Presentation iSGA4 - A. Sauciuc -2015

PERFORMANCES OF A NON-SULFIDED CoMo/SiO2-Al2O3 HYDROCRACKING

CATALYST USED IN BTL TECHNOLOGY

Anca SAUCIUC [email protected] GANEALucia DUMITRESCUReinhard RAUCHHermann HOFBAUER

iSGA4 2014, September 3

mailto:[email protected]

Running R&D projects and offering technical solution for clients in the field of biotechnology – alternative fuels & chemicals synthesis, upgrading and characterization

Activities

Objectives

• Solutions in FT synthesis, refining, heterogeneous catalysts, analytical techniques for alternative fuels & chemicals characterization

• Carrier and catalysts characterization (surface morphology, composition, metal dispersion, mechanical strength

• Experimental work design• Coordination of analytical &

research projects• Data processing and

interpretation

• Customer satisfaction by high quality services in technical area, efficient research projects ongoing within the deadline

• Finding new solutions for clients requirements with minimum costs of investment

• Exclusivity and priority for existing clients

• Confidentiality of projects and results

• Flexibility to client requirements


ABOUT MYSELF PhD in Materials Engineering

Fischer-Tropsch synthetic diesel from biomass by synthesizing, characterizing and optimizing the performances of non-sulfided CoMo hydrocracking catalysts using amorphous γ-Al2O3 and SiO2-Al2O3 as supports

Scientific contributions:

• Patent proposal• 6 ISI Papers• 1 Book Chapter published by

Elsevier – The Role of Catalysis for Sustainable Production of Bio-fuels and Bio-chemicals, 1st Edition



MOTIVATIONS OF THE RESEARCH FT products – more than 80 wt.% hydrocarbons with carbon number

higher than C5 Hydroprocessing FT products – possibility to obtain synthetic fuels

with superior properties (cold flow properties)

High conversion of hydrocarbons – high pressure 60 bar → few reports dealing with mild hydrocracking

FT products – zero sulfur concentration → non-sulfided hydrocracking catalysts Pd Pt based hydrocracking catalysts – non-sulfurization → 300-1300 times more

expensive than Ni, Co → non-sulfided CoMo/SiO2-Al2O3

• Mo>W>Pt>Pd>Ni– hydrogenating activity

• Ni, Co, Pt – promoters, prevent catalyst deactivation and coke deposition

• Sulfurization – decrease of hydrogenation function• Support - strong acidity – cracking function

• SiO2-Al2O3 – acidity ↑↑, “ideal” hydrocracking

• USY, HZSM-5, SAPO-5 – surface area ↑↑ conversion ↑↑↑, isomerization

CoMo/SiO2-Al2O3 CATALYST SYNTHESISiSGA4 2014, September 3

Simple and low cost technology applied for hydrocracking catalysts synthesis – incipient successive wet impregnation → Minimum reagent require

Applicability at large scale – 500 g for testing in Fischer-Tropsch pilot plant

SiO2-Al2O3 SUPPORT CHARACTERIZATIONiSGA4 2014, September 3

Crystallites size (XRD)

AlOOH, SiO2 – 3-6 nm → dense structure

Al(OH)3 – 21-27 nm → loose structure

γ-Al2O3 – 4.5 nm

Transition phases (DSC)

calcination temperature→ 550 ºC SiO2-Al2O3

SEM-EDX supports morphology – dense structure,

irregular shaped aggregates interconnected → meso, macro pores

Support composition EDX [wt.%] SiO2-Al2O3

TheoreticallyAl 39.1

Si 5.6

Calculated Al 38.9

Si 3.2

CoMo/SiO2-Al2O3 CATALYST CHARACTERIZATION


Metals composition [wt.%] CoMo/SiO2-Al2O3

Theoretically

Co 1.8

Mo 6.6

Co/(Co+Mo) 0.3

Calculated

Co 1.8

Mo 5.9

Co/(Co+Mo) 0.33

Crystallites size (XRD)

Peaks attributed to CoO and MoO3

Crystallites size increase – 6.35 nm → metal dispersion on support surface

SYNGAS GENERATION - CHP PLANT GÜSSING


FISCHER-TROPSCH PILOT PLANTiSGA4 2014, September 3


FISCHER-TROPSCH SYNTHESIS

Operating conditions: H2/CO 1.6-1.8, 240 °C, 20 bar, 5 Nm3/h, 2 m3kg-1h-1

CO Conversion % 68.9

α value - 0.87

Productivity kg/h 0.275

C10-C20 Selectivity wt.% 58.26

C21-C30 Selectivity wt.% 28.9

C31+ Selectivity wt.% 11.73




TESTING NON-SULFIDED Co-Mo/SiO2-Al2O3 AND COMMERCIAL HYDROCRACKING CATALYST

Synthesized CoMo/SiO2-Al2O3

Commercial hydrocracking catalyst


CARBON NUMBER DISTRIBUTION OF ALKANES AND ALKENES




CARBON NUMBER DISTRIBUTION IN SOLID AND LIQUID FT PRODUCTS




Property M.U.EN

590:2004

ASTM

D975

Petroleum

diesel

FT

diesel

HFT

diesel

Cetane number - < 51 > 40 - 69.8 81.2

Cetane index > 46 > 40 52 61.1 78.2

Density kg/m3 820-845 829 765 755

Viscosity mm2/s 2-4.5 1.9-4.1 2.54 2.45 1.45

Pour point ºC - - -9,3 3 -7

Alkanes wt.% - - 19.8 78.5 84

Alkenes wt.% - - - 11,18 7.08

Aromatics wt.% - max 35 21.3 1.4 6.3

CHARACTERIZATION OF HYDROTREATED FISCHER-TROPSCH DIESEL

Annealing the support at 550 ºC proved the transition of boehmite into amorphous γ-Al2O3

The morphology of SiO2-Al2O3 → amorphous aggregates interconnected as chain-like structure with meso and macro pores

High Co and Mo dispersion on the support surface has been achieved using incipient wet impregnation

Long-time operation of CoMo/SiO2-Al2O3 hydrocracking catalyst in the continuous flow and under low operating pressure proved the efficiency of the catalyst

Maximum hydrocarbons conversion - 63% → with only 5% lower than the maximum conversion of a commercial hydrocracking catalyst

Selectivity for middle distillate has been improved by increasing the operating temperature

Pour point property has been remarkable improved, increasing the capacity of hydroprocessed FT synthetic diesel fuel to be pumped under cold conditions

NEXT WORK → optimizing the recipe and further tests of hydrocracking FT wax

CONCLUSIONSiSGA4 2014, September 3

THANK YOU FOR ATTENTION!

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Presentation iSGA4 - A. Sauciuc -2015

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