature is at least 280 °C; and even more preferably still wherein the
feed temperature is at least 300 °C.
3. A process according to Claim 1 or Claim 2, wherein the upper limit of the feed
temperature is 350 °C; preferably wherein the upper limit of the feed temperature is
325 °C.
4. A process according to any of Claims 1 to 3, wherein the pressure inside the reactor
is from 0.90 MPa to 1.60 MPa; preferably wherein the pressure inside the reactor is from
0.95 MPa to 1.30 MPa; and most preferably wherein the pressure inside the reactor is from
1.00 MPa to 1.20 MPa.
5. A process according to any of Claims 1 to 4, wherein the feed stream pressure is
from 1.00 MPa to 1.80 MPa; preferably wherein the feed stream pressure is from 1.20 MPa
1.60 MPa; and more preferably wherein the feed stream pressure is from 1.30 MPa to 1.50
MPa, for example 1.40 MPa.
6. A process according to any of Claims 1 to 5, wherein the effluent stream pressure is
from 0.80 MPa to 1.40 MPa; preferably wherein the effluent stream pressure is from 0.85
MPa to 1.20 MPa; and more preferably wherein the effluent stream pressure is from 0.90
MPa to 1.10 MPa, for example 1.00 MPa.
7. A process according to any of Claims 1 to 6, wherein the feed further comprises
water and/or ethoxyethane.
8. A process according to any of Claims 1 to 7, wherein the catalyst is provided in the
form of one or more catalyst beds in the reactor, preferably.
9. A process according to Claim 8, wherein the catalyst is provided in the form of
multiple catalyst beds, preferably wherein the multiple catalyst beds are arranged in series
or in parallel.
10. A process according to Claims 8 or Claim 9, wherein at least one of the one or more
catalyst beds is a tubular fixed bed or a fluid bed.
11. A process according to any one of Claims 1 to 10, wherein the amount of
heteropolyacid in the supported heteropolyacid catalyst is in the range of from 10 wt.% to
50 wt.% based on the total weight of the supported heteropolyacid catalyst.
12. A process according to any of Claims 1 to 11, wherein at least a portion of the
supported heteropolyacid catalyst has previously been employed in a process for the
preparation of an ethene from a feed comprising ethanol and preferably further comprising
water and ethoxyethane.
13. A process according to any of Claims 1to 12, wherein the supported heteropolyacid
catalyst is a supported heteropolytungstic acid catalyst.
14. A process according to Claim 13, wherein the supported heteropolytungstic catalyst
is a supported silicotungstic acid catalyst, preferably 12-tungstosilicic acid
(H4[SiW 2O40].xH2O).
15. A process according to Claim 1 characterised in that the supported
heteropolytungstic acid catalyst has the following characteristic:
PV > 0.6 - 0.3 x [HPA loading/Surface Area of Catalyst]
wherein PV is the pore volume of the dried supported heteropolytungstic acid catalyst
(measured in ml/g catalyst); HPA loading is the amount of heteropolyacid present in the
dried supported heteropolyacid catalyst (measured in micro moles per gram of catalyst)
and Surface Area of Catalyst is the surface area of the dried supported heteropolytungstic
acid catalyst (measured in m2 per gram of catalyst).