Chemical Engineering Journal 295 (2016) 370–375

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Green and efficient epoxidation of propylene with hydrogen peroxide

(HPPO process) catalyzed by hollow TS-1 zeolite: A 1.0 kt/a pilot-scale
study
Min Lin a, Changjiu Xia a,b,⇑, Bin Zhu a, Hua Li c, Xingtian Shu a
a
State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, 100083 Beijing, PR China
b
Department of Material and Environmental Chemistry, Stockholm University, Stockholm SE 106 91, Sweden
c
Changling Petrochemical Co. Ltd., SINOPEC, Yueyang 414012, Hunan Province, PR China

h i g h l i g h t s

Hollow TS-1 zeolite is an good catalyst for HPPO process at pilot scale.

Increasing the solubility of propylene favors fast conversion rate.

Shortening the residence time of H2O2 insider benefits high PO selectivity.

The lifetime of hollow TS-1 zeolite in HPPO process is very long.

a r t i c l e i n f o a b s t r a c t

Article history: The propylene epoxidation catalyzed by hollow TS-1 zeolite with 30 wt% H2O2 solution as oxidant at
Received 4 September 2015 1.0 kt/a pilot plant has been examined. Rising reaction temperature is in favor of increasing TOF of
Received in revised form 3 February 2016 H2O2 but reduces the selectivity of PO, due to the promotion of major and side reactions at the same time.
Accepted 19 February 2016
Enhancing the CH3OH amount and the WHSV of H2O2 is preferential to improving the TOF of H2O2 and
Available online 26 February 2016
the selectivity of PO, but increase capital and energy consumption as well. Taking all into consideration,
the optimized epoxidation has been confirmed: T is 40–50 °C; molar ratio of CH3OH/H2O2 is 5–15, and the
Keywords:
WHSV of H2O2 is more than 1.2 h1. When the epoxidation of propylene carried out over 6000 h, the TOF
Epoxidation
Hollow TS-1
of H2O2 is 30.9–32.2 mmol g1 h1 and the PO selectivity is 96–99%, respectively. The final PO product
Zeolite from this plant is at 99.97% purity, which has been used as an intermediate to synthesize kinds of
Pilot scale chemicals.
Propylene oxide Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction
Propylene oxide (PO) is one of key propylene based chemical
intermediates for producing fine chemicals, such as polyurethane
plastics, polyglycol esters, unsaturated resins and surfactants
[1–3]. As the fast development of material and environmental tech-
nologies, the demand of PO is continuously growing in the world,
for example, the global PO market is over 7.5 million tons in
2010. Several of synthetic methods have been exploited for produc-
ing PO in academic and industrial sections, i.e. chlorohydrin pro-
cess, styrene monomer propene oxide (PO/SM) process, tert-butyl
alcohol (PO/TBA) process, cumene hydroperoxide (CHP) process
⇑ Corresponding author at: State Key Laboratory of Catalytic Materials and
Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, 100083
Beijing, PR China.
E-mail address: xiachangjiu@gmail.com (C. Xia).
and hydrogen peroxide propene oxide (HPPO) process [4–9]. Com-
pared with other four routes, HPPO route is much more
environmental-friendly, without the generation of toxic by-
products and wastes. HPPO process is based on titanium silicate
(TS-1) zeolite as catalyst, [10–13] low concentration (30–50 wt%)
aqueous H2O2 solution as oxidant under mild conditions (usually
lower than 70 °C) [14,15]. The first commercial HPPO propylene
epoxidation plant at 100 kt/a capacity was launched by Evonik
and SKC at Korea in 2008 [16]. Then, several more HPPO process
units were set up gradually in Belgium by BASF and DOW (300 kt/
a, 2009), [17] in China by Evonik and Uhde (230 kt/a, 2013), [18]
and in Thailand by DOW (390 kt/a, 2012) [19]. In HPPO process,
PO is produced directly from propylene in a one-step reaction, as
illustrated in Fig. 1. However, epoxidation is a cascade reaction,
and these side products lower the yield of PO via secondary reac-
tion. Among them, propylene glycol monomethyl ethers (MME,

http://dx.doi.org/10.1016/j.cej.2016.02.072
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
 M. Lin et al. / Chemical Engineering Journal 295 (2016) 370–375 371

O hydroxide (TPAOH) was selected as organic structure directing

TS-1 zeolite
H3C CH CH2 + H2O2 H3C C CH2 + H2O
Methanol H (a)
30-70 oC
OH OH
H 3C C CH2
2O H
O +H
H 3C C CH2
H +C CH3
H O OH OH O Then, the mixture was transferred to Teflon autoclave and
3 OH
H 3C C CH2 + H3C C CH2
H H
Fig. 1. Major and side reactions involved in the epoxidation of propylene catalyzed
by TS-1 zeolite in mild conditions: (1) major reaction of propylene epoxidation; (b)
side ring-opening reactions of PO with CH3OH and H2O2.
with two isomers, as shown in Fig. 1) and 1,2-propylene glycol (PG)
are the two main byproducts, which are formed by ring-opening
reactions of PO with CH3OH and H2O. Thus, it is of ultra-
importance to optimize the operating parameters, such as reaction
temperature, CH3OH concentration, and weight hourly space veloc-
ity (WHSV) of H2O2, to avoid these side reactions occurred.
However, the conversional TS-1 zeolite usually has poor cat-
alytic activity and reproducibility, due to the mismatch of hydrol-
ysis and crystallization rates between Si and Ti species under
hydrothermal conditions [20]. To solve these problems, the hollow
TS-1 zeolite was produced by post-synthesis method in the pres-
ence of TPAOH solution at high temperature [21–23]. Compared
with conventional TS-1, hollow TS-1 zeolite is of abundant
intracrystalline cavities and high framework Ti species content.
In our previous working, hollow TS-1 zeolite exhibits higher cat-
alytic performances and stability in several oxidation reactions
with aqueous H2O2 solution as oxidant, such as cyclohexanone
ammoxidation, aromatic oxidation, phenol hydroxylation at indus-
trial scale and propylene epoxidation in lab. Herein, the epoxida-
tion of propylene catalyzed by hollow TS-1 zeolite has been
carried out at 1.0 kt/a pilot scale. Thus the effects of several major
important parameters on epoxidation reaction have been systemi-
cally investigated, for obtaining the optimized reaction conditions
to support the even larger pilot scale test [24].
2. Experimental
2.1. Synthesis of hollow TS-1 zeolite catalyst
Hollow TS-1 zeolite was synthesized as previously published
method [25,26]. In a general procedure, tetrapropylammonium
agent (OSDA) for synthesis of the TS-1 zeolite, as described in
ENI method. The molar ratio of SiO2:TiO2:TPAOH:H2O is
1:0.04:0.36:40, the hydrothermal synthesis temperature is
170 °C, under the autogenous pressure. Firstly, the tetraethyl
orthosilicate (TEOS) and tetrabutyl orthotitanate (TBOT) was dis-
solved in the aqueous TPAOH solution, and this mixture was
heated at 80 °C for evaporating the ethanol and butanol molecules.
CH3 (b)
hydrothermally synthesized at high temperature for 3 days. After
that, the as made TS-1 zeolite was calcined at 550 °C for 3 h. In sec-
ond step, the calcined TS-1 zeolite was post-synthesized at 170 °C
for 1 day in the presence of OSDA under autogenous pressure, as
illustrated in the literatures [21]. In addition, the calcined hollow
TS-1 zeolite was characterized by multiple characterization meth-
ods, and sharped as catalyst for HPPO process.
2.2. Characterization of hollow TS-1 zeolite
X-ray powder diffraction patterns (XPRD) were collected on a
Bruker (Siemens) D5005 diffractometer using nickel filtered Cu
Ka radiation (k = 1.5418 Å) under ambient conditions in the 2h
range of 5–35° with a step size of 0.02° and exposure time of 1 s
per step. N2 adsorption/desorption isotherms were collected at
77 K using a Micromeritics ASAP 2010 apparatus. Before the mea-
surement, about 50 mg of the sample was dehydrated under vac-
uum (103 Torr) at 300 °C overnight. The specific surface areas
were determined from the linear part of the BET equation. Trans-
mission electron microscopy (TEM) was carried out on a FEI G2
F20S-TWIN electron microscope. Scanning electron microscopy
(SEM) was operated on a FEI Quanta 200F instrument.
2.3. Catalytic testing at 1.0 kt/a scale
The pilot-scale propylene epoxidation reaction was carried out
on a fixed bed reactor, and the corresponding schematic diagram
is illustrated in Fig. 2. In a typical procedure, hollow TS-1 zeolite
was sharped into about £ 1–3 mm particles, and then they were
added into a stainless tube reactor. Then, the mixture of CH3OH,
H2O2 (30 wt%), H2O and propylene was injected into the bottom
of reactor, and the reaction temperature was 30–70 °C. After the
epoxidation of propylene with H2O2, the mixture of solvent, prod-
ucts and reagents went into the C@ 3 separation tower for evaporat-
ing the remainder propylene, which can be reused as starting
material for this process. Moreover, the mixture from the bottom
of C@ 3 separation tower went into the PO separation tower, for

Fig. 2. Schematic process flow diagram of propylene epoxidation at 1.0 kt/a pilot scale.
372 M. Lin et al. / Chemical Engineering Journal 295 (2016) 370–375

Fig. 3. Multiple characterization results of hollow TS-1 zeolite catalyst: (a) TEM image; (b) SEM image; (c) PXRD pattern; (d) low temperature N2 adsorption–desorption
isotherm; (e) UV–Vis spectrum; and (f) FT-IR spectrum of hollow TS-1 zeolite.

separating raw PO from the aqueous CH3OH solution. After that, selectivity of PO, MME and PG were calculated as following equa-
the raw PO was refined in the PO purification tower, while the tions, respectively.
CH3OH was purified in the H2O/CH3OH separation tower. In the
n0H2 O2  nH2 O2
end, the H2O was removed from this process, and the purified X H2 O2 ¼  100%
CH3OH was recycled as solvent for this reaction. n0H2 O2
Propylene and epoxidation products were qualitatively ana-
lyzed by the ThermoFisher Trace ISQ mass spectroscopy (MS) WHSVH2 O2  X H2 O2
TOFH2 O2 ¼
equipment, and quantatified by the Agilent HP-6890 gas chro- MH2 O2
matography (GC) apparatus, with a hydrogen flame ionization
detector and a 30 m  0.25 mm  0.33 lm HP-5 weak polar GC nPO
SPO ¼  100%
column. Conversion and turnover frequency (TOF) of H2O2, the nPO þ nMME þ nPG
 M. Lin et al. / Chemical Engineering Journal 295 (2016) 370–375 373

nMME
SMME ¼
nPO þ nMME þ nPG
 100% (a)
32.2

TOF of H2O2 molecules/(mmol.gCat .h )

-1
nPG

-1
SPG ¼  100% 32.0
nPO þ nMME þ nPG
31.8

3. Results and discussion

31.6

3.1. Characterization of hollow TS-1 zeolite

31.4

Multiple characterization results of hollow TS-1 zeolite are

31.2
illustrated in Fig. 3. From the result of XRD pattern, five diffraction
peaks between 22° and 25° are apparently detected, which indi-
31.0
cates that this material is of typical MFI topology and in high crys- 40 50 60 70
tallinity [27,28]. Meanwhile from high magnification SEM image, o
Reaction Temperature/ C
we can observe that the hollow TS-1 zeolite particle is of aggregate
morphology, and the crystal size ranges from 250 to 300 nm. AS 100 (b)
shown in TEM image, hollow TS-1 zeolite is of abundant intracrys- PO
MME
talline pores, which are in favor of mass diffusion inside zeolite

Selectivity of major and side product/%

crystal. The size distribution of hollow cavities is not very uniform
(ranging from several to tens nanometers), which is favor of high
catalytic activity by enhancing the accessibility of reagent and pro-
duct molecules to active sites [29,30]. Moreover, the intracrys-
talline mesopores are confirmed by low temperature (77 K) N2
adsorption–desorption isotherm method. Obviously, there is a H4
hysteresis loop at P/P0 > 0.45 for hollow TS-1 zeolite, due to the
capillary condensation effects of blocked mesopores [31,32].
Furthermore, the pore parameters of hollow TS-1 zeolite are calcu-
lated by using Brunauer–Emmett–Teller (BET) model, which gives
a specific surface area of 437 m2 g1 and a micropore volume of
0.173 cm3 g1. It is noteworthy that the pore parameter of hollow
TS-1 zeolite is larger than that of common TS-1 zeolite in the liter-
atures. With respect to the chemical statue of Ti species, two
apparent bands at 210 nm and 330 nm are observed in the
UV–Vis spectrum, which are attributed to the tetrahedral frame-
work Ti species and anatase TiO2, respectively [33,34]. In addition,
there is a band near 960 cm1 appeared in the FT-IR spectrum,
which is usually considered as the evidence of the TiAOASi bond’s
stretching vibration [35]. Consequently, the incorporation of iso-
lated Ti species into the framework matrix in tetrahedral coordina-
tion has been confirmed. Thus, the high catalytic performance of
hollow TS-1 in propylene epoxidation reaction can be expected,
due to the enhancement of mass diffusion property and much
more active sites.
3.2. Effect of reaction temperature on propylene epoxidation
It is widely accepted that the reaction temperature plays an
important role in the conversion rate of H2O2 molecules, which is
attributed to the propylene epoxidation is a strongly exothermic
reaction [4,36]. However, when reaction temperature increases,
some side reactions, such as ring-opening and hydrolysis, will be
happened, causing the reducing of the selectivity of PO. In our
study, when reaction temperature passing from 40 to 70 °C as
shown in Fig. 4(a), the TOF of H2O2 molecule slightly increases
from 31.16 to 32.20 mmol g1cat h
1
. However, the selectivity of PO
decreases from 98.9% to 95.6%, while the selectivity of MME and
PG increases continuously as a function of the reaction tempera-
ture in this range, as shown in Fig. 4(b). Moreover, it is suggested
that increasing reaction temperature can accelerate the ring-
opening reactions of PO and H2O2 decomposition under the impact
of H2O, CH3OH molecules and catalyst. That is because raising tem-
perature can improve the self-ionization of H2O and CH3OH mole-
cules, with the increasing formation of H3O+ and OH ions [37].
Then, these acidic and basic groups can serve as catalysts for
PG
95
90
10
5
0
40 50 60 70
o
Reaction temperature/ C
Fig. 4. Effect of reaction temperature on reaction rate (TOF) of H2O2 molecules (a)
and the selectivity distribution of products (b) in propylene epoxidation reaction.
Reaction conditions: P = 1.5 MPa, WHSV of H2O2 molecules is 1.1 h1, nCH3 OH =nH2 O2
is 6, nPropylene =nH2 O2 is 2.5.
hydrolyzed ring-opening and H2O2 decomposition reactions,
producing much more MME and PG and reducing the utilization
efficiency of H2O2. On the other hand, if propylene epoxidation
carried out at very low temperature, the amount of remainder
H2O2 will be increased. It is related to safety issue and reduces
the utilization efficiency of H2O2. Here, the optimized reaction
temperature is 40–50 °C, for achieving high PO selectivity.
3.3. Effect of solvent methanol amount on propylene epoxidation
Due to epoxidation reaction is extremely exothermic, adding
solvent amount is preferential to removing the heat from reaction
system, to limit the adiabatic temperature rise inside reactor and
avoid safety problem. Moreover, it has been proposed that the sol-
vent CH3OH participate propylene epoxidation reaction via form-
ing five-membered rings between TiAOOH species and an
adsorbed CH3OH molecule, as described by Clerici and his cowork-
ers [38,39]. Fig. 5(a) presents the effect of solvent amount on the
propylene epoxidation catalyzed by hollow TS-1 zeolite. We
observe that the TOF of H2O2 molecules increases dramatically
from 29.9 to 31.7 mmol g1 cat h
1
, along with the increasing of molar
ratio of CH3OH/H2O2 between 5 and 21. Although adding large
amount of CH3OH reduces the concentrations of H2O2, much more
propylene can be dissolved in the CH3OH solution [2.6  101 mol/
(L atm), at 40 °C], [40,41] increasing the concentration of adsorbed
374 M. Lin et al. / Chemical Engineering Journal 295 (2016) 370–375

32.0 (a) 35 (a)

TOF of H2O2 molecules(mmol.gcat .h )

-1
TOF of H2O2 molecules(mmol.gCat .h )
-1

-1
31.6
30
-1

25
31.2
20
30.8
15

30.4 10

30.0 5

0
29.6 0.0 0.2 0.4 0.6 0.8 1.0 1.2
4 8 12 16 20 24 -1
WHSV of H2O2 molecules/(h )
CH3OH/H2O2 molar ratio

(b)
100 (b) 99.0

98.5
99

98.0

Selectivity of PO/%
Selectivity of PO/%

98
97.5

97 97.0

96 96.5

96.0
95
95.5
94
0 5 10 15 20 25 30 35
4 8 12 16 20 24
-1 -1
CH3OH/H2O2 molar ratio TOF of H2O2 molecules(mmol.g .h )

Fig. 5. Effect of molar ratio of CH3OH to H2O2 on epoxidation of propylene with
H2O2 over hollow TS-1 zeolite catalyst. (a) TOF of H2O2 molecules as a function of
CH3OH/H2O2 molar ratio; (b) selectivity of PO along with CH3OH/H2O2 molar ratio.
Reaction conditions: T = 35 °C, P = 2.0 MPa, WHSV of H2O2 molecules is 1.2 h1,
nPropylene =nH2 O2 is 2.0.
Fig. 6. Effect of WHSV of H2O2 on epoxidation of propylene with H2O2 over hollow
TS-1 zeolite catalyst. (a) TOF of H2O2 molecules as a function of WHSV of H2O2; (b)
selectivity of PO along with WHSV of H2O2. Reaction conditions: T = 65 °C,
P = 1.0 MPa, WHSV of H2O2 molecules is 1.2 h1, nCH3 OH =nH2 O2 is 7, nPropylene =nH2 O2
is 1.4.

propylene molecules. Furthermore, high molar ratio of CH3OH/
H2O2 is favor of the formation of five-membered ring intermedi-
ates, which is one central step of epoxidation reaction mechanism.
As a result, increasing solvent amount is useful for the high conver-
sion rate of H2O2 molecules. As shown in Fig. 5(b), high molar ratio
of CH3OH/H2O2 also leads to the high selectivity of PO (the maxi-
mum value is close to 100%), which is attributed to CH3OH of
weaker nucleophilic capability than H2O for reacting with PO ring.
However, from the viewpoint of application, high molar ratio of
CH3OH/H2O2 means high energy consumed and large towers
needed for purifying the CH3OH as shown in the Fig. 2. Therefore,
by taking all issues into account, we suggest that the optimized
molar ratio of CH3OH/H2O2 lines in 5–15.
3.4. Effect of WHSV of H2O2 molecules on epoxidation of propylene
The TOF of H2O2 molecules and selectivity of PO at 65 °C as a
function of WHSV of H2O2 is illustrated in Fig. 6(a). It is observed
that the TOF of H2O2 molecules increases gradually from 2.94 to
34.27 mmol g1 cat h
1
as a function of WHSV of H2O2 from 0.12 to
1.2 h1, which is in good agreement with other research results
in literatures. It is ascribed to abundant tetrahedral Ti active sites
existed for propylene epoxidation reaction in the range of WHSV
of H2O2 molecules described in Fig. 6. Furthermore, it is worth not-
ing that the selectivity of PO increases significantly from 95.6% to
98.9% along with the increase TOF of H2O2 molecules, as shown
in Fig. 6(b). It suggests that low reactant residence time of H2O2
molecules inside catalyst is preferential to avoiding the deep
epoxide-opening of major product PO. That is to say, these side
reactions can be catalyzed by hollow TS-1 zeolite and binders.
However, when the WHSV of H2O2 molecules is too high, the
corresponding residence time inside the channel of catalyst is too
short to complete epoxidation of propylene. Thus, it is optimized
to select high WHSV of H2O2 (1.2 h1 under the conditions
described in Fig. 6, or even higher than it) for achieving high selec-
tivity of PO.
3.5. The stability of hollow TS-1 zeolite at 1.0 kt/a scale
From the previous sections, it has been confirmed that hollow
TS-1 zeolite catalyst is of high catalytic activity and PO selectivity
in the HPPO process. It is contributed to its hierarchical structure
and the incorporation of isolated tetrahedral Ti species into the
framework matrix of MFI zeolite, which can act as effective Lewis
acid catalyst. To verify the stability of this catalyst, the lifetime of
hollow TS-1 based catalyst was detected at pilot scale, working
at T = 30–70 °C, P = 0.5–2.0 MPa, WHSV of H2O2 molecules is
0.12–1.2 h1, nCH3 OH =nH2 O2 is 5–25, nPropylene =nH2 O2 is 1.2–2.5. In
our previous work, hollow TS-1 zeolite presents even higher cat-
alytic activity and lifetime than conventional TS-1 zeolite in the
cyclohexanone ammoxidation process from lab to industrial scale.
That is because much more TiAOASi and SiAOASi bonds formed
after the recrystallization treatment, reducing the amount of
framework defects (SiAOH and TiAOH groups) and extraframe-
 M. Lin et al. / Chemical Engineering Journal 295 (2016) 370–375
100
98
Selectivity of PO/%
96
94
Selectivity of PO
TOF of H2O2 molecules
92
90
0 1000 2000 3000 4000 5000
Reaction time/h
Fig. 7. The TOF of H2O2 molecules and the selectivity of PO in propylene
epoxidation catalyzed by hollow TS-1 zeolite as a function of reaction time at
1.0 kt/a polite scale. Reaction conditions: T = 30–70 °C, P = 0.5–2.0 MPa, WHSV of
H2O2 molecules is 0.12–1.2 h1, nCH3 OH =nH2 O2 is 5–25, nPropylene =nH2 O2 is 1.2–2.5.
work Ti species. As shown in Fig. 7, the HPPO process catalyzed by
hollow TS-1 zeolite runs very smoothly far than 6000 h at pilot
plant, with almost the same catalytic performance as the initial
catalytic activity. Under the wide operation conditions, the TOF
of H2O2 is around 31–32 mmol g1 h1 (X H2 O2 is 96–99%) and selec-
tivity of PO is 96–99%, which is much better than that reported by
BASF and DOW (the selectivity of PO is 93.2%) [15].
Furthermore, the raw propylene oxide produced in the fixed-
bed reactor is purified in the PO purification column, obtaining
the final PO product at 99.97% purity. And then, the purified PO
has been used as chemical intermediates to manufacture 1,2-
ethyl glycerol, oilfield demulsifier, propylene carbonate, triiso-
propanolamine, hydroxypropyl, dimethyl carbonate in China. By
using these result obtained at 1.0 kt/a pilot plant, one 100 kt/a
industrial demonstration propylene epoxidation unit at SINOPEC
has already been set up and run for a long period smoothly [19].
4. Conclusion
The epoxidation of propylene catalyzed by hollow TS-1 zeolite
based catalyst at 1.0 kt/a pilot scale, operating in a fixed-bed reac-
tor and under mild conditions, has been investigated. Hollow TS-1
zeolite, which is of abundant intracrystalline mesopores and high
framework Ti species, presents high catalytic activity and long life-
time (over 6000 h) in this process. Rising reaction temperature
accelerates the major epoxidation, H2O2 decomposition and ring-
opening reactions at the same time, enhancing the TOF of H2O2
and the selectivity of side-products (such as MME and PG). Increas-
ing CH3OH solvent amount is of ultra-importance to improve the
TOF of H2O2 and PO selectivity, due to adding CH3OH is in favor
of the solubility of propylene and removing the reaction heat to
avoid H2O2 decomposition and epoxide-opening reactions. How-
ever, increasing molar ratio of CH3OH/H2O2 causes the high cost
and energy consumption. Moreover, it is confirmed that hollow
TS-1 based catalyst is of high transformation capacity for epoxida-
tion reaction (WSHV of H2O2 P 1.2 h1). And reducing the resi-
dence time of H2O2 and PO inside catalyst is useful to obtain
high H2O2 TOF and PO selectivity, but reducing H2O2 conversion.
Therefore, taking all factors into consideration, when the reaction
pressure and molar ratio of propylene/H2O2 are fixed at
0.5–2 MPa and 1.2–2.5, respectively, other optimized reaction con-
ditions at 1.0 kt/a pilot scale have been confirmed: T is 40–50 °C;
molar ratio of CH3OH/H2O2 is 5–15, and the WHSV of H2O2 is no
less than 1.2 h1. According to these optimized parameters, an
even larger demonstration unit has been designed and run success-
375
32 fully. And the purified PO from this process has been used as a use-
ful intermediate to produce a variety of chemicals.
TOF of H2O2 molecules/(mmol.g .h )
-1
-1
31
Acknowledgments
30
This work was financially supported by the National Basic
Research Program of China (973 Program, 2006CB202508), China
Petrochemical Corporation (SINOPEC Group 20673054). Changjiu
29 Xia thanks Swedish Research Council (VR) and Swedish Govern-
mental Agency for Innovation Systems (VINNOVA) and the
Göran-Gustafsson Foundation for Natural Sciences and Medical
28 Research.
6000
References
[1] T.A. Nijhuis, M. Makkee, J.A. Moulijn, B.M. Weckhuysen, Ind. Eng. Chem. Res. 45
(2006) 3447–3459.
[2] M.J. Climent, A. Corma, S. Iborra, Chem. Rev. 111 (2) (2011) 1072–1133.
[3] T. Hayashi, K. Tanaka, M. Haruta, J. Catal. 178 (2) (1998) 566–575.
[4] G. Wu, Y. Wang, L. Wang, W. Feng, H. Shi, Y. Lin, T. Zhang, X. Jin, S. Wang, X.
Wu, P. Yao, Chem. Eng. J. 215 (2013) 306–314.
[5] V. Russo, R. Tesser, E. Santacesaria, M. Di Serio, Ind. Eng. Chem. Res. 52 (3)
(2013) 1168–1178.
[6] C. Wang, B. Wang, X. Meng, Z. Mi, Catal. Today 74 (2002) 15.
[7] Z. Xi, N. Zhou, Y. Sun, K. Li, Science 292 (5519) (2001) 1139–1141.
[8] G.F. Thiele, E. Roland, J. Mol. Catal. A: Chem. 117 (1) (1997) 351–356.
[9] W. Song, Y. Zuo, G. Xiong, X. Zhang, F. Jin, L. Liu, X. Wang, Chem. Eng. J. 253
(2014) 464–471.
[10] M. Taramasso, G. Perego, B. Notari. US 4410501, 1983.
[11] B. Notari, Catal. Today 18 (1993) 163.
[12] X. Liu, C. Yang, Y. Wang, Y. Guo, Y. Guo, G. Lu, Chem. Eng. J. 243 (2014) 192–
196.
[13] X. Wang, X. Zhang, Y. Wang, H. Liu, J. Wang, J. Qiu, H.L. Ho, W. Han, K.L. Yeung,
Chem. Eng. J. 175 (2011) 408–416.
[14] Gema Blanco-Brieva, M. Carmen Capel-Sanchez, M. Pilar de Frutos, Ana
Padilla-Polo, Jose M. Campos-Martin, Jose L.G. Fierro, Ind. Eng. Chem. Res. 47
(21) (2008) 8011–8015.
[15] P. Bassler, M. Weidenbach, H. Goebbel, Chem. Eng. Trans. 21 (2010) 571–576.
[16] http://corporate.evonik.com/en/company/locations/location-asia/pages/skc-
evonik-peroxide-korea-co-ltd.aspx.
[17] http://www.chemicals-technology.com/projects/basf-hppo/.
[18] http://corporate.evonik.com/en/media/press_releases/Pages/news-details.
aspx?newsid=45021.
[19] http://newsroom.dow.com/press-release/company-news/scg-dow-group-
achieves-successful-thailand-hppo-plant-start.
[20] C. Shen, Y.J. Wang, J.H. Xu, G.S. Luo, Chem. Eng. J. 259 (2015) 552–561.
[21] Y. Wang, M. Lin, A. Tuel, Microporous Mesoporous Mater. 102 (2007) 80.
[22] A. Zheng, C. Xia, Y. Xiang, M. Xin, B. Zhu, M. Lin, G. Xu, X. Shu, Catal. Commun.
45 (2014) 34.
[23] S. Li, A. Tuel, D. Laprune, F. Meunier, D. Farrusseng, Chem. Mater. 27 (1) (2015)
276–282.
[24] http://urethaneblog.typepad.com/my_weblog/2014/01/sinopec-hppo-plant.
html.
[25] Y. Wang, A. Tuel, Microporous Mesoporous Mater. 113 (2008) 286.
[26] M. Lin, X. Shu, X. Wang, B. Zhu. US 6475465[P], 2002.
[27] A. Carati, C. Flego, D. Berti, R. Millini, B. Stocchi, C. Perego, Stud. Surf. Sci. Catal.
125 (1999) 45–52.
[28] G. Bellussi, A. Carati, M.G. Clerici, G. Maddinelli, R. Millini, J. Catal. 133 (1992)
220.
[29] X. Mu, D. Wang, Y. Wang, M. Lin, S. Cheng, X. Shu, Chin. J. Catal. 34 (2013) 69–
79.
[30] C. Xia, L. Ju, Y. Zhao, H. Xu, B. Zhu, F. Gao, M. Lin, Z. Dai, X. Zou, X. Shu, Chin. J.
Catal. 36 (6) (2015) 845–854.
[31] J. Mielby, J.O. Abildstrøm, F. Wang, T. Kasama, C. Weidenthaler, S. Kegnæs,
Angew. Chem. 126 (2014) 12721–12724.
[32] J. Zečević, C.J. Gommes, H. Friedrich, P.E. de Jongh, K.P. de Jong, Angew. Chem.
Int. Ed. 51 (2012) 4213–4217.
[33] C. Li, G. Xiong, Q. Xin, J. Liu, P. Ying, Z. Feng, J. Li, W. Yang, Y. Wang, G. Wang, X.
Liu, M. Lin, X. Wang, E. Min, Angew. Chem. Int. Ed. 38 (1999) 2220–2222.
[34] S. Bordiga, A. Damin, F. Bonino, G. Ricchiardi, C. Lamberti, A. Zecchina, Angew.
Chem. 114 (24) (2002) 4928–4931.
[35] W. Lin, H. Frei, J. Am. Chem. Soc. 124 (31) (2002) 9292–9298.
[36] R. Sanz, D.P. Serrano, P. Pizarro, I. Moreno, Chem. Eng. J. 171 (3) (2011) 1428–
1438.
[37] H. Lawrence Clever, J. Chem. Educ. 45 (1968) 231.
[38] M.G. Clerici, P. Ingallina, J. Catal. 140 (1993) 71–83.
[39] M. Neurock, L.E. Manzer, Chem. Commun. (1996) 1133–1134.
[40] Y. Miyano, K. Fukuchi, Fluid Phase Equilib. 226 (2004) 183–187.
[41] X. Liu, X. Wang, X. Guo, G. Li, Catal. Today 93 (2004) 505–509.