Catalysts for glycerol hydrogenolysis: production of glycols from biomass derivatives

Daniela Zanchet Instituto de Química, UNICAMP, Campinas, SP

daniela@iqm.unicamp.br 2007/51754-4 - PITE project as part of FAPESP-OXITENO and BIOEN initiative

Term: 10/2008-03/2011

LNLS-CNPEM (ABTLuS)

Dr. Cristiane B. Rodella

Dr. Silvia Fernanda Moya

Dr. Ricardo J. Chimentão

Lígia S.Rodrigues (tech. – TT2)

Rafael A. Ferreira (tech. - TT2)

Oxiteno Ind. & Com. Ltda

Dr. Valéria P. Vicentini

Ms. Carla M. S. Queiroz

Team

Collaborators

Dr. Roberto Rinaldi (Max-Planck)

Prof. Victor Teixeira (UFRJ)

Glycerol Hydrogenolysis

Glycerol major by-product of biodiesel production (low cost, large

volume) . New opportunites (“glycerochemistry”)

Goal

H2

H2

Evaluation and development of heterogeneous catalysts

(industrial application at OXITENO);

Understanding of the kinetics and mechanism of the catalytic

hydrogenolysis - Selectivity to EG or 1,2-PG

Correlation with physical and chemical properties of the catalysts

Model catalysts based on nanoscience approach

Goal

A. Torres et al., Ind. Eng. Chem. Res. , 2010; C.J. Mota et al. Quimica Nova, 2009.

+H2

-H2O

H

H

Scientific challenges Glycerol hydrogenolysis is a complex chemical reaction →

parallel pathways and reactions (reforming, WGS, methanation)

Coupled reactions Reforming+ hydrogenolysis

Roy et al, Cat. Today, 156 (2010), 31; Yin et al., Green Chem., 11 (2009), 1514.

For the reaction:

Coupled reactions - maximize activity and selectivity to either EG

and 1,2-PG; minimize the formation of gas products (conc., T, P)

For the catalyst:

Tuning catalysts properties (electronic configuration, particle size,

defects, metal dispersion, etc.): active sites that enhance different

type of bond cleavage: C-C, C-O, C-H, O-H

Keeping in mind… to find the best compromise considering the

specific needs of OXITENO

Scientific challenges

High pressure reactor installed in an explosion-proof room – similar to OXITENO set-up

Integration and automation of reactor operation software and safety interlocks

Fixed bed reactor set-up

Gas chromatograph

Infrastructure at LSQ-LNLS

Catalysts development and testing:

Conventional catalyst: Ru/C best catalyst to promote C-C cleavage,

but high cost and severe catalytic reaction conditions

Alternatives :

•Ni Raney low cost and mild catalytic reaction condition (no need

of external H2)

• Tungsten carbides supported on carbon platinum-like catalytic

behavior, efficient for cellulose hydrogenolysis, low cost but severe

catalytic reaction conditions

•Model catalysts based on colloidal nanoparticles

Catalysts

5% Ru/C

Samples: 5% Ru/C (Acros) 5% Ru/C – LNLS (dry impregnation RuCl3)

1wt.% glycerol, 110 mg of catalyst, 4MPa of H2

Ni2Al3

NiAl3

Al

Ni-Al alloy

Raney Ni catalyst

C.B. Rodella, G. Kellermann, M.S.P. Francisco, M.H. Jordão, D. Zanchet, Ind. Eng. Chem. Res. 2008, 47, 8612.

Samples: Raney Ni 3111A - Grace Co. (1% Mo) Raney Ni 2800 - Grace Co. Raney Ni - LNLS

Raney Ni

10wt.% glycerol, 1,67g of catalyst

Raney Ni x Ru/C

Both produce large amounts of gas (CO2, CH4)

Raney Ni →1,2-PG Ru/C → EG

H2 pressure favors EG. Raney Ni favors the reforming

of glycerol

Selectivity to EG decreases with time

Degradation of EG is more pronounced in Ru/C

The results pointed out that high selectivity to EG will

be difficult to be achieved in batch reactor

(Temperature transient at the beginning).

Ru/C

C-A C-B C-MERCK

Conversion (%) 26,0 23,7 30,7

Selectivity

(%)

EG 19,4 29,6 27,2

1,2-PG 13,5 15,3 11,9

CO2 1,6 0,4 -

CH4 59,1 43,5 48,4

Others 6,4 11,2 13,5

Selectivity to liq. (%) 34,0 50,2 44,1

*All samples presented traces of acetol .

Carbon support Dependence on the carbon support supplier

P.Trecco (Undergraduate project)

Improves surface area

Tungsten Carbides -Synthesis

Temperature Programmed Carburization (TCP)

WO3 WOx (0x3) W W2C WC

7000C 8500C

9000C 100 – 200 ml.min-1 pure H2 or 10%CH4/H2

+

W

bcc

C

amorphous

W2C

hcp

WC

hex

Temperature or

Promoters like Ni, Fe and Co decrease carburization temperature and improve catalytic activity

Structural characterization XRD - in situ

X Ray beamline

Furnace

θ

Structural and surface properties - dependent on the gas used in

the carburization process and presence of Ni

H2 → well crystallized W2C, carbon deposition and low conversion

20%CH4/H2 → smaller particles, less carbon deposition and

higher conversion.

Ni → carburization at lower temperature (100 K)

Glycerol hydrogenolysis favors 1,2-PG (acetol pathway).

WxC

Preliminary results showed low activity in the hydrogenolysis of propane

Ru-NPs NiPt-NPs

Collaboration with Dr. C.S. Claro and F. Requejo - Univ. La Plata, Argentina

Colloidal nanoparticles

Conclusion

Evaluation of catalysts for hydrogenolysis of glycerol: EG is favored at short times. No satisfactory results were found with batch reactor Selectivity to gas products excessively high.

Raney Ni - favors H* generation through glycerol reforming Ru/C – higher selectivity to EG WxC - carburization with CH4/H2 and presence of Ni improve the performance. Selectivity towards 1,2-PG

Influence of the C support (?)

Other results: invited talk at CBCAT/11, CatBior/11, 2 articles in preparation

Acknowledgments

Dr. Cristiane Rodella (WxC - LNLS) Dr. Silvia Moya (CTBE) Dr. Ricardo Chimentão Ligia Rodrigues Rafael Ferreira LNLS staff

Dr. Valéria Vicentini Carla Queiroz Oxiteno staff

Funding: FAPESP, Oxiteno, LNLS

Dr. Roberto Rinaldi (Max-Planck) Prof. Victor Teixeira (UFRJ)

Prof. Jose Maria C. Bueno Debora M. Meira Renata U. Ribeiro

Dr. Cecilia Claro (ULP) Dr. Felix Requejo (ULP)

Dr. Jose L. Zotin (CENPES) Sandra Chiaro (CENPES)