Biomass conversion in Brazil: main challenges in heterogeneous Catalysis

1. Biomass conversion in Brazil: main challenges in heterogeneous Catalysis Eduardo Falabella Sousa-Aguiar Carla A. F. Melo, Cristina P. B. Quitete, Jefferson R. Gomes, Márcio Portilho, Nei Pereira Jr. EQ/UFRJ and Petrobras/CENPES/CB

2. Spring SleepBai Juyi Introduction The pillow's low, the quilt is warm, the body smooth and peaceful, Sun shines on the door of the room, the curtain not yet open. Still the youthful taste of spring remains in the air, Often it will come to you even in your sleep. Spring SleepBai Juyi, famous chinese poet

3. Introduction • Brazil is the 10th largest energy consumer in the world and the largest in South America. At the same time, it is an important oil and gas producer in the region and the world's second largest ethanol producer. Petroleum and sugar cane represent the major components of the Brazilian energy matrix

4. PRODUCTION EXPLORATION Traditional Oil Industry OIL TRANSPORTATION DISTRIBUTION REFINING Introduction. The main segments of the Traditional Oil Industry

5. The survival of the oil industry will depend on many factors . Indeed, the refiner of the future will have to face multiple challenges. Introduction E. Falabella et al. Catalysis Today (Print), v. 234, 13-23, 2014.

6. Introduction • The main challenges of the refinining industry in the future are the following: • Increasing stringent environmental regulation • Growing demand for cleaner fuels • Globalisation • Increase in the production of derivatives from declining quality oil • Uncertainty about the consumer’s choice • Growing pressure of several segments of the society aiming at the reduction of GHG • Maintenance of its profitability • Search for alternative raw materials such as biomass and coal

7. The refinery must search for intelligent alternative solutions to meet all those requirements. Therefore, the search for alternative feedstock such as biomass has become a must in order to cope with more stringent regulations. Also, alternative refining routes such as synthetic fuels are striking back. Introduction

8. PRODUCTION EXPLORATION BIOMASS OIL Industry of the Future NATURAL GAS OIL TRANSPORTATION DISTRIBUTION BIOFUELS/ BIOCHEMICALS REFIN. XTL PROCESSES Introduction

9. Introduction Hence, the refining of the future will encompass the concept of BIOREFINERIES. According to the 2008 Farm Act, the term means a facility (including equipment and processes) that converts renewable biomass into biofuels and biobased products, and may produce electricity.www.ers.usda.gov/Briefing/bioenergy/glossary.htm More recently, the term INTEGRATED BIOREFINERY has been coined. An integrated biorefinery is capable of efficiently converting a broad range of biomass feedstocks into affordable biofuels, biopower, and other bioproducts. The integrated biorefinery must cope with the problem of residues.

10. Introduction Regarding biomass, Brazil is undoubtedly one of the greatest world’s biomass producers. Nevertheless, such agricultural production implies an enormous generation of residues

11. Introduction Brazilian agribusiness: increasing opportunities due to low land occupancy

12. Introduction Production of Residues from the Main National Cultures Bagasse and straw Sugar cane

13. Introduction Biomass conversion is surely the solution not only for the requirements of the refinery of the future, but also to solve the problem of agricultural residues.

14. Introduction Fuels/Chemicals Biomass feedstock Hydrolysis/ Lignocellulosic Ethanol fermentation biomass Diesel Bio - oil Hydro treating Pyrolysis Paraffin, Syngas Fischer - Tropsch Gasification Lubricants, SUCROCHEMISTRY Naphtha, LPG Modified Mixed alcohols Fischer - Tropsch THERMOCHEMICAL ROUTES Methanol/ Methanol synthesis DME Sugar/starch Hydrolysis/ Ethanol , Butanol, OLEOCHEMISTRY fermentation crops Hydrocarbons Vegetable oils Transesterification Biodiesel and fats Esterification H - Bio ( green diesel) Hydro treating

15. Introduction Actually, biofuels and bio-based products may replace several fuels obtained via traditional oil refining.

16. Lignocellulosic biomass • The lignocellulosic materials are the most abundant organic compounds in the biosphere, participating in approximately 50% of the terrestrial biomass; • The term lignocellulose structure is related to the part of the plant which forms the cell wall, basically constituted of polysaccharides [cellulose (40-60%) and hemicellulose (20-40%)]. • These components are associated to a macromolecular structure containing aromatic substances, denominated lignin (15-25%) • Those materials possess in their compositions approximately, 50-70% of polysaccharides (in a dry basis), which contain in their monomeric units valuable glycosides (sugars).

17. Lignocellulosic biomass Cellulose and hemicellulose have different compositions, hence distinct potentials for chemical transformation

18. Lignocellulosic biomass Different raw materials present different compositions and different potential utilisation In Brazil, sugar cane bagasse and sugar cane straw are the most promising raw materials

19. Lignocellulosic biomass • Several processes have been developed aiming at using lignocellulosic biomass; • Most use biochemical transformations (enzimes) to produce sugars from lignocellulosic materials; • Petrobras is developing, together with BIOeCON BV and TU-Delft, the BICHEM technology, which uses heterogeneous catalysis.

20. Lignocellulosic biomass - Production of isosorbide from bagasse BICHEM STEPS 1 – Separation of lignin and hemicellulose 2 – Hydrolysis (molten salt as catalyst) 3 – Hydrogenation 4 - Dehydration R. Menegassi, J. Moulijn et al. ChemSusChem Volume 3(3), 325–328, 2010

21. Lignocellulosic biomass - Production of isosorbide from bagasse BICHEM Reactions involved glucose cellulose isosorbide sorbitol

22. Lignocellulosic biomass - Production of isosorbide from bagasse BICHEM Main catalytic challenges 1 – Increase the acidity of the molten salt used as catalysts in the hydrolysis step; 2 – Carry out hydrogenation and dehydration in a single step, using a bi-functional catalyst (ex. Metal containing zeolite).

23. Thermochemical route Thermochemical route • Biomass is converted thermo-chemically into intermediates • The processing technologies can be categorised as gasification, pyrolysis, or hydrothermal processing. • Intermediate products include clean syngas (CO + H2), bio-oil (pyrolysis or hydrothermal product), and gases rich in methane or hydrogen. • These intermediates can further be converted into gasoline, diesel, alcohols, ethers, synthetic natural gas etc. and also high-purity hydrogen, which can be used as fuels and electric power generation.

24. Thermochemical route Thermochemical route • The main thermochemical routes involving heterogeneous catalysts are the following: - H-BIO (also called green diesel); • BTL (comprising gasification, Fischer-Tropsch and hydrotreating); • Bio dimethylether (DME)/Bio methanol; • - Pyrolysis

25. Thermochemical route H-BIO • H-BIO is a technology developed by Petrobras which allows the production of diesel from renewable feedstock such as vegetable oils by processing them in the existing refining scheme; • In the H-BIO technology vegetable oils are co-processed with petroleum in hydro treating units; ; • The converted product contributes to improve the diesel pool quality in the refinery, increasing the cetane number, reducing the sulphur content.

26. Thermochemical route Untreated Diesel Fraction Vegetable Oil Petroleum Straight Run Diesel Atmospheric Distillation Existing HDT Atmospheric Residue Gasoil LCO Vacuum Distillation FCC Diesel Pool H-BIO Process Vacuum Residue Coker Gasoil Delayed Coking H-BIO

27. Thermochemical route YIELDS 96 litres of Diesel 100 litres Soybean oil Soybean Oil Diesel 35 NM3 H2 + 2.2 NM3 of Propane H-BIO Very high yield ( at least 95% v/v to diesel) without residue generation and a small propane production as a by-product

28. Thermochemical route H-BIO • Main catalytic challenges • Biomass conversion in HDT units generates CO and CO2 which are hydrogenated to methane, increasing hydrogen consumption and reducing catalytic activity; • The main challenge is to develop a catalyst with high HDT activity which, notwithstanding, produces less CO and CO2 from biomass conversion; • Petrobras has developed such catalyst (PI 0900789-0).

29. Thermochemical route Slurry (Co) or Tubular (Fe) reactor Waxes (>C20) Low T FTS BIOMASS Hydrocracking Clean syngas (CO + H2) Gas cleaning & conditioning Gasifier DIESEL Air or oxygen stream High T FTS CFB or FFB (Fe) reactor Olefins (C3 – C11) Particulate Removal Wet Scrubbing Catalytic Conversion of Tar Sulphur Scrubbing Water Gas Shift Oligomerisation Isomerisation Hydrogenation GASOLINE BTL Biomass-to-liquids BTL comprises: • Gasification • Gas cleaning • Fischer-Tropsh • Upgrade All those steps have catalytic challenges

30. Thermochemical route BTL Gas Cleaning

31. Thermochemical route BTL Gas Cleaning – Catalytic conversion Main reactions CnHm + n CO2 → (m/2) H2 + (2n) CO Dry reforming CnHm + n H2O → (m/2 + n) H2 + n CO Steam reforming • Main catalytic features • High tar conversion • Deactivation resistance • Easy regeneration • Low cost • Capable of promoting methane reforming • Main catalysts tested • Non-metallic oxides • Ni-containing catalysts • Noble metal-containing catalysts

32. Thermochemical route BTL Gas Cleaning – Catalytic conversion Many catalysts, promoters and supports have already been tested (Yung, 2009)

33. Thermochemical route BTL Gas Cleaning – Catalytic conversion

34. Thermochemical route Challenge – small Co particles with narrow PSD Optimum  6 to 8 nm average particle size BTL • Fischer-Tropsch synthesis • Activity correlates well with the increase in Co surface area; • For particles smaller than 6nm, activity drops suddenly; • K. P. de Jong et al. • J. AM. CHEM. SOC. 9 ,128, 12, 2006

35. Thermochemical route Co nanoparticules dispersed in BMI.BF4 E. Falabella, J. Dupont et al. ChemSusChem, Vol.1 (4), 291–294, 2008 BTL Co nanoparticles with a narrow PSD can be stabilised by Ionic liquids via thermal decomposition of Co(CO)8 .

36. Thermochemical route Fischer-Tropsch Also, the use of new reactor technology such as microractors has been proposed. 20 µm BTL Challenge Microreactors with a homogeneous distribution on the walls and a convenient width of the catalyst layer L. Almeida, F. Echave, O. Sanz, M. Centeno, G. Arzamendi, L. Gandia, E. Falabella, J. Odriozola, M. Montes Chemical Engineering Journal, Volume 167 (2-3), 536-544, 2011

37. Thermochemical route PROPERTIES High cetane number (60) Net heating value 6,900 kcal/kg Physicochemical properties similar to those of propane and butane, main LPG components Neither particulate nor sulphur oxides emissions upon burning No greenhouse effect or harm to ozone layer Non-toxic substance Bio-DME DME – the fuel of the 21st century

38. Thermochemical route Routes to produce DME from biomass BIOMASS RESIDUES Bio-DME E. Falabella, L. Appel et al. Catalysis Today Volume 101 (1), 39-44, 2005

39. Thermochemical route methanol catalyst + solid acid catalyst Bifunctional catalyst Bio-DME Reactions involved in one step DME production

40. Thermochemical route CH3OCH3 CH3OCH3 H2 H2 CH3OH CH3OH CO H2O H2O CO CO2 methanol catalyst acid sites Bio-DME E. Falabella, L. Appel, C. Mota. Catalysis Today Volume 101 (1), 3-7, 2005

41. Thermochemical route DME direct synthesis Bio-DME The addition of acidic oxides to a methanol catalyst promotes DME formation, but also CO2 yield E. Falabella, L. Appel et al. Fuel Processing Technology Volume 91 (5), 469-475, 2010

42. Thermochemical route Main Catalytic Challenges • Decrease catalyst deactivation • Improve CO2 hydrogenation • Real bifunctionalcatalyst (not a mixture) • The role of acidic sites (is a conjugated pair Bronsted-Lewis really required?) Bio-DME

43. Oleochemistry • Oleochemistry refers to the transformation of fats and vegetable oils through different processes; • The main basic products of the oleochemical complex are Fatty Acids, Fatty Esters, Fatty Alcohols, Glycerine; • Several important commercial products may be obtained via oleochemistry.

44. Oleochemistry

45. Oleochemistry • In Brazil, the first oleochemical plant has been working since 2008, with capacity to produce about 100 tons of fatty alcohols; • Using coconut oil and palm kernel oil, the main products are: • lauryl alcohol, keto-stearyl alcohol and its fractions, cetyl alcohol and stearyl alcohol; • caprylic-capric acid. • Also, highly pure, thermally stableUSP / Kosher glycerine is produced.

46. Oleochemistry HYDROLYSIS ESTERIFICATION FAME I – Hydroesterification, comprising two steps: Brazil has three plants in operation, where conversions above 99% are reached

47. Oleochemistry Main catalytic challenges - Development of acidic and basic solid catalysts; - Development of new catalysts/new reaction systems (microreactors) for glycerol upgrade via reforming. D. Hufschmidt, L. Bobadilla, F. Romero-Saria, M. Centeno, J. Odriozola, M. Montes, E. Falabella. Catalysis Today, 149 (3-4), 394-400, 2010. FAME I – Transesterification: • In the process of transesterification, oils or fats react with short chain alcohols producing esters (methyl or ethyl) and glycerol; • Currently, there are 64 biodiesel industrial plants in Brazil running with transesterification processes. Total capacity of production is about 5 billion liters/year

48. Final Conclusions • In Brazil biomass is widely available from agro-based industry. Therefore, biomass conversion technologies seem to be an attractive alternative to recycle biomass residues and produce high added value fuels and chemicals in a environmentally friendly way. • Biomass conversion processes can enhance the agriculture economy and reinforce other industries (ex.: sugar, alcohol, paper industry, etc). Furthermore, the process integration could allow more efficient biomass utilisation (cost reduction, energy production and parallel production of fuel and chemicals). GREEN IS THE SOLUTION !

49. Final Conclusions Haizi (1964-1989) Brilliant Chinese poet From tomorrow on, I will be a happy man; Grooming, chopping, and traveling all over the world. From tomorrow on, I will care foodstuff and vegetable, Living in a house towards the sea, with spring blossoms. From tomorrow on, write to each of my dear ones, Telling them of my happiness, What the lightening of happiness has told me, I will spread it to each of them. Give a warm name for every river and every mountain, Strangers, I will also wish you happy. May you have a brilliant future! May you lovers eventually become spouse! May you enjoy happiness in this earthly world! I only wish to face the sea, with spring flowers blossoming