Chemie

Ingenieur Communication 159

Technik

Incorporation of Microreactor Measurements

into a Pilot-Scale Phthalic Anhydride Reactor
Nico Fischer*, Patrick Hubach, and Christian Woll
DOI: 10.1002/cite.201400002

A major obstacle in the development of industrial catalysts is the scalability of both catalyst performance and synthesis.
While utilizing pilot-scale test reactors allows for a direct transfer from the development stage to the application, it comes
at the cost of flexibility. The amount of catalyst required in a pilot-scale test reactor often surpasses the yields of novel syn-
thesis procedures, requiring extensive scale-up efforts. Here, pilot-scale reactors are combined with small lab-scale reac-
tors, using the example of oxidation of o-xylene to phthalic anhydride.
Keywords: Microreactor, Selective oxidation catalysis, Vanadium on anatase, o-Xylene
Received: January 13, 2014; revised: February 10, 2014; accepted: October 10, 2014

1 Introduction [11, 12]. To facilitate the testing of small amounts of such

Phthalic acid [1] and its anhydride (PA), first described in
1836, were initially produced on industrial scale from naph-
thalene [2, 3] via a catalytic liquid phase process and later
via a catalytic gas phase oxidation with air as oxidant. In
1945, the first industrial production of PA via the gas phase
oxidation of o-xylene (o-X) was conducted [4]. Due to the
higher selectivity and lower exothermicity, the o-X route
subsequently replaced naphthalene as feed molecule. Today,
approximately 84 % of the world-wide operating PA plants
use o-X as feed stock [5]. However, due to the different
sources of the feed molecules (o-X from crude oil, naphtha-
lene mainly from coal), the naphthalene-based PA produc-
tion is economically viable in areas were cheap coal is avail-
able.
Since the operation of the first gas phase oxidation reac-
tors to yield PA, vanadium based catalysts were utilized [3].
Over the years, the catalyst systems developed to convert
o-X to PA, without selectivity losses due to total combus-
tion, became more and more complex. Today, four or more
different catalyst layers are filled in each reactor tube on a
total catalyst bed length of 3 – 4 m. While all are based on
vanadium on TiO2 (V/Ti) supported on a non-porous inac-
tive carrier material, the different layers are designed to
show different activities and selectivities via the addition of
various promoter elements [6 – 10].
To further increase the selectivity, researchers explore
new active materials not based on the classic V/Ti system
– testing of new materials in small scale under relevant reac-
1
Dr. Nico Fischer (nico.fischer@uct.ac.za), University of Cape
Town, Department of Chemical Engineering, Rondebosch, Cape
Town 7700, South Africa; 2Dr. Nico Fischer, Patrick Hubach,
Christian Woll, BASF SE, Carl-Bosch-Straße 38, 67063 Ludwigs-
hafen, Germany.
materials under realistic feed gas conditions, i.e. for their
usability in different catalyst layers, a small screening reac-
tor concept was developed, allowing the testing of new and
potentially active/selective materials in the off-gas streams
of a multiport/multizone pilot tube reactor.
2 Reactor Setup
The catalytic performance of catalysts is tested in single-
tube pilot tube salt bath reactors. Each tube has the same
dimensions as in industrial multitubular reactors. To gain
more insight into the performance of the different layers of
catalysts [6 – 10], multiport reactor tubes are employed,
allowing for online analysis of the product and intermediate
[13] concentrations in the reaction gas stream at different
catalyst bed lengths. To avoid condensation of the high boil-
ing compounds, the different sample ports and correspond-
ing lines have to be continuously heated to temperatures
above 200 °C. To also guarantee this constant temperature
level in the stream selectors, managing the sample injection
to the online GCs, the setup is installed inside a ventilated
heating cabinet. The gas flow to the GCs is controlled via a
calibrated needle valve.
Small amounts of potentially active/selective catalyst ma-
terials can be tested in a heated reaction tube installed in a
bypass to the analysis line inside the heating cabinet (Fig. 1).
As reaction tube, the design allows using various different
inner diameters from 6 to 12 mm. This setup facilitates the
tion gas mixtures, present at different depths of an industri-
al catalyst system, without the need to prepare gas mixtures
or engage in scale-up efforts in an early stage of the devel-
opment/screening process.

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 Chemie
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The targeted vanadium concentration of

a) b) 2
0.3 wt % V2 O5 mTiO 2 support
(equal to 8.1 wt % V 2 O5 or
4.5 wt % V) was not reached. Losses in vanadium during the
catalyst preparation resulted in a approx. 7 % reduced over-
all vanadium loading. Of the 4.2 wt % V in the sample, two
thirds are present as crystalline V2O5. The residual vana-
dium is spread as a mixture of V4+ (CAT-red = 51 %;
CAT-ox = 45 %) and V5+ (CAT-red = 49 %; CAT-ox = 55 %)
amorphous species on the TiO2 support [15].

4 Micro Reactor Feed Gas Composition

The multiport reactor was filled with an industrial catalyst

Figure 1. (a) Schematic representation of the reactor setup. For
simplicity reasons, a multiport reactor with only two ports is
as described in patent literature [16, 17]. The full catalyst
shown; Port 2 is selected for the analysis/feed of the screening bed was 320 cm long and five sampling points could be se-
microreactor; (b) image of microreactor in a brass heating block. lected (after 0, 75, 160, 245, and 320 cm catalyst bed length).
The gas streams of the first and third sampling point, at a
3 Preparation of Model Catalysts reactor load of 80 go-xyleneNmair3 and an air flow of
4 NmSTP 3 h–1, were selected as feed gas for the screening
Two simple V/Ti catalyst systems were prepared to validate
reactor (for the gas compositions, see Tab. 2). As reported
the reactor setup. For both catalysts, the vanadium species
previously [13 – 15], the oxidation of o-xylene to phthalic
are deposited on a TiO2 in the anatase modification with a
anhydride is a multiple step consecutive reaction. While
BET surface area of 27 m2g–1. The catalysts differ in the oxi-
Marx et al. [13] report a total of 20 intermediates and over-
dation state of the vanadium source as well as of the vanadi-
oxidation products, this study is focused on the 8 most
um species which is deposited on the support. An overall
prominent ones.
vanadium loading, calculated as V2O5, of 0.3 wt % m–2 BET
is targeted. This corresponds roughly to a Vox-coverage of
Table 2. Gas composition at the first and third sampling point
2 monolayers under operating conditions [14, 15] in the gas of the multiport reactor used as feed gas for the screening reac-
phase oxidation of o-xylene to PA. tor (reaction conditions: Tsalt bath = 361 °C, air flow = 4 Nm3STP h–1,
For the model catalyst CAT-red, V2O5 is dissolved in a o-X = 80 g Nm3air ).
heated solution of oxalic acid. The resulting V4+ solution is
added to a TiO2/water suspension and dried under nitrogen Reactant / product [vol-%] catalyst bed length
atmosphere in a laboratory spray dryer at a nozzle tempera- 0 cm 160 cm
ture of 245 °C (Büchi Mini Spray Dryer B-290). CAT-ox is
C8 intermediates
prepared by dissolving V2O4 in a 10 % HNO3 aqueous solu-
tion. The resulting V5+ solution is added to the TiO2/water o-xylene (o-X) 1.638 0.261
suspension and also spray dried. Both catalysts were calcined tolualdehyde (o-TA) 0.000 0.050
in a rotary kiln at 400 °C for 2 h with a heating ramp of 2 °C
min–1 under a constant flow of air (10 LSTPh–1). After calcina- toluic acid (o-TAc) 0.000 0.008
tion both catalysts were characterized for their crystalline phthalide (PHD) 0.000 0.046
phases (powder X-ray diffraction and Rietveld refinement for
over-oxidation products
quantitative analysis), vanadium oxidation state (titration),
total vanadium content and BETsurface area (Tab. 1). phthalic anhydride (PA) 0.000 1.182

Table 1. Characterization results of prepared model catalysts maleic anhydride (MA) 0.000 0.069
after calcination.
citraconic anhydride (CA) 0.000 0.006
catalyst XRD [wt %] Voxa) [–] Vb) [wt %] BET [m2g–1] benzoic acid (BA) 0.000 0.005
CAT-red TiO2, Anatase = 4.83 4.2 26 CO 0.000 0.480
95
V2O5 = 5 CO2 0.044 1.140

CAT-ox TiO2, Anatase = 4.85 4.2 24

95
V2O5 = 5
a) Oxidation state of vanadium species; b) Vanadium content cal-
culated as V.

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5 Microreactor Performance
The microreactor was charged with approximately 1 g of
800 – 1200 mm splitting of the two model catalysts. Splitting
was prepared by mixing 2 wt % graphite with the calcined
catalyst samples and forming a tablet in a hand press, fol-
lowed by crushing in a mortar and sieving to yield the
desired size fraction. The microreactor inlet gas was set to a
volume stream resulting in a gas hourly space velocity of
2600 h–1.
Fig. 2 displays the catalytic performance of CAT-red at
300 and 370 °C charged with a pure o-xylene in air stream
(Fig. 2a) and a feed gas composition originating from the
samples after the 160 cm of catalyst bed in the multiport
reactor (Fig. 2b).
a)
b)
Figure 2. Microreactor inlet and outlet gas compositions for
catalyst CAT-red at 300 and 370 °C. (a) Feed gas from the 0 cm
catalyst bed length in the multiport reactor; (b) feed gas from
the 160 cm catalyst bed length in the multiport reactor. For ab-
breviations, see Tab. 2.
Even at 300 °C, 99.6 % of the reactant in the pure o-xylene
stream was reacted. While at lower temperatures, 42 % of
the reactive carbon feed was converted to the desired prod-
uct PA, the detected by-products were all over-oxidation
products with an overwhelming amount being COx and to
a lesser extend maleic anhydride (MA) and benzoic acid
(BA). Trace amounts of citraconic anhydride (CA) could al-
so be detected. No C8 intermediates from the reaction path-
way to PA, i.e., tolualdehyde (o-TA), toluic acid (o-TAc) or
phthalide (PHD), were found. At elevated temperatures, the
main product was COx and the concentration of PA of 98 %
was lower than the one measured at 300 °C.
Chem. Ing. Tech. 2015, 87, No. 1–2, 159–162 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
161
The o-X in the intermediates feed stream was fully con-
verted in the microreactor at both temperatures. While the
feed stream contained all analyzed compounds (Tab. 2), no
C8 intermediates were detected in the reactor outlet gas at
the set temperatures. The oxidation of PA in the reactor at
300 °C resulted in a decrease in concentration of 20 %, at
370 °C the inlet PA concentration was reduced by over
97 %. While at 300 °C the concentration of over-oxidation
products besides COx increased, only trace amounts of MA
remained at 370 °C.
Compared to CAT-red, CAT-ox showed an only slightly
lower activity at 300 °C (conversion o-X: 99.5 %) for the
pure o-X in air feed stream (Fig. 3a). However, the tendency
to over-oxidation is significantly lower. The selectivity to PA
is by 11 % higher and the concentration of MA, CA and BA
as well as COx is significantly lower. Additionally, C8 inter-
mediates such as PHD and trace amounts of o-TA and
o-TAc were identified in the reactor outlet gas. At 370 °C,
no difference between the two catalysts could be measured.
The PA concentration in the reactor outlet gas is by 99 %
lower than measured at 300 °C and no compounds but COx
could be detected.
a)
b)
Figure 3. Microreactor inlet and outlet gas compositions for
catalyst CAT-ox at 300 and 370 °C. (a) Feed gas from the 0 cm
catalyst bed length in the multiport reactor; (b) feed gas from
the 160 cm catalyst bed length in the multiport reactor. For ab-
breviations, see Tab. 2.
Charging the reactor with the intermediates feed gas
composition (Tab. 2), CAT-ox showed a very similar behav-
ior to CAT-red. However, an overall higher oxidation poten-
tial can be observed. While in the case of CAT-red the inlet
PA concentration is decreased by 20 % at 300 °C, for
CAT-ox this concentration is decreased by 52 %. Further-
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162
more, the CO2/CO ratio is clearly higher for CAT-ox, i.e., References
3.00 vs. 2.86 at 300 °C and 3.36 vs. 2.42 at 370 °C, again sup-
porting the observed higher oxidation potential of CAT-ox. [1]
[2]
[3]
[4]
6 Conclusion [5]
[6]
A microreactor for screening purposes has successfully been
incorporated into an existing setup of a pilot-scale multi- [7]
zone multitubular reactor. This new setup allows the testing
of novel active masses from lab-scale preparation routes in [8]
regards to their activity and selectivity under realistic indus-
[9]
trial conditions. This is an often observed gap between
industrial and academic research [18], and the new setup [10]
can as such potentially simplify the search for new catalyti-
cally active lead structures. Although the above discussed [11]
model catalyst systems chosen for the demonstration of the
reactor setup are inspired from our research in the field of [12]
the selective o-xylene oxidation to phthalic anhydride, the
[13]
reactor concept can easily be applied to other reactions and
catalyst systems such as the formation of acrylic acid, the [14]
oxidative dehydrogenation of n-butane, the oxidation of [15]
n-butane to maleic anhydride, and in fact all other gas [16]
phase and catalyst based reactions. Due to the presence of
multiple high boilers in the feed and product gases of the [17]
o-xylene oxidation, the shown application can be assumed
[18]
to be a worst case scenario for the screening reactor.
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