Zeolite nano-reactor for investigating sintering effects of cobalt

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Kinetics, Catalysis, and Reaction Engineering

Zeolite nano-reactor for investigating sintering effects of cobalt-catalyzed Fischer-Tropsch synthesis Jin Hee Lee, Wouter Bonte, Steven Corthals, Frank Krumeich, Matthijs Ruitenbeek, and Jeroen A. van Bokhoven Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b05755 • Publication Date (Web): 04 Mar 2019 Downloaded from http://pubs.acs.org on March 5, 2019

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Industrial & Engineering Chemistry Research

Zeolite nano-reactor for investigating sintering effects of cobalt-catalyzed Fischer-Tropsch synthesis Jin Hee Lee1,2, Wouter Bonte3, Steven Corthals3, Frank Krumeich,4 Matthijs Ruitenbeek3.*, and Jeroen A. van Bokhoven1,4,* 1 Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland 2 Center for Environment & Sustainable Resources, Korea Research Institute of Chemical Technology, 34114 Daejeon, South Korea 3 Dow Benelux BV, Hydrocarbons R&D, PO Box 48, 4530 AA Terneuzen, The Netherlands 4 Department of Chemistry and Applied Bioscience, ETH Zurich, 8093 Zurich, Switzerland *Corresponding authors. Email: [email protected], [email protected],

ACS Paragon Plus Environment

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Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT. In this study, hollow zeolite nano-reactor are applied which promote uniform nanoparticle formation and inhibit sintering of active nanoparticles during Fischer-Tropsch synthesis. Cobalt oxide nanoparticles are selectively placed in the hollow zeolite cage. The confinement effect of hollow zeolite cage results in the formation of uniformly sized cobalt oxide nanoparticles. In addition, the nano-reactor seems to inhibit the sintering of the nanoparticles located in the cavity during Fischer-Tropsch synthesis. The similar Fischer-Tropsch synthesis activity and durability of sintered and non-sintered catalysts indicate that other mechanisms than sintering apply to the deactivation of this specific cobalt Fischer-Tropsch synthesis catalyst.

KEYWORDS. nano-reactor, sintering, Fischer-Tropsh synthesis, cobalt oxide, hollow zeolite


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1. Introduction Protection of the catalytic active sites is of great interest particularly in industrial applications. The harsh reaction conditions often result in the sintering of active particles and deterioration of catalytic activity. Encapsulation of nano-particles by carbon,1-2 metal oxides,3-6 and zeolites7-10 is a decent strategy to prevent particle agglomeration. The confined nanoparticles found interesting catalytic applications, for instance the control of reaction selectivity by cages that hosts the nanoparticles,9-10 and improvement of catalyst durability by protecting active particles in the hollow structure.7-8 Fischer-Tropsch synthesis (FTS) is a versatile reaction that converts syngas to liquid hydrocarbon such as gasoline and diesel.

11-13

The typically-applied cobalt FTS catalysts often

undergo deactivation and numerous research has focused on understanding and overcoming catalyst deactivation.14-16 The re-oxidation of surface cobalt is an important deactivation mechanism.17-18 Carbon deposition on FTS catalysts lowers catalyst performance by blocking and reconstructing the active surface.19-20 Formation of inactive cobalt-support compounds such as cobalt aluminate and cobalt silicate occurs over alumina and silica.21-22 Catalyst sintering, which reduces the number of active sites, is accelerated at high carbon monoxide conversion levels, i.e. at high steam concentration.23-25 Despite the importance of the deactivation mechanism in developing durable catalyst, the full recognition of deactivation behaviors of cobalt FTS catalyst is complicated, because several deactivation processes can occur simultaneously. Therefore, the development of selective methods that monitor a single deactivation factor is required. In this study, we employed a cobalt oxide-single crystal zeolite nano-reactor as a model system to demonstrate the effect of confined space and to determine the roles of particle sintering on FTS catalyst deactivation. The encapsulated cobalt oxide has a resistance to the sintering under a FTS


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reaction condition. The comparison between the nano-reactor catalyst and normal catalyst enabled the sole exploration of particle sintering on FTS. Moreover, dual-functions of cobalt oxide-single crystal zeolite nano-reactor are presented.

2. Experimental section 2.1. Material synthesis The hollow ZSM-5 was synthesized by preferential dissolution of the ZSM-5 core (Si/Al = 100) using aqueous sodium hydroxide solution according to previous reports.26 After acid exchange of ZSM-5, 20 wt% of cobalt oxide was introduced in the hollow ZSM-5 by incipient wetness impregnation of cobalt nitrate.27 The same procedure was repeated using non-hollow ZSM-5 to yield CoOx/ZSM-5.

2.2. Material characterizations Brunauer–Emmett–Teller (BET) surface area, pore characteristics of the catalysts were measured by nitrogen physisorption at 77 K with a Triflex (Micromeritics). The samples were degassed at 300 °C under reduced pressure for 12 h. The surface area, micropore volume were derived from BET model and t-plot. The total pore volume was calculated by a single point nitrogen adsorption at 0.95 P/P0. X-ray diffractions (XRDs) of the materials were implemented on a D8 advance diffractometer (Bruker) using Cu K radiation. For transmission electron microscopy (TEM), the sample was dispersed in ethanol and some droplets were deposited on a holey carbon foil supported on a Cu grid. TEM was performed on a Tecnai F30 microscope (FEI, now: Thermo Fisher Scientific) at an acceleration voltage of 300 kV (field emission gun, point resolution ca. 0.2 nm).


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2.3. Catalytic activity tests Catalysts performance testing was done in a fixed-bed reactor set-up described elsewhere.28-29 For these experiments, 1 gram of sample (20-40 mesh) was diluted with 8 gram (5 ml) of SiC (36 mesh) and placed in the isothermal zone of the reactor with 100% SiC at the inlet and outlet. Samples were first reduced in 60 ml/min H2 at 400 °C for 60 minutes. After cool down in H2 to reaction temperature (220 °C), syngas was fed to the reactor at 37.5 ml/min (62% H2, 31% CO and 7% He as an internal standard) and the system was pressurized to 10 bar. After 144 h time on stream, temperature was increased to 230 °C to increase conversion levels.

3. Results and Discussions 3.1. Physical and chemical properties of the catalysts 17±4.2 nm

0

(b)

10 20 30 40 50 Size of particles (nm)

17±8.6 nm

Number of particles

(a)

Number of particles

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0


20 nm

Figure 1. TEM images of (a) CoOx/hollow ZSM-5 and (b) CoOx/ZSM-5, scale bars are 20 nm.


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Cobalt oxide particles with a diameter of ca. 17 nm were located in the cavity of the hollow zeolite with a narrow size distribution (Figure 1a). Most of the hollow crystals hold one or two nanoparticles in the cavity (Figures 1a and S1). The TEM tomography confirmed the presence of the cobalt oxide nanoparticles inside of the hollow zeolite cavity.27 Cobalt oxide nanoparticles on the non-hollow ZSM-5, CoOx/ZSM-5, was synthesized for the comparison by identical procedure except employing the non-hollow ZSM-5 as a support. The average size of cobalt oxide nanoparticles of CoOx/ZSM-5 was same as CoOx/hollow ZSM-5 but the particle size distribution was larger (Figures 1b and S2). These results demonstrate that the formation of uniform sized nanoparticles is promoted by the hollow cavity. The confined pores of the ZSM-5 crystals, which can accumulate uniform amounts of precursor solution might help to form the homogeneous size nanoparticles.12, 30 Previous studies reported that cobalt catalyzed FTS showed the highest activity on 6 nm cobalt particles, however turn over frequency (TOF) was steady over 6 nm.31-32 Our materials of 17 nm cobalt oxide particles are not the best catalyst for FTS but similarly sized CoOx/hollow ZSM-5 and CoOx/ZSM-5 are considered to be appropriate to demonstrate the impact of nano-reactor concept on the investigation of sintering effects.


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(a)

Co3O4

Intensity (a.u.)

(200) (400) (111) (311)

(422)(911)

CoOx/hollow ZSM-5 CoOx/ZSM-5 ZSM-5 10

20

30

40

50

60

70

2 (degree)

(b)

600

ZSM-5 CoOx/ZSM-5

500

hollow ZSM-5 CoOx/hollow ZSM-5

3 -1

Adsorped quantity (cm g )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


400 300 200 100 0 0.0

0.2

0.4

0.6

0.8

1.0

Relative pressure, P/P0

Figure 2. (a) XRD patterns of ZSM-5 (black), CoOx/ZSM-5 (red), and CoOx/hollow ZSM-5 (blue), (b) nitrogen adsorption-desorption isotherm plots of ZSM-5 (■), CoOx/ZSM-5 (▲), hollow ZSM-5 (○), and CoOx/hollow ZSM-5 (▽).

The crystallinity of ZSM-5 was not affected by the sodium hydroxide leaching and the cobalt oxide impregnation (Figure 2a). The diffraction patterns of ZSM-5, CoOx/ZSM-5, and CoOx/hollow ZSM-5 showed characteristic features of MFI zeolite. The XRDs of CoOx/ZSM-5 and CoOx/hollow ZSM-5 confirmed the exclusive presence of spinel Co3O4 phase in both catalysts. Nitrogen physisorption indicated that the surface areas had decreased for both hollow and nonhollow materials after cobalt addition. The hysteresis in the range of P/P0>0.4 indicates the formation of mesopores in the hollow ZSM-5. The micropore area of non-hollow ZSM-5 was


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somewhat decreased from 190 m2g-1 to 158 m2g-1 after cobalt oxide incorporation but that of hollow ZSM-5 was unchanged (Table 1, entries 1 and 2). The decrease of micropore volume was also more prominent in non-hollow ZSM-5 (0.0979 m2g-1 to 0.0706 m2g-1) than hollow ZSM-5 (0.0902 m2g-1 to 0.0852 m2g-1) (Table 1, entries 1-4). These observations indicate that cobalt oxide particles might block the micropores of ZSM-5, but not the micropores of hollow ZSM-5.

Table 1. Surface areas and pore volumes of ZSM-5, hollow ZSM-5, CoOx/ZSM-5, and CoOx/hollow ZSM-5 SBETa

Smicrob

Vmicroc

Vtotd

(m2g-1)

(m2g-1)

(cm3g-1)

(cm3g-1)

Entry

Materials

1

ZSM-5

296

190

0.0979

0.233

2

CoOx/ ZSM-5

280

158

0.0706

0.212

3

hollow ZSM-5

402

195

0.0902

0.381

4

CoOx/hollow ZSM-5

400

196

0.0852

0.360

a

Derived from the BET model. measured at P/P0 = 0.95

b, c

Derived from the t-plot. d Derived from single point


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3.2. Catalytic activity

Figure 3. Time on stream catalytic FTS activity of CoOx/ZSM-5 (black) and CoOx/hollow ZSM5 (red), (a) carbon monoxide conversion, (b) C1 selectivity, (c) C2-C4 selectivity, and (d) C5-C12 selectivity. The FTS performance of CoOx/ZSM-5 and CoOx/hollow ZSM-5 was tested at 220 °C and 10 bar of syngas flow at a H2 to CO ratio of 2. The general catalytic behavior is similar over investigated two catalysts (Figure 3). The carbon monoxide conversion was initially equal about 60% and gradually decreased to 40% after 150 h. The catalyst deactivation occurred on both of the CoOx/ZSM-5 and the CoOx/hollow ZSM-5. The product selectivity of the two catalysts was identical (Figures 3b-d). To increase conversion level, the temperature was increased to 230 °C, resulting in a jump of the conversion level without a significant change of selectivity (Figure 3a,


9


150 h). Wherever the cobalt oxide particles are located, the deactivation of FTS catalyst was not inhibited.

(a)

20

(b)

CoOx/ZSM-5

15

10

5

0

20

CoOx/hollow ZSM-5

15

Selectivity (%)

Selectivity (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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20 10

5

5

10

15

20

Carbon number

0

5

10

15

Carbon number

20

Figure 4. Product distributions of FTS catalyzed by (a) CoOx/ZSM-5 and (b) CoOx/hollow ZSM-5 at 40% carbon monoxide conversion Figure 4 displays the product distributions of FTS at 40% carbon monoxide conversion level. Both catalysts showed low selectivity to long chain products over C15, due to the hydrocracking ability of acidic ZSM-5 that limits the formation of long chain hydrocarbon.33 There were no considerable differences in the carbon monoxide conversion and the carbon product profiles of CoOx/ZSM-5 and CoOx/hollow ZSM-5 catalyzed FTS products (Figure 3). However, the iso-tonormal ratios of C10-C13 fractions were lower over CoOx/ZSM-5 than over CoOx/hollow ZSM5, indicating lower isomerization rates on the former. Bifunctional cobalt-zeolite FTS catalysts follow consecutive two step reactions; a chain growth on cobalt sites to produce linear hydrocarbon followed by a hydrocracking and/or isomerization to form branched hydrocarbons. Products formed in the hollow zeolite must diffuse through the zeolite wall which may result in the longer


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isomerization rate. Such confinement effects on the product selectivity of bifunctional FTS

(a)

18±4.0 nm

0

(b)


Number of particles

catalysts are also reported by other studies.34-35 Number of particles

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


34±32 nm

0


20 nm

Figure 5. TEM images of (a) CoOx/hollow ZSM-5, and (b) CoOx/ZSM-5 after 200 h FTS reaction, scale bars are 20 nm. Although CoOx/ZSM-5 and CoOx/hollow ZSM-5 exhibited comparable catalytic behavior, the features of the spent catalysts (after 200 h FTS reaction) were significantly different. The CoOx/hollow ZSM-5 maintained its initial particle size and narrow distribution, which successfully demonstrates the strategy to apply zeolite nano-reactor to avoid particle sintering (Figures 5a and S3). However, the CoOx/ZSM-5 severely sintered after the FTS reaction (Figures 5b and S4). The average particle size was increased from 17 nm to 34 nm. Moreover, the standard deviation of the cobalt particles greatly increased from ±8.6 nm to ±32 nm due to the aggregation and larger crystal formation of over 60 nm. Regardless of sintering occurring or not, the two catalysts showed similar deactivation trends during FTS experiments. These results therefore demonstrate that sintering is not a major reason


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of catalyst deactivation in this particular catalytic system. Other factors than catalyst sintering such as cobalt oxidation, cobalt-support compound formation, and/or coke formation would be responsible for the catalyst deactivation.

4. Conclusion The ZSM-5 nano-reactor that contains cobalt oxide in the hollow cage were developed. During the cobalt oxide impregnation the uniform internal pore of hollow ZSM-5 provided the sites for the uniform nanoparticle formation and the internal mesopores inhibited the blocking of zeolite micropores by cobalt oxide nanoparticles. The confined space protected the active cobalt particles from sintering during FTS. Although the cobalt particles were protected from sintering, the FTS activity gradually decreased at the same rate with the sintered catalyst. This result remarks that the sintering does not affect FTS performance so other deactivation mechanisms such as cobalt oxidation, cobalt-support compounds formation, and/or carbon-deposition apply. The nano-reactor offers the sintering free-catalyst which helps to keep the active surface area of catalysts. In addition, the nano-reactor can be utilized as a chemical tool to understand sintering effects in conventional catalysis.

ASSOCIATED CONTENT Supporting Information. The additional TEM images of fresh and used catalysts are available. Figure S1. TEM images of CoOx/hollow ZSM-5 before FTS reaction, Figure S2. TEM images of CoOx/ZSM-5 before FTS reaction, Figure S3. TEM images of CoOx/hollow ZSM-5 after 200 h of FTS reaction, Figure S4. TEM images of CoOx/ZSM-5 after 200 h of FTS reaction


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AUTHOR INFORMATION Corresponding Aurthour *Matthijs Ruitenbeek, Email: [email protected] *Jeroen A. van Bokhoven, Email: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

ACKNOWLEDGMENT We thank to Paul Scherrer Institute for the financial supports

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Table of Contents CO + H2

zeolite nano-reactor

C nH n

After

Before 17±4.2 nm

0


Number of particles

Number of particles

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


18±4.0 nm

0



17

Zeolite nano-reactor for investigating sintering effects of cobalt

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