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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
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
iSGA4 2014, September 3
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
iSGA4 2014, September 3
iSGA4 2014, September 3
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
iSGA4 2014, September 3
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
iSGA4 2014, September 3
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
iSGA4 2014, September 3
FISCHER-TROPSCH PILOT PLANTiSGA4 2014, September 3
iSGA4 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
C21+ Selectivity wt.% 40.63
C5+ Selectivity wt.% 90.13
iSGA4 2014, September 3
TESTING NON-SULFIDED Co-Mo/SiO2-Al2O3 AND COMMERCIAL HYDROCRACKING CATALYST
Synthesized CoMo/SiO2-Al2O3
Commercial hydrocracking catalyst
iSGA4 2014, September 3
CARBON NUMBER DISTRIBUTION OF ALKANES AND ALKENES
Synthesized CoMo/SiO2-Al2O3
Commercial hydrocracking catalyst
iSGA4 2014, September 3
CARBON NUMBER DISTRIBUTION IN SOLID AND LIQUID FT PRODUCTS
Synthesized CoMo/SiO2-Al2O3
Commercial hydrocracking catalyst
iSGA4 2014, September 3
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!
ROCAT SYNFUELS22 Valea Cetatii Street
500289, Brasov, RomaniaRO Phone: +40 743 157 131USA Phone: +1 713 370 2783
iSGA4 2014, September 3