catalytic hdo of phenolics in the gas and liquid phase ...eu project, fp7-nmp: fast...

SINTEF Materials and ChemistryEU project, FP7-NMP: FAST industrialisation by CAtalysts Research and DevelopmentCoordinator: SINTEF

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FASTCARD (2014 – 2017)Fast industrialization by Catalyst R&D

Catalytic HDO of phenolics in the gas and liquid phase over supported MoO3 and its pre-carburized analogues

Senior Scientist Rune Lødeng (SINTEF)PhD candidate Chanakya Ranga and Prof. Joris Thybaut (UGent)

CALL NMP.2013.1.1-1"Exploration, optimisation and control of

nano-catalytic processes for energy applications"

Cascatbel workshop18 – 20 May, Porto Carras, Greece 2016


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Biofuels in NorwayNorway; • "A laboratory for electric cars"• Share of new cars sold spring 2016; 20% hybrid cars, 18% electrical cars

Do we need biofuels?• October 2015: Tax on bio-fuels was lowered as part of a campaign to increase

biofuel share towards 5.5% (assist market development)• February 2016: Surprise when it was discovered that 60% of biofuel on market

("HVO100") is based on palm oil (NOT sustainable was politicians opinion)• Other sustainable options still not easily available with relevant capacity• Discussion then triggered in media about to what degree use of wood etc is

climate friendly and sustainable, or if it just contributes to increased levels of CO2 in the atmosphere (waste wood ok, whole trees not?), politicians remains confused

FASTCARD is based on lignocellulose as raw materialNorway is committed to the EU-30-30-30 targetsA national research centre for renewable energy is planned


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Fastcard global objectives

●To speed up catalyst industrialisation in Europe Compatible with existing refinery infrastructure in Europe Or breaking investment costs for new units By a systematic demonstration at pilot scale

●To speed up catalyst development Decreasing failure risks

Down and upscaling solutions to enable unbiased catalyst design and R&D Increasing success rates

Parallel testing on long runs to monitor deactivation

●Scale integration of knowledge-based designapproaches Miniaturisation: by reactor simulations laboratorypilot scales Rational design: by µkinetics supported by DFT & in-situ tech.


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Structure, strategy, deliverables

WP3


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FAST implementation strategy


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Liquid value-chain / Partners

FAST PYROLYSIS Stabilization Deep HDO

(Phenolics) Co-FCC

BTG, WP3 leadR. Venderbosch Boreskov(BIC) SINTEF, UGent Repsol, Grace, CNRS, SINTEF

UGent, modeling (feed descriptors, Nano-descriptors)

PDC, techno-economic evaluation (TEE), life-cycle analysis (LCA)

NiCu/SiO2Piqula

MoOx/ZrO2 + carburized analoguesSoA: CoMoOx/ZrO2 and Al2O3

• Key words; Next generation catalysts for producing high quality co-feed to FCC plants• Challenges; Robustness of performance, hydrogen consumption and pressure,

improved durability, and selectivity at varying depth of O removal

BIOMASS

Fuels


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Catalyst materials

Preparation inspired by:Composition and procedure inspired by; Y.S. Al-Zeghayer, et al., Activity of CoMo/γ-A2O3 as a catalyst in hydrodesulfurization: effects of Co/Mo ratio and drying conditions, Appl. Catal. A: General 282 (2005) 163 - 171

MoO3/ZrO2• 7 wt.% Mo (oxide + two levels of carburization severity)• 15 wt.% Mo ( - " -)• 25 wt.% Mo ( - " -)

"CoMo" reference materials (SoA)• 15 wt.% Mo 3.68 wt.% Co/Al2O3• 15 wt.% Mo 3.68 wt.% Co/ZrO2

Supports• ZrO2-A (ca. 51 m2/g, 160/600 Å bimodal pores, 0.3 cm3/g)• ZrO2-B (ca. 90 m2/g, 80/400 Å bimodal pores, 0.31 cm3/g)• Al2O3 ((ca. 100 m2/g, 100Å, 0.49 cm3/g Vp)

CarburizationGas; CH4/H2 = 4/1Severity; 550 oC and 700 oC


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ICP / Elemental analysis

*) Data from UGent

Mo loading [wt.%]Nominal 7 15 25Analysed 7 12 19


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Temperature Programmed Reduction (TPR)

• Carburization decreases the reducible phase of the "MoO3/ZrO2" system• SoA more complex reduction, Al2O3 supported is the least reducible

-20

0

20

40

60

80

100

120

140

160

180

200

0 100 200 300 400 500 600 700 800

Sign

al

Temperature

15 MoO3/ZrO2 (A)15 MoOxCy/ZrO2 (A)15 Mo2C/ZrO2 (A)

15 MoO3/ZrO215 MoOC/ZrO2 ("550 oC")15 Mo2C/ZrO2 ("700 oC")

-20

0

20

40

60

80

100

120

140

160

180

0 100 200 300 400 500 600 700 800

Sign

al

Temperature

15Mo3.68Co/Al2O315Mo3.68Co/ZrO2 (A)

15 Mo 3.7 Co/Al2O315 Mo 3.7 Co/ZrO2

Mo-oxide & carburized analogues SoA; Mo-oxide & (Co) metal

Support; ZrO2-A (ca. 51 m2/g, 160/600 Å bimodal pores, 0.3 cm3/g)


X-ray diffraction spectrometry (XRD)

• The high temperature treatment appears to be associated with– reduction of MoO3 to MoO2– formation of molybdenum carbide – possible formation of carbon

MoO3/ZrO2 and carburized analogues


• Rather low D values• D decreases with Mo loading• D decreases with carburization severity

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Dispersion (D) by CO chemisorption

Mo loading 15 MoO3/ZrO2 15 Mo - carburized 550 oC 15 Mo - carburized 700 oC[wt.%]

7 1,6 0,7 0,6

12 1 0,3 0,3

19 1,1 0,3 0,1

Support; ZrO2-B (ca. 90 m2/g, 80/400 Å bimodal pores, 0.31 cm3/g)


X-ray photoelectron spectroscopy (XPS)

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Relative atomic Mo/Zr ratios in surface layers

Catalyst Mo/Zr ratio[atomic]

7 MoO3/ZrO2 A 0.16

7 MoO3/ZrO2 B 0.1712 MoO3/ZrO2 A 0.22

19 MoO3/ZrO2 A 0.23

19 MoO3/ZrO2 B 0.28

• Low loading gives better Mo distribution

• Particle size on "7 Mo" and "25 Mo" smallest on high SA support

Spectra of Mo 3d core level shows• Dominant MoO3• Growing peak of Mo2O5 (beam sensitive samples)• Carbon is located on surface


TEM; 7 MoO3/ZrO2 (A) catalyst

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• The crystallite typical size is around 20 nm. Crystallites tended to aggregate so that it is only possible to observe individual crystallites at the edges of the aggregates clearly

For the 25 wt.% catalyst crystal particle size distribution from 20nm to larger aggregates


STEM/EDS analysis of 7 MoO3/ZrO2 (A) catalyst

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• Figures shows EDS analysis of an other aggregate of the 7Mo/ZrO2 (A) catalyst. This indicated compositional homogeneity of the sample

STEM Zr Mo O

For the 25 wt.% catalyst it was some visible coarse scale inhomogeneity within the aggregates of the materials


Combustion IR / Carbon content

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Catalyst Carbon content[wt.%]

15 MoO3/ZrO2 0,02415 MoOC/ZrO2 0,02415 Mo2C/ZrO2 0,0977 Mo2C/ZrO2 0,07425 Mo2C/ZrO2 0,061

Higher C content in the 15 and 25wt% samples than "base level"

Amounts are large enough to make a difference, if on surface

Base level of C


200 mm

¼" o.d. stainless steel tube i.d. = ca. 4 mm

VCR

Trickle-bed reactor1/8"

1/8"

VCR

T < 550 oC, < 100 bars

Thermo-couple / aligned at inner wallPositioned at bed inlet

115 mm

Catalyst bed

SiC inert

Downflow mode


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Single (model) feed components

Phenol Anisole Guaiacol

Strategy: Target kinetics of simple feeds and models with different functionality

https://en.wikipedia.org/wiki/File:Phenol2.svg

https://en.wikipedia.org/wiki/File:Phenol2.svg

https://en.wikipedia.org/wiki/File:Anisol.svg

https://en.wikipedia.org/wiki/File:Anisol.svg

https://en.wikipedia.org/wiki/File:Guaiacol.png

https://en.wikipedia.org/wiki/File:Guaiacol.png


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Typical test conditions (liquid and gas phase)

Parameter Liquid phase Gas phase

Space time [Kgcat.s.mol-1] 100 - 1500 120 - 200

H2/phenolic ratio ca. 100 50

Pressure [bar] 30 - 70 5

Temperature [oC] 300 - 375 300 - 360Inert oil n-decane n-hexanePhenolic conc. [wt.%] 0.75 - 1.5 ca. 10 - 15Particle size [mm] 0.1 - 0.3 0.1 - 0.2

SINTEF Univ. Gent

Standard pretreatment = reduction in H2

No effect of reduction observed at 350 oC (1.5 to 19 hours)


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Phenolics and O removal potential

Gua

Gua / O -removal


Effect of Mo-oxide loading / Phenol HDO

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0

20

40

60

80

100

0 1 2 3 4 5 6 7 8 9

Conv

ersi

on o

f Phe

nol [

%]

Time on stream [h]

R14 7MoO3/ZrO2-A

R13 15MoO3/ZrO2-A

R33 25MoO3/ZrO2-A

Support ZrO2 - A: SSA = 50 m2/gPores = 160/600Å

LHSV = ca. 1.07 h -1

72

55

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LHSV = ca. 1 gPh/gcat,h

7MoO3/ZrO2

15MoO3/ZrO2

25MoO3/ZrO2


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Operating conditions

Temperature (K) 613

Pressure (MPa) 0.5

Space time (kgcat.s/molanisole) 124

H2/anisole (mol.mol-1) 50

Performance comparison MoO3 catalysts

0.1

0.2

0.3

0.4

0.5

0 10 20 30 40 50 60 70 80 90 100

Conv

ersio

n (m

ol.m

ol-1

)

TOS (h)

7MoO3 15MoO3 25MoO3

0

0,1

0,2

0,3

0,4

0,5

613 593 573

Conv

ersi

on (m

ol.m

ol-1

)

Temperature (K)

7MoO3/B-ZrO215MoO3/B-ZrO225MoO3/B-ZrO2


Pressure (MPa) 0.5

Space time (kgcat.s/molanisole)

156



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Effect of carburizing severity

0

20

40

60

80

100

0 1 2 3 4 5 6 7 8 9

Conv

ersio

n of

Phe

nol [

%]

Time on stream [h]

R13 15MoO3/ZrO2 - A

R20 15MoOC/ZrO2 - A

R23 15 Mo2C/ZrO2 - A73

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Temperature = 350 oCPressure = 60 bars1.5wt% phenolLHSV = ca. 1.07 h -1

SeverityMoO3

"MoOxCy"

"Mo2C"

Fingerprint of product composition is also basically similar


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Effect of carburization severity

0.1

0.2

0.3

0.4

0.5

0 10 20 30 40 50 60 70 80 90 100

conv

ersio

n (m

ol.m

ol-1

)

TOS (h)

15MoO3 15MoOxCy 15Mo2C


Temperature (K) 613

Pressure (MPa) 0.5

Space time (kgcat.s/molanisole)

124


340 oC5 bars



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Anisole HDO, conversion and products

0

20

40

60

80

100

0 2 4 6 8 10

Conv

ersi

on /

Sel

ectiv

ity [%

]

Time on stream [hours]

Conv - feed basis

Conv - product basis

Benzene

CyclohexEne

Toluene

Phenol

Cresol

Temperature = 350 oCPressure = 60 barsLHSV (anisole) = 0.24 g/gcat,h

Conversion

Benzene = main

Side products

Benzene

Toluene

Cresol Phenol

Conversion

Green = O-free product


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Typical product selectivity distributionMoO3/ZrO2 and carburized analogues

0

0.1

0.2

0.3

0.4

0.5

0 10 20 30 40 50 60 70 80 90 100

Sele

ctiv

ity

TOS (h)

Benzene ToluenePhenol methylanisoleCresol di methylphenol

0

0,1

0,2

0,3

0,4

0,5

Sele

ctiv

ity/c

onve

rsio

n (m

ol.m

ol-1

)

benz

ene

phen

ol

cres

ol

Dim

ethy

l phe

nol

Met

hyl a

niso

le

tolu

ene

Aniso

le

conv

ersio

n


Temperature (K) 613

Pressure (MPa) 0.5Space time

(kgcat.s/molanisole) 124


340 oC5 bars

Anisolconversion

Benzene

CresolMethyl anisole

Phenol

TolueneDimethyl phenol

40 – 50% oxygen removal efficiency


Main Pathways Phenol HDO (Systems; MoO3 and carburized analogues)

OH

H2 + H2O

+ H2

+ H2

Carbonaceous, coverage and/or polymerization

"Pre-stage of gum?"

Same basic fingerprint withvery high hydrogenolysis to hydrogenation ratio.96%


Main pathways Phenol HDO(SoA system: CoMo/ZrO2)

OH

+ H2O

+ H2

+ H2

OHOH

+ H2O

n-C6

+ H2

Cyclohexanol not observed (350 oC)

H2

H2

+ H2

Co introduces higher hydrogenationactivity and poorer stability


Main Pathways Anisole HDO Liquid Phase(MoO3 on ZrO2)

OCH3

H2

+ CH3OH+ H2O+ CH4

+ H2

OH

+ H2OH

CH3

Anisole

Phenol

Toluene

Cyclohexenes

Cresol

CH3

+H2O/TA

+CH4/TA

Light prod.: HydrogenolysisTA: transalkylation

70%

10% 10%

< 5%

< 2%


Conclusions

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Catalyst and active phase• A loading of 12 wt.% Mo more optimal than 7 and 19 wt.%• The first 7 wt.% Mo has highest activity, though• Activity is related to Mo oxide in a high oxidation state

Carburization• Causing reduction• Some surface carbon formed, but position/state is not clear• Carburization is not providing positive effects on performance

Liquid phase versus gas phase HDOSimilar order of activity

• Loading; 7, 12, 19 wt.% MoO3/ZrO2

• Carburization severity; MoO3/ZrO2 and its carburized analogues

Differences in O removal efficiency• Transalkylation and isomerization reactions more prominent at gas phase conditions, i.e. at

higher reactant concentrations and lower H2 pressures


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ACKNOWLEDGEMENT

The funding of the FASTCARD project (Grant agreement 204277) and the iCAD project (Contract no. 615456) is highly acknowledged!

Contributions from SINTEF: Research Scientists Hilde Bjørkan, Svatopluk Chytil, Dept. Kinetics and catalysisResearch Scientist Ingeborg H. Svenum, Senior Scientist John Walmsley, Dept. Materials Physics;


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Norway

11th Natural Gas Conversion symposium, Tromsø – June 5 – 9, 2016

catalytic hdo of phenolics in the gas and liquid phase ...eu project, fp7-nmp: fast...

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