Review

pubs.acs.org/IECR

Chemical and Technical Aspects of Propene Oxide Production via

Hydrogen Peroxide (HPPO Process)
V. Russo, R. Tesser, E. Santacesaria, and M. Di Serio*
Department of Chemical Sciences, University of Naples “Federico II”, via Cintia 80126 Napoli, Italy

ABSTRACT: Propene oxide is a very important chemical whose production technology has changed a lot during the last 30
years. Nowadays, the most promising technology is the HPPO process in which the propene oxide is produced by oxidizing
propene with hydrogen peroxide, via titanium silicalite-1 (TS-1) catalysis. Even if this technology has been patented in the early
1980s and some chemical plants are already in production, only few papers have been published until now dealing with the
catalytic and kinetic aspects of the process. In this paper, the state of the art of the scientific knowledge and technical aspects
related to propene oxide synthesis in the presence of TS-1 catalyst have been reviewed.

1. INTRODUCTION Successively, some processes based on the use of oxygen as

Propene oxide (formula C3H6O) is a colorless, low-boiling, oxidant via the preformation of hydroperoxide have been
highly volatile liquid with a sweet ether-like odor. It is developed. The hydroperoxide formed in a first stage is used to
flammable and reactive, so storage and unloading areas must epoxidize propene via homogeneous organometallic catalysis
be specifically designed and monitored. Propene oxide is a (Mo based catalyst10) or heterogeneous catalysis (Ti support
highly reactive chemical used as an intermediate for the on silica11,12); in this reaction an alcohol is formed as coproduct
production of several commercial materials. It reacts readily (Coproduct Route). Eventually in a third stage the obtained
with compounds containing active hydrogen atoms, such as alcohols are dehydrated to olefinic products. The more diffuse
alcohols, amines, and acids. Therefore, propene oxide is used processes are based on the use of hydroperoxide derived from
worldwide to produce versatile products as polyether polyols ethylbenzene or isobutane. The process based on ethylbenze is
(polyglycol ethers), propene glycols, and propene glycol called styrene monomer propene oxide (SMPO) process,
ethers.1 In 2010, the PO worldwide production runs at about because, styrene is the related coproduct (see scheme 2).
7.5 Mtonns/y.2
Even though until now a lot of synthetic routes have been
developed to produce PO,1,3 in this paper, only the most
important processes that have found an application in the
modern chemical industry will be reviewed.
The direct oxidation of propene, in gas phase, with oxygen is
still a holy grail. Several catalysts and several reaction conditions
have been tested until now, but the results are very far from the
industrial targets.4−7 Duma and Hö nicke in 2000 have
proposed the use of N2O as oxidant for propene epoxidation The process based on isobutane is called the Ter-butil Alchol
to PO in gaseous phase, using silica supported iron oxide (TBA) process becase its coproduct is the ter-butyl alcohol
promoted with Na.8 However, this route suffers of low which can eventually be dehydrated to iso-butene (see scheme
selectivity due to the formation of both carbonaceous deposits 3).
and other high molecular weight products.9
The most ancient industrial process developed to produce
PO from propene is based on the dehydrochlorination of
chlorohydrins (Chlorohydrin Route) (see scheme 1).

The coproduct route was more environmentally safe than the

chlorohydrin one, but its economy depends strongly on the
marketability of the obtained coproducts. To solve this

Received: September 4, 2012

However, the coproducts of this process are brine of chlorine Revised: December 11, 2012
salts which lead to great problems in their disposal because it Accepted: December 24, 2012
can also contain harmful byproducts. Published: December 24, 2012

© 2012 American Chemical Society 1168 dx.doi.org/10.1021/ie3023862 | Ind. Eng. Chem. Res. 2013, 52, 1168−1178
Industrial & Engineering Chemistry Research Review

Figure 1. (A) PO suppliers distribution with related technologies (2009).33 (B) Worldwide PO consumption (2012).34

problem, in 2006 the Sumitomo Co. started a new process reagent, allowing its use as an aqueous solution without catalyst
based on cumene hydroperoxide (CH process) in which the deactivation.23−27 By using this catalyst, the reaction is carried
final alcohol is reduced to the starting cumene (see scheme 4). out under mild conditions (around 40 °C), and theoretically,
In this case, the catalyst was a silicon oxide catalyst with a only water is generated as byproduct. In 2008, after about 25
mesoporous structure containing Ti in the framework.13 years from the first ENI patent, Evonik (former Degussa), and
SKC have launched the first commercial-scale propene oxide
plant, based on the HPPO technology,28 with a capacity of 100
kton/y. The next year BASF and DOW Chemical started with a
new plant based on a similar technology, with a 300 kton/y
capacity.2,29
The absence of the unit operations, necessary for collecting
and purifying the coproduct of the previous hydrogen peroxide
processes, reduces the investment cost up to 25%. Moreover
the HPPO process reduces the wastewater (70−80%) and the
energy need (35%) with respect to the most traditional
The use of peroxiacids was developed by Bayer and Degussa. technologies.30
Hydrogen peroxide was used to produce peracids via acid The advantage of this new technology is proven by the fact
catalysis (peracetic or perpropionic).14−16 The peracid was that Evonik (formerly Degussa) and Uhde are going to set up
used as an epoxidizing agent (Prilezhaev reaction) for another plant in China based on HPPO technology, with a
producing PO, and the related acid that can be recycled (see capacity of 230 kton/y,31 while DOW is setting up a 390 kton/
scheme 5). y of propene oxide plant in Thailand.32
However, the previously described processes are still the
more diffused ones; in Figure 1A, the worldwide distribution of
the PO suppliers, referred to 2009, is reported,33 while in
Figure 1B, the worldwide consumption of propene oxide
referred to 2012 is shown.34
As can be seen, among the old technologies, the chlorohydrin
However this route did not achieve a real industrial success route is still the most diffused one, but the HPPO process is the
probably because of the intrinsic low selectivity of the process. trend of the modern industry, considering the advantages
The direct use of hydrogen peroxide for epoxidizing propene
expressed before.
is a much more interesting from both environmental and
Even if in the scientific literature there are a lot of studies on
economic points of view, because the only coproduct is water
(see scheme 6). the synthesis and characterization of TS-1 catalyst,26,35,36 only
few studies have been published on both the reaction
mechanism1,26 and the kinetics of the propene epoxidation
reaction.35,36 On the contrary, a large number of patents have
Several attempts have been made to find the right catalyst to been published on propene epoxidation claiming different
epoxidize propene directly with hydrogen peroxide.17−22 The process conditions, reactors, and additives, to improve the
right catalyst was found by ENI at the end of the 1970s, that conversion and selectivity to propene oxide.
patented the use of titanium silicalite-1 (TS-1) for the direct All the previous cited aspects (both chemical and technical)
epoxidation of propene with hydrogen peroxide (HPPO will be reviewed in this paper for presenting a complete state of
hydrogen peroxide propene oxide).21 The TS-1 catalyst opened the art of propene oxide production, via epoxidation with
the possibility to the use of hydrogen peroxide as an oxidizing hydrogen peroxide, in the presence of titanium silicalite catalyst.
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2. TS-1 CATALYST species in TS-1.23,47 The absence of other peaks demonstrates

that there is no octahedral Ti or anatase TiO2.47−49
Titanium silicalite is a crystalline zeotype material in which
TS-1 catalyst is normally used in both packed bed and
tetrahedral [TiO4] and [SiO4] units are arranged in a MFI
continuous slurry reactors (see section 6). The industrial
structure.37 The chemical nature of Ti species in TS-1 catalyst
catalyst is constituted by zeolite dispersed in a binder phase.
is made by Ti(OSi)4 tetrahedral sites (called “close” sites), that The pellets used in packed bed are generally obtained by
contain some defective “open” Ti(OSi)3(OH) sites, as EXAFS extruding the binder paste containing the TS-1, while, the
studies have demonstrated on well manufactured TS-1 catalyst for the slurry reactors can be obtained by spray-drying
samples.23−25,38 Owing to this structure, TS-1 shows a three- technique.50 The characteristics of the binder are important for
dimensional system of channels having molecular dimension of the mechanical proprieties of the final catalyst, but also for
5.1−5.6 Å and which constitutes the zeolitic micropores of the saving the selectivity in the epoxidation reaction.51 As a matter
material. of fact, for example, Li et al.51 have demonstrated that the use
The TEM micrograph exhibits well-ordered lattice fringes of of alumina as binder, instead of silica, leads to a strong increase
the MFI structure of TS-1, which is indicative of high in byproducts formation, giving place to a PO selectivity of
crystallinity. This confirms that the TS-1 catalyst has uniformly respectively 32.39 and 73.90% with the same hydrogen
sized micropores of about 0.5 nm.39−42 peroxide conversion, of about 95%.
BET analysis has been applied to TS-1 catalyst to obtain the
specific surface area, although the BET theory do not take into 3. REACTIONS OCCURRING IN THE HPPO PROCESS
account micropore filling. In this case, a linear “BET” range is AND THE CATALYST DEACTIVATION
found at 0.005 < P/P° < 0.1 that is lower than the usual used In general, propene epoxidation with hydrogen peroxide is
one 0.05 < P/P° < 0.3. Starting from this approximation, the performed at 40−60 °C, keeping propene at 20−25 bar and
results of the BET analysis reported in the literature gave a using methanol as solvent (see scheme 6). However in addition
surface area of 420−450 m2 g−1 and a pore volume of 0.18− to propene oxide other products can be formed by secondary
0.26 cm3 g−1.23,35 reactions that lower the yield.52−55
The synthesis of TS-1 catalyst, normally, starts with the A detailed scheme of all the possible occurring reactions after
hydrothermal crystallization of zeolite structure by using the propene epoxidation is reported in schemes 7−10.
different silicon (for example: TEOS, fumed silica, colloidal
silica, amorphous silica) and titanium sources (for example:
TEOT, TBOT, TOPT, TiCl3, TiCl4, rutile), templating (for
example: TPA+, TBP+/TEP+, TPA+/TEA+), and mineralizing
agents (for example: OH−, NH3) (see the work of Perego and
reference therein43). Then, the obtained solid is dried (100 °C)
and calcined at high temperatures (500−550 °C). The different
synthesis routes produce crystal agglomerates in a mean size of
0.1−80 μm43 and also the structural properties can change (the
Ti dispersion and its coordination number).44
The use of a right synthesis route is fundamental to obtain an
active and stable catalyst. As a matter of fact the TS-1 activity is
correlated with the presence of isolated framework Ti(IV)
sites27 and to the crystal morphology of the zeolite,27 while an
increase in local disorder and/or coordination number of Ti
(from IV to VI) is responsible for the lower stability under
H2O2 treatment of the catalyst.44
IR, XRD, and UV−vis are the characterization methods
usually applied to confirm the presence of Ti(IV) in the
framework.43
H 2O2 → 0.5O2 + H 2O (8)
The XRD pattern of TS-1 catalyst presents single peaks at
24.4° and 29.3° demonstrating a conversion from a monoclinic CH3OH + 2H 2O2 → HCOOH + 3H 2O (9)
symmetry (silicalite) to an orthorhombic symmetry (titanium
silicalite).23,45 The Ti sites, in the TS-1 catalyst, lead to a CH3OH + HCOOH → HCOOCH3 + H 2O (10)
regular change in unit cell volume (UCV), with a correlation The reactions of scheme 7 are all related to the ring-opening
between UCV and Ti in the order of 3% (as TiO2) of Ti reactions. Two possible main reactions can occur between
loading, after which the correlation starts to be no longer valid, propene oxide and either water or methanol, giving propene
clearly indicating an upper limit for Ti (IV) insertion in the glycol and methoxy propanol, respectively. These two products
zeolite framework.45 are the major byproducts reported in every paper or patent
From the FT-IR spectrum of TS-1 catalyst it is possible to published in the literature; moreover, with the methanol
observe an absorption band at about 970 cm−1 that is not concentration usually being greater than that of water, the
present in the spectrum of either pure silicalites or titanium probability to form methoxypropanol instead of glycol is very
oxides. In general, the intensity of this band increases with the high26 (for example, Paparatto et al.56 for the output stream of a
amount of titanium that substitutes the silicon in the framework first reactor operating at 50 °C reported the following
of silicalites.23,46 The UV−vis spectrum shows an absorption composition: 4.83 wt % propene oxide, 0.12 wt %
band near 215 nm indicating the presence of tetrahedral Ti methoxypropanol, 0.03 wt % 1,2-propene glycol). Of course,
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propene oxide can also react with methoxypropanol or glycol

giving dimers that can react further forming heavier adducts.
The formation of these byproducts reducing the selectivity is
also one of the causes of catalyst deactivation.26,35
Hydrogen peroxide decomposition (reaction 8) must be
taken into account mainly at high temperatures.57
The formation of formic acid (reaction 9) and methylformate
(reaction 10) has been reported (without quantitative data) by
BASF58 that underlined the propene oxide purification
problems.
Several papers and patents have been published until now Alternative mechanistic proposals are generally based on
devoted to the catalyst deactivation and catalyst regener- density functional theory (DFT) studies with sometimes the
ation.36,59−69 Zuo et al.69 have shown that in a tubular reactor support of spectroscopic evidence. However, these data are
the catalyst deactivation increases along the bed, being normally obtained under conditions that are very different from
maximum at the reactor outlet where also the concentration the real ones present in industrial reactors.75
It is important to point out that only two papers have been
of byproducts is maximum. The most commonly used
published until now concerning the HPPO kinetics,35,76 and
techniques to regenerate the TS-1 catalyst are thermal
these papers are both focused only on the main reaction.
treatment, at temperatures from 300 to 700 °C in the presence Liang et al.76 have tested several possible kinetic equations
of different media, such as air, steam, and inert gas,60−65 deriving from different hypothesized reaction mechanism to
oxidation by diluted hydrogen peroxide, at temperatures below simulate their kinetic data. Even if the experimental runs have
than 100 °C,62,67,68 and extraction by different solvents, such as been performed in conditions far from the one used in the
methanol, at different temperatures in the range of 140−240 industrial reactors (T = 30−50 °C, P = 0.1−0.6 MPa, H2O2 = 2
°C.70−72 In particular, Wang et al.36 have very recently wt %, solvent = isopropanol76), the results seem to confirm the
performed a detailed study on the TS-1 deactivation and its reaction mechanism proposed by Clerici et al. on the basis of
regeneration. The authors have verified that the best perform- spectroscopic studies.21 As a matter of fact, the kinetic analysis
ances, in terms of activity, in the TS-1 regeneration, are performed by Liang et al.76 pointed out that the best kinetic
obtainable by calcinations and by treatment with hydrogen equation for fitting the experimental data obeys an Eley−Rideal
peroxide. From BET analysis, it has been verified that these two model (see eq 12).
methods warrant an almost complete recovery of the surface
kK1[H 2O2 ][C3H6]
area, while, the treatment with the solvent does not lead to a r=
satisfactory recovering of the surface area. This fact has been 1 + K1[H 2O2 ] + K 2[C3H6] + K3[PO] (12)
justified by the presence of the propene oxide condensation According to the mentioned authors, the reaction takes place
products that are produced as byproducts in the PO synthesis, between the adsorbed hydrogen peroxide on the titanium active
such as dimers of propene oxide and methoxypropanol. As a sites and propene in the free state.
matter of fact, the molecules of these compounds, formed in Recently, Shin et al.35 have published a kinetic study using
the micropores of the zeolites, cannot diffuse outside from the methanol as solvent (T = 40 °C, P = 0.7−7 bar, H2O2 = 0.34 wt
channels, and part of them resides there. The regeneration with %, solvent = methanol at 40−90 wt %35). Also in this case, the
hydrogen peroxide has also been patented by Degussa, that conditions were far from the industrial reactors. The authors
performed batch runs in order to verify the possibility of have tested different kinetic rate laws, on the collected
regenerating the catalyst with a treatment of different solvents/ experimental data, finding that the best mechanism, in terms
reactants (methanol, water, a solution of H2O2 at 5 wt %) at of statistical analysis, is a dual-site Langmuir−Hinshelwood (see
reflux condition.73 Degussa claimed the reflux treatment with eq 13).
hydrogen peroxide for 4 h as the best method, because, with
r=
this treatment, the catalyst recovers almost completely the kK1K 2[H 2O2 ][C3H6]
activity of a fresh catalyst.73
(1 + K1[H 2O2 ] + K3[CH3OH])(1 + K 2[C3H6] + K4[CH3OH])
(13)
4. REACTION MECHANISM AND KINETICS
However, these kinetic expressions contains four adsorption
In both the scientific literature and the patent library only the parameters (K1−K4) and one kinetic constant (k), with a total
mechanism of the main reaction of the HPPO process has been of five adjustable parameters that have been regressed on a few
studied. Clerici e al.21 have shown that the key factor for this number of experimental data, and the conclusions of the
mechanism is the reversible splitting of one Ti−OSi bond by authors cannot be considered definitive. More experimental
H2O2 with the resulting formation of a Ti−OOH species and work is, therefore, necessary to individuate the correct kinetics
the coadsorption of one alcohol or water molecule stabilizing in the presence of methanol as solvent and determine the
the hydroperoxide through a five-membered ring (see scheme related parameters.
11).27,74 Then, the epoxidation step occurs, where the peroxy
oxygen vicinal to Ti is transferred to the double bond, with the 5. REACTION CONDITIONS
contemporary formation of a Ti-alkoxide and a molecule of 5.1. Role of Temperature and Pressure. Shin et al.35
water. Finally, the desorption of the epoxide and the reaction of have reported that an increase of the reaction temperature
Ti-OR with H2O2, to form again the active species, complete corresponds to an increase of the hydrogen peroxide
the catalytic cycle (see scheme 11).21 conversion. In particular, passing from 30 to 50 °C, the
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hydrogen peroxide conversion increases 1.3 times, working at

0.7 bar of propene, 0.35 wt % H2O2, 50 wt % CH3OH, and 0.28
g TS-1 in powder for 1 h of reaction time. In the meantime, the
selectivity to propene oxide decreased from 99 to 96%. The
same evidence has been described by Clerici et al.26 This fact
shows that temperature needs to be kept low in order to avoid
the ring-opening reactions. At this purpose, being the
epoxidation reaction extremely exothermic, Degussa reported
in a patent77 that by working with a jacketed packed bed
tubular reactor, it was not possible to work under isothermal
conditions, and they attributed the lowering of selectivity to this
aspect.
The pressure is also a very important operative variable. In
fact, as propene is gaseous at standard conditions, the operative
pressure needs to be chosen carefully in order to decide to Figure 2. Influence of the reaction media on the epoxidation of
work either in a gas−liquid−solid state or in a liquid−liquid− propene, at 60 °C, 0.4 MPa, 0.4 wt % TS-1, 32 cm3 solvent, 2 cm3 30
wt % H2O2 m, time 1.5 h.83
solid state. Actually, at pressure lower than 16 bar and at 40 °C,
propene is in a gas state. By working in gas−liquid−solid state
and by increasing the propene pressure, the propene both hydrogen peroxide conversion and propene oxide
concentration in the liquid phase increases, consequently selectivity. In particular, the ARCO company has performed a
increasing the reaction rate.35,76 Recently, some patents deep investigation on the role of both basic (B) and nonbasic
published by Degussa78−80 have verified and claimed that the (NB) salts by performing experimental runs with different salts
HPPO system, at pressures greater than 16 bar, is composed by in the same experimental conditions.87 In particular, it has been
two different liquid phases: (i) a phase rich in propene found that the nonbasic salts lead to a higher hydrogen
containing also propene oxide and (ii) a methanol rich phase peroxide conversion and propene oxide selectivity. Then, in a
containing water, hydrogen peroxide, and some amount of much more recent patent,88 the role of ammine on the TS-1
propene oxide. They have experimentally observed that by activity and selectivity has been investigated finding that in
working at 40−60 °C, at a pressure of 25 bar, with a 300 cm3 general the addition of an amine leads to a higher propene
tubular reactor (4 m length and 1 cm diameter) and using oxide selectivity but to a higher decrease in the hydrogen
methanol as solvent, it is possible to obtain a 96% H2O2 peroxide conversion degree.
conversion with a 96−97% of propene oxide selectivity. By In general, the behavior of both the salts and the additives
observing the samples in a sight glass window, two immiscible containing nitrogen on TS-1 activity has been also observed by
liquid phases have been observed. Degussa.73,89−91 In particular, they have demonstrated that by
5.2. Role of the Solvent. The propene epoxidation treating TS-1 catalyst with salts, such as Na2SO4, (NH4)2SO4,
reaction rate strictly depends on the reaction medium in NH4NO3, and NaH2PO4, the catalyst shows a lowering in
which the reaction is carried out. As a matter of fact, several activity but an increase in propene oxide selectivity.73 Then,
papers have pointed out that methanol is the best Degussa has demonstrated that by working at pH > 7, by using
solvent.76,81−84 In general, the epoxidation rate decreases in NaOH, it is possible to increase the propene oxide selectivity
alcohol solvents in the order, methanol > ethanol > i-propanol against a lowering in hydrogen peroxide conversion.89 In
> t-butanol, with the two extremes differing by more than 1 further patents,90,91 Degussa has claimed that by using
order of magnitude.26,27,84,85 Moreover, by using methanol also ammonia salts, it is possible to obtain the same results.
the selectivity to propene oxide is strongly increased. A The same kind of behavior has also been observed both by
comparison of several tested solvents for the propene oxidation Polimeri Europa56,92 and then by Dow.93 In particular Dow
to PO, in terms of both hydrogen peroxide conversion and PO found that by adding zinc carbonate to the solution, it is
selectivity is reported in Figure 2.83 It is evident from the figure possible to keep the same hydrogen peroxide conversion but
that methanol is the best solvent for the HPPO process. the selectivity to PO is increased from 93 to 98%.
Figure 2 shows also that the activity to propene oxide is not In conclusion, it has been demonstrated that basic additives
increased by using an aprotic solvent like acetone (Me- poison the acid sites of TS-1 catalyst leading to a reduction of
COMe).83 In this case, selectivity stays high because acetone is the catalyst activity, but also to a slower ring-opening reaction
not a nucleophilic molecule which can react with a PO ring. rate, that means to increase propene oxide selectivity.
It has been further verified that water dissolved in methanol
solvent has a moderately negative effect on the reaction, 6. REACTORS
because of both competing in the adsorption on the TS-1 sites A detailed analysis on the existing patent literature showed that
and lowering the concentration of propene in solution; propene there is a large variety of reactor setups that have been used
being much more soluble in methanol (2.6 × 10−1 mol/ until now for the HPPO process. In particular, in Table 1, a list
(L·atm), at 40 °C) than in water (8.3 × 10−3 mol/(L·atm), at of all the patented type of reactors and related reaction
40 °C).85,86 This fact can also be appreciated from Figure 2, conditions is reported.
comparing the results obtained by two experimental runs Stirred batch reactors39,73,88,92,94−98 have normally been
performed in the same operating conditions but by using pure employed to test both the activity and the selectivity of TS-1
methanol or water as solvent (92% and 40% H2O2 conversion, catalyst in powder, evaluating the effect of the presence of
respectively). several salts and basic substances.
5.3. Role of Additives. ARCO and Degussa companies For what concerns the continuously stirred tank reactor
have investigated in several patents the role of the additives on (CSTR) use, Degussa67 found that the best operating
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Table 1. Reaction Conditions and Reactor Types Patented

until 2012
reactor T (°C) P (bar) ref
batch reactor 0−40 1−20 39, 73, 88, 92,
94−98
continuously stirred tank 50−65 13 56, 67, 99
reactor (CSTR)
packed bed reactor (PBR) 40−50 15−20 67, 77, 100−103
trickle bed reactor (down-flow) 40 25 89, 104
bubble siphon reactor 35−56 1 98, 105, 106
recycle reactor 55 >15 107
heat exchangers reactor 30−60 25 79, 103, 108, 109

conditions have been reached by working at a medium pH of

8.12, reaching an hydrogen peroxide conversion of 50% and a
propene oxide selectivity of 92.1% (T = 65 °C, P = 6 bar, TS-1
= 0.12 g/cm3, H2O2/methanol = 0.17 w/w, LHSV (liquid
hourly space velocity) ≈ 1.5 h−1). Polimeri Europa56,99 Figure 3. Maximum temperature reached inside the catalytic bed is
reported that by using a CSTR reactor working at 50 °C, 1.2 plotted against the inlet temperature.77
bar, with a hydrogen peroxide solution pH of 6.5 and a TS-1
concentration of 6 wt %, it is possible to obtain a hydrogen
peroxide conversion of 96% and a propene oxide selectivity of
97% (no information are given about the residence time).
Some reactors operated as PBR, using TS-1 is in the form of
pellets, by working at 40−60 °C, feeding propene as liquid
(pressures of 20−25 bar), with an inlet hydrogen peroxide
concentration in a range of 3−8 wt %. Obviously, for this type
of reactor, the liquid−solid transport phenomena both inside
and outside of the catalytic particle must be considered,
because, they strongly affect the catalyst efficiency.92 For what
concerns the spatial velocities, some patents have worked with
LHSW values ranging from 3 to 5 cm3 gcat−1 h−1.100−102 By
considering, instead, the LHSV values, BASF has worked with
two different reactors. In the first patent, 20 g of catalyst in
pellets were loaded in a 50 cm3 reactor (LHSV ≈ 0.8 h−1),100
while, in the second patent 20 g of catalyst were loaded in two
reactors each of 190 cm3 (LSHV ≈ 3.7 h−1).101 Being the TS-1 Figure 4. Hydrogen peroxide conversion (XH2O2) and propene oxide
extruded density of about 0.48 g/cm3, in the second case the selectivity (ΦPO) against the inlet temperature, at different flowrates.77
catalytic bed has been diluted with an inert material (no
information are given about this aspect). This fact is crucial, temperature at a desired safety level, solving the heat transfer
because, by diluting the catalytic bed with an inert material, it is problem, BASF and DOW described the use of reactors with
possible to reach a better thermal control of the reactor, during high thermal exchange efficiency for olefin epoxidation (see
the epoxidation reaction, and to work with higher spatial Figure 5).103 DOW and BASF proposed different solutions,
velocities, that means much more turbulent regimes with a ranging from PBR in series with an external heat exchanger
lowering in the liquid−solid mass transfer limitations. At this (Figure 5-1), recycle PBR reactors with external heat exchanger
purpose, Degussa77 has claimed the use of a jacketed packed (Figure 5-2), and heat exchanger plate reactors filled with TS-1
bed tubular reactor of 1 cm of diameter and 4 m length for the (Figure 5-3). In all cases, hydrogen peroxide conversion of 95−
propene oxide synthesis. By packing completely the tubular
reactor with extruded TS-1 catalyst, hot-spots have been
observed due to the exothermicity of the epoxidation reaction.
In Figure 3, the maximum temperature reached inside the
catalytic bed is plotted against the inlet temperature, at different
flow-rates, while in Figure 4, both the hydrogen peroxide
conversion (XH2O2) and propene oxide selectivity (ΦPO) are
plotted against the inlet temperature, varying the flowrates.
As it can be seen, by increasing the inlet temperature, the
maximum temperature reached in the catalytic bed increases
too, both at 0.35 and 0.7 kg/h. Moreover, even if at higher
temperatures the hydrogen peroxide conversion is higher,
Degussa has observed a decrease in the propene oxide
selectivity, due to the higher ring-opening reaction rate. Figure 5. Efficient heat exchange reactors: (1) PBR in series with
The problem of temperature control is common also to other external heat exchange, (2) recycle PBR reactors with external heat
epoxidation processes.108 In order to keep the reaction exchange, (3) heat exchanger plate reactors.

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97% can be reached, with a propene oxide selectivity in the the presence of a their developed catalyst. The claimed plant is
range of 90−95%. composed by three sections:56,92,118 a first section for the
Degussa and Uhde have, then, patented the use of heat hydrogen peroxide formation, from the reaction between
exchanger reactors,79 working in a trickle bed state, to produce hydrogen and oxygen catalyzed by a Pd/Pt catalyst,56,92,118
propene oxide, by either packing or coating the catalyst on the operating directly in methanol, reaching a composition of about
heat exchanger walls. Even if the pressure drops for this type of 6 wt % hydrogen peroxide, 89.7 wt % methanol, and the
reactor are higher, it is possible to obtain a very good thermal resulting parts in water; a second section where hydrogen
control. Degussa has claimed that the use of a trickle bed peroxide reacts with propene in a CSTR in the presence of TS-
reactor with down-flow feeding produces the formation of two 1; and a third purification section where it is possible to reach
liquid phases: one rich in propene, the other in methanol, 99.99 wt % in propene oxide.
water, and hydrogen peroxide. In this case, propene oxide is
partitioned between the two liquid phases, and the amount that 8. HPPO INDUSTRIAL PLANTS
is dissolved in the apolar phase cannot degrade. This fact leads BASF and DOW patented a process102,119 in which propene
to an increase of the overall propene oxide selectivity.104 oxide is formed in a high efficient heat exchanger reactor, with a
BASF and DOW have recently demonstrated that by hydrogen peroxide conversion of 99.8% and a propene oxide
working with two reactors in series, separating the produced selectivity of 93.2%. This type of plant has been in production
propene oxide in between, it is possible to increase the since 2008 in Antwerp with a plant capacity of 300 kton/y of
selectivity from 80.3% to 96%, with hydrogen peroxide propene oxide.2 A scheme of the plant is reported in Figure 6.
conversion greater than 95%. As a matter of fact, by separating
propene oxide, the ring-opening reactions rate are prevented
and the selectivity increases.2 Then, Solvay has patented the use
of a bubble siphon reactor.98,105,106 In this case, the reactor
works with a propene gaseous feeding at 1 bar. Working with
this reactor, propene oxide is stripped away with the unreacted
propene, while the alcoholic solution is partially recycled. The
catalyst regeneration, is performed in flux with air at 300 °C for
about 7 h. This system has recently been improved107 using a
reactor, that works under pressure, with recycle, taking a
contact time with the catalyst of 5.5 min and an overall
residence time of 4 h. Also in this case, good results have been Figure 6. DOW and BASF HPPO plant scheme (after the work of
obtained in terms of both hydrogen peroxide conversion and Bassler et al.2).
propene oxide selectivity.
The reactor is a tubular reactor working at about complete
7. PRODUCTION OF HYDROGEN PEROXIDE conversion. The purification section is composed by five
One of the main problems related to the technologies using distillation columns in series, useful to remove first the off-gas
hydrogen peroxide is the reduction of the cost of this reagent (1), then to purify propene oxide (2 and then 5), separate
and, in general, the economy of the HPPO process is justified water and glycols (3), and recycle methanol (4). In order to
only if the HPPO reactor is coupled with a hydrogen peroxide obtain a better separation of propene oxide, BASF and DOW
synthesis plant. Nowadays, the developed commercial HPPO have patented an extractive distillation column that uses either
plants produce hydrogen peroxide by the oxidation and water or glycol as solvent.120
reduction of anthraquinones.110−112 Evonik (formerly Degussa) and Uhde have built in 2008 in
The BASF−DOW plant in Antwerp is fed with hydrogen Ulsan, Korea, an HPPO plant based on TS-1 catalyst of 100
peroxide produced with Solvay’s high-productivity hydrogen kton/y of propene oxide121 (see the scheme in Figure 7). The
peroxide technology.113 Solvay’s technology is based on reaction is carried out in one of the patented very efficient heat
ethylanthraquinones reduction/oxidation cycle. removal reactors.79 As the reaction mixture leaves the reactor, it
Polimeri Europa has patented an integrated plant where is sent to a flash unit (1) that separates propene from the liquid
hydrogen peroxide is produced in situ via anthraquinones phase. Propene is purified and recycled to the reactor (2), while
reduction/oxidation cycle in methanol.95 This process has the the liquid phase is treated in a battery of three distillation
advantage to eliminate the necessity of hydrogen peroxide columns (3−5). The first (3) is a preseparation column that
extraction with water from the anthraquinones working separates propene oxide from water/methanol; the second (4)
solution and the successive concentration by distillation. is a stripping column where propene is recycled to the flash unit
However the reported yield of propene oxide was lower than (2). Finally, propene oxide is purified in the last column and is
that reported for ex-situ HPPO processes.114 obtained at 99.9% purity. Water and methanol are collected in a
A very interesting approach from the conceptual point of final distillation column (6), and methanol is recycled to the
view is the use of a bifunctional catalyst to produce hydrogen oxidation reactor.
peroxide from direct reaction of oxygen and hydrogen and in
the meantime catalyze the epoxidation reaction of propene (see 9. CONCLUSION
for example115−117). The catalyst are in general TS-1 Propene oxide is an important product for the chemical
supporting metals (Pt, Pd, Os, Ru, Ir;115 Au;116 Pd, Re117). industries because of its wide range of applications. A new
However, this approach suffers from low selectivity, because of production technology (HPPO) has been developed in several
the hydrogenation of propene to propane.117 years of research activity but only recently have new plants
Polimeri Europa proposed an integrated plant in which been built on the basis of this very competitive technology, with
hydrogen peroxide is produced from hydrogen and oxygen in respect to the older ones. In the HPPO technology, propene
1174 dx.doi.org/10.1021/ie3023862 | Ind. Eng. Chem. Res. 2013, 52, 1168−1178
Industrial & Engineering Chemistry Research Review

Figure 7. Evonik and Uhde HPPO plant scheme.122

oxide is produced starting from propene and hydrogen (5) Ren, Y.; Xu, L.; Zhang, L.; Wang, J.; Liu, Y.; He, M.; Wu, P.
peroxide in the presence of TS-1 as catalyst. The process is Selective epoxidation of propylene to propylene oxide with H2 and O2
environmental friendly, because, only water is formed as a over Au/Ti-MWW catalysts. Pure Appl. Chem. 2012, 84 (3), 561−578.
byproduct of the main reaction. In the patented processes, (6) Zheng, X.; Zhang, Q.; Guo, Y.; Zhan, W.; Guo, Y.; Wang, Y.; Lu,
hydrogen peroxide conversion, that is the limiting reagent, is G. Epoxidation of propylene by molecular oxygen over supported Ag−
Cu bimetallic catalysts with low Ag loading. J. Mol. Catal A: Chem.
reported between 95 and 98% with a selectivity to PO of 90−
2012, 357, 106−111.
98%. The problems related to this technology are the following: (7) Pulido, A.; Concepción, P.; Boronat, M.; Corma, A. Aerobic
the high exothermicity of the reaction, the catalyst mass transfer epoxidation of propene over silver (111) and (100) facet catalysts. J.
limitation, the factors affecting the selectivity, the catalyst Catal. 2012, 292, 138−147.
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hydrogen peroxide production plant. All these aspects have Nitrous Oxide over Silica-Supported Iron Oxide Catalysts. J. Catal.
been considered and widely discussed on the basis of the 2000, 191, 93−104.
published literature, and we have seen that they bring to (9) Thömmes, T.; Gräf, I.; Reitzmann, A.; Kraushaar-Czarnetzki, B.
different choices of operative conditions and plant design. Catalytic Vapor Phase Epoxidation of Propene with Nitrous Oxide as
At last, the kinetic interpretation of the whole reaction an Oxidant: Investigations on Catalyst Composition and Reaction
network of the HPPO process has not been sufficiently Conditions. Ind. Eng. Chem. Res. 2010, 49, 2624−2637.
investigated yet and more investigation, therefore, are necessary (10) Lines, E. L.; Fairbrother, R. J.; Herbst, J. A. Catalytic epoxidation
of alkylene compounds. US 4157346, Olin Corporation; 1979.
for getting a fruitful optimization of the HPPO process.

■
(11) Rameswaran, M.; Cochran, R. N. Epoxidation process. US
5081267, Arco Chemical Technology, L.P.; 1992.
AUTHOR INFORMATION (12) Zajacek, J. G.; Pa, D.; Crocco, G. L. Integrated process for
Corresponding Author epoxide production. US 5214168, Arco Chemical Technology, L.P.;
*E-mail: [email protected]. 1993.
(13) http://www.sumitomo-chem.co.jp/english/rd/report/theses/
Notes docs/20060100_ely.pdf (accessed Jan 2013).
The authors declare no competing financial interest. (14) Prescher. G.; Schreyer, G.; Weiberg, O.; Wirthwein, R.;

■ ACKNOWLEDGMENTS
This study was funded by CONSER S.p.A.
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