Hydrotreating Process Development for the Production of Biofuels from Vegetable Oils Suchada Butnark Researcher Petroleum Products and Alternative Fuels Research Department August 1, 2013 PTT RTI Disclaimer
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The information contained in our presentation is intended solely for your personal reference only. In addition, such information contains projections and forward- looking statements that reflect our current views with respect to future events and financial performance. These views are based on assumptions subject to various risks and uncertainties. No assurance is given that future events will occur, that projections will be achieved, or that our assumptions are correct. Actual results may differ materially from those projected. Outline
• Global Energy System • Thailand Current Energy Status • Overview on Biofuels • R&D of BHD Production at PTT-RTI – Phase I(A): lab-scale BHD production – Phase I(B): Lab-scale Catalyst Syntheses – Phase II(A): Pilot-scale Production of Standalone BHD – Phase II(B): Pilot-scale Production of Co-processed BHD – Phase III: Plant Trial of Co-processing of Palm oil and Refinery Stream • Conclusion and Future Works
3 GLOBAL ENERGY SYSTEM
Page 4 The current global energy system is fossil fuel dominated
1. Fossil fuel still dominates 2. Bioenergy is leading amongst (85%) RE, followed by hydropower
Source: The IPCC Special Report on Renewable Energy Sources and Climate Change Mitigation, IPCC, 2011 Welcome Speech “World Renewable Energy Congress WREC 2011 – Sweden”
5 Analyzed by Dr. Kunn Kungvansaichol Energy accounts for 79% of Global Greenhouse Gas Emissions
GHG share in 2008
Source: Energy: the EU and the World - WREC 2011 6 Analyzed by Dr. Kunn Kungvansaichol International Energy Outlook by Fuel Type from 1990-2035
• Liquids (including biofuel) increases due to the demand in Transportation sector, while other sectors are flat. Also liquids still dominate.
• Natural gas grows well in power generation sector
• Coal will provide the largest share for power generation
• The share of renewable power increases from 18% in 2007 to 23% in 2035 (within power sector only) • Within RE, hydro and wind accounts for 54% and 26 % Source: International Energy Outlook 2010, EIA, USA, July 2010 Page 7 Analyzed by Dr. Kunn Kungvansaichol THAILAND CURRENT ENERGY STATUS
Page 8 Thailand Current Energy Status : Gas and Oil Lead
Source: EPPO 9 Analyzed by Dr. Kunn Kungvansaichol Thailand’s Commercial Primary Energy Consumption
Actual Projection KBD Others 25% •Oil and gas are major sources of energy and Transportation 3500 will remain so for many years; 38% Renewables • Transportation sector still occupies the largest 3000 Industrial Hydro & portion of total energy demand or around 38% 37% followed by industrial sector unlike the world 8% Imported Electricity 2500 situation 2006: ~1,440KBD 3% 15% Coal & Lignite 2000 2.7% Natural 43% Gas 1500 1.4% 17% 1000 32% 500 47% 31% Oil
0
1985 1990 1995 2000 2005 2010 2015
Note: feedstock excluded and information for Renewables from 2005 Source: Energy Policy and Planning Office, Ministry of Energy Thailand’s National Policy on Biofuel
Low Carbon Society Development
R&D Alternative Energy Development Plan Private and Community Budget (AEDP: 2012-2021) Investment
Target: Alternative Energy 25% within 2021
Solar Power Wind Hydro New Energy Biomass Biofuel (2000 MW) (1200 MW) (1608 MW)
Wave Biomass Ethanol (2 MW) (3630 MW) (9 MMLPD)
Geothermal Biogas Biodiesel (1 MW) (600 MW) (5.97 MMLPD)
Waste Diesel Substitute (160 MW) (25 MMLPD)
Page 11 Source: http://www.dede.go.th : AEDP 2012-2021 New Biofuels Replacing Diesel as of Thailand’s AEDP: 2012-2021
Plan Deliverables Phase I Phase II
1. R&D Plan 2014 1.1 ED95 - Proper information of on ED 95 1.2 Diesohol development of new Diesohol 2015 1.3 FAEE biofuels FAEE 1.4 BHD - Preparation on pilot BHD 2016 1.5 Algae projects and Algae 1.6 Jatropha commercialization of new BTL Jatropha 1.7 BTL biofuels
2. Pilot Project and - Pilot projects 2014-2016 Fleet Test - Fleet test on new Pilot Projects: ED 95 or Diesohol or FAEE 2015-2017 biofuel Pilot Projects: Algae, Jatropha and BHD - Decision making on 2015-2017 investment of new Pilot Projects: Bio-Derived Jet Fuel and BHD feasible biofuel Commercialization 3. Commercialization - Commercialization with capacity of 2 MMLPD in 2018 2019 2020 2021 2018 2 6 15 25 - Up to 25-MMLPD capacity in 2021 Page 12 Source: Thailand’s Alternative Energy Development Plan: AEDP 2012-2021 OVERVIEW ON BIOFUELS
Page 13 PTT Biofuels and Biorefinery R&D Program Overview
14 PTT R&D overview on biofuel
1st gen. R&D 2nd gen. Processes
Biodiesel/ BHD Oil Palm Jatropha Curcas Microalgae Biodiesel BHD
Bioplastics
sugarcane Ag. Residue Molasses & & Waste Sugarcane Juice EtOH Ethanol
Sweet Sorghum Grasses Animal Feed
Cassava EtOH Cellulosic EtOH
Cassava Woody Crops
Biochemicals Synthetic Fuels Aquatic Plants Pyrolysis BTL others Page 15 Source: Dr.Kunn Kangvansaichol Issues of Low Quality Biodiesel (FAME) in Thailand: FAME Properties to be remarked
Estimated Trouble Properties to be remarked
Damage on Fuel line parts – Acid Value metal corrosion, rubber swell – Methanol etc. – Oxidation Stability Pump failure sticking – Poly unsaturated fatty acid methyl ester content adhesive material – Ester content Filter plugging – Tri-glyceride →Engine stop – Mono-glyceride by stopping fuel supply – Di-glyseride Worsen exhaust gas – Glycerine – Solid foreign material – Water Hard start – Cold performance at low temperature – Metals Deterioration of – Phosporous after treatment system 16 Source: Petroleum Products and Alternative Fuels Research Department Issues of FAME: Example of Market Experience
(FAME) Stick inside FIE Pressure Discharging Pressure Valve Sensor Common Rail
Supply Pump
Fuel Injector Valve Filter Filter
Forming Carbonic Acid Salt ECU Fuel Tank No.2 (Adhesive material) ECU
Poor oxidation stability FAME corrodes fuel tank and clogging in nozzle of common rail engine. 17 Source: Petroleum Products and Alternative Fuels Research Department The Comparison between FAME, BHD and Diesel
FAME BHD Diesel
18 Source: Petroleum Products and Alternative Fuels Research Department Fatty Acid Methyl Ester (FAME or Biodiesel) & Bio-hydrogenated Diesel(BHD) FAME
Oil and Fat Transesterification Biodiesel Bxx Blending Glycerine Methanol & Catalyst
Bio-hydrogenated Diesel(BHD) Process
BHD-blended Oil and Fat Hydrotreating BHD Diesel (ULSD) Blending Propane/Water Hydrogen & Catalyst BHD-Standalone
VGO/Diesel Oil and Fat Distillate BHD-ready Diesel Hydrotreater (ULSD)
Preheater Hydrogen & Catalyst BHD-Coprocess
19 Source: Dr.Kunn Kangvansaichol BHD : World Status
Company Technology Status Neste Oil Standalone • Summer 2007: Neste Oil’s Porvoo refinery 170,000 t/a (NExBTL) • 2008: 100% NExBTL in Helsinki Buses & Green Diesel (BHD10) • 2009: 2nd Porvoo 170,000 t/a of NExBTL diesel • 2010: 800,000 t/a in Singapore (550 Million EURO), shifting towards palm oil certified by the Roundtable on Sustainable Palm Oil (RSPO) • 2011: 800,000 t/a in Rotterdam (25-hectare site close to oil refineries and petrochemical plants) Petrobras Co-processing • 2008-2012 : Investment in PETROBRAS refineries (5 ready) (H-BIO) • 2012 Target : Using up to 1.6 Million m3/year of vegetable oil (compared to 938 thousand m3/year Biodiesel production) ConocoPhillips Co-processing • Dec 2006: Whitegate Refinery, Cork, Ireland at 1,000 BPD • 2007: Pilot with Tyson On hold due to lack of gov. subsidy BP Co-processing • 2008Q1: 1.5% Tallow BP’s Bulwer Refinery (tallow) in (Renewable Queensland Diesel) • 2009: Plan to commercial up to 5% Tallow Cetane Energy Standalone • 2009: Produced 300 bbls of renewable diesel from tallow
20 Source: www.greencarcongress.com, Neste, Petrobras, Conoco, BP, ENI, UOP, Cetane Energy BHD : World Status (cont.)
Company Technology Status Nippon Oil Co-processing • 2007-2008: BHD10 trial in 2 buses in Tokyo (with TOYOTA) Shell N/A • Pilot Test with Alberta Renewable Diesel Demonstration Project compared with Biodiesel • The test is Canada’s largest Renewable Diesel demonstration Dynamic Fuels BiofiningTM by • 2009: Constructing a $135 million, 75 MMgy facility that aims Syntroleum to start producing renewable diesel and jet fuel in 2010. Canmet, Natural Standalone • Technology available for licensing Resources • 2006: Completed the economic feasibility Canada •The simulated plant location was set in Edmonton, (SUPERCETANETM) Alberta, Canada. •The capital cost to build an 800 barrels/day plant would be about US$12.7 million (2005). The payout time would be about 2.4 years based on a price of hydrogen of US$2.96/kg, a feedstock price of US$0.33/kg and a SUPERCETANETM selling price of US$0.69/kg. PTT Standalone/ • R&D stage (from Palm, Jatropha and FFA) (BHD) Co-processing • 2009Q4: PTT pilot plant completed • 2008-2011: MOU with TMT/TMAP-EM to study the feasibility of BHD in Thailand • 2012: 1.3 ML co-processed BHD from IRPC plant trial 21 Source: www.greencarcongress.com, ENEOS, Shell, Dynamic Fuels, Canmet, PTT internal BHD : World Status (cont.)
Company Technology Status Diamond Green Co-processing • 2013: 1.5 MLPD green diesel produced from recycled animal fat Diesel (DGD) and used cooking oil in Narco, Louisiana, USA using UOP Eco- fining process
22 Source: www.greencarcongress.com, ENEOS, Shell, Dynamic Fuels, Canmet, PTT internal BHD by Company (in 2012):
Neste oil dominates the market followed by Petrobras
0% 1% 5% BP 6% 23% Cetane Energy 7% ConocoPhillips
Dynamic Fuels (Tyson Foods/Syntroleum JV) ENI
Neste Oil
Petrobras 58%
Source: PTT RTI Analysis BHD by Feedstock (in 2012):
Palm oil dominates as feedstock of choice
5% 1% 11%
N/A Palm Soy and Palm 23% Soybean oil Soybean oil and others Tallow 53%
7%
Source: PTT RTI Analysis R&D OF BHD PRODUCTION AT PTT-RTI
25 R&D at PTT-RTI
• Feedstock Selection – Feedstock Types by Generation
• Phase I: – Lab-scale BHD production – Lab-scale catalyst syntheses: hydrotreating, hydrocracking and isomerization catalysts for production of bio-jet, bio-gasoline and iso-BHD
• Phase II: – Pilot-scale production of standalone BHD – Pilot-scale production of co-processed BHD
• Phase III: – Plant trial of co-processing of palm oil and refinery stream
26 R&D on Feedstock Types by Generation : 1st vs 2nd vs 3rd
1 st Generation Biofuels i.e. food crop on arable land
2 nd Generation Biofuels i.e. crop residues from food/agro crops (rice straw, cane leftover) + energy crop on non-arable land (jatropha, grass, wood)
3 rd Generation Biofuels i.e. microalgae on non-arable land
27 Source: Dr. Kunn Kangvansaichol and Mr. Supachai Reakasame, PTT RTI BHD Process Technology Roadmap
28 PHASE I(A): LAB-SCALE BHD PRODUCTION
29 Overview of Production of BHD, Bio-jet and Bio-gasoline (Standalone hydrotreating process) n-BHD can be blended with conventional diesel fuel with more than 5% weight
Hydrogen & Catalyst Hydrogen & Catalyst
Hydrocracking/ Hydrotreating n-BHD Oil and Fat Isomerization Propane/Water
Bio-Gasoline
Bio-Jet
iso-BHD
30 Micro-hydrotreating Units at TU, PPC and PTT-RTI
31 Variation of feedstock, catalyst and conditions
• Feedstock – Free fatty acid (FFA) – Crude palm oil (CPO), refined palm oil (RPO) and palm olein – Crude jatropha oil (CJO) – Used cooking oil (UCO) • Catalyst – NiMo/Alumina – CoMo/Alumina – Pd/C • Conditions – Pressure: 15-50 bar – Temperature: 250-400C
– H2/Oil: 500-1000 NL/L – LHSV: 0.1-2 h-1
32 Chromatogram of Jatropha-BHD
C17 Condition : Temperature : 375 ºC Pressure : 600 psi
H2/Feed Ratio : 38.59 LHSV : 0.5 h-1 BHD
Intermediates and impurities
Bio-jet fuel C15 C18 Octadecanol
Oleic acid Bio-gasoline Monoglyceride Steric acid
C16 Hexadecanol Diglyceride C9 C8 Palmatic acid Triglyceride C7 C10 C11 C12 C6 C14C13 33 Unknown
33 34 Compositions of palm-BHD and jatropha-BHD
Fatty Acid Component Palm (%) Jatropha (%)
C15 5.2 2.3 C16 32.0 12.0 C17 9.0 11.0 C18 49.0 68.0
• The difference in fatty acid component is the main reason for difference in cloud point
• Jatropha BHD with higher portion of C18 has higher cloud point than that of Palm BHD Freezing Point of Different Hydrocarbon Types
Hydrocarbon Freezing Point (C)
C12H26 -10
C14H30 5.5
C15H32 10.0
C16H34 18.1
C17H36 22.5
C18H38 28.0
Normal paraffin resulted in wax crystallization at more than 20C. 35 PHASE I(B): LAB-SCALE CATALYST SYNTHESES:
(HYDROTREATING, HYDROCRACKING AND ISOMERIZATION CATALYSTS FOR PRODUCTION OF BIO-JET/BIO-GASOLINE AND ISO-BHD)
36 Overview of Production of BHD, Bio-jet and Bio-gasoline (Standalone hydrotreating process) iso-BHD can be produced from isomerization process for improvement of cold flow properties.
Hydrogen & Catalyst Hydrogen & Catalyst
Hydrocracking/ Hydrotreating n-BHD Oil and Fat Isomerization Propane/Water
Bio-Gasoline
Bio-Jet
iso-BHD
37 Isomerization Catalyst and Isomerized BHD
• Collaboration with Thammasart University • Synthesis of catalyst – Zeolites – Noble and transition metals • Condition: T = 300-400˚C, P = 20 bar • Result: Some isomerization molecules and improvement of cold flow properties
Degree of Isomerization
n-BHD iso-BHD
Isomerization Catalyst Condition: 4˚C 38 Relationship between n-paraffins and Estimated Cloud Points
nC15-nC18, %wt.
120
• Low n-paraffin (high iso-paraffin) components 100 tend to improve cold flow properties of the product
80
60
40
20
0 -25 -20 -15 -10 -5 0 5 10 15 20 25 o Estimated Cloud Test,Point fromC DSC,C 39 Overview of Production of BHD, Bio-jet and Bio-gasoline (Standalone hydrotreating process)
Bio-gasoline and bio-jet can be produced from hydrocracking and isomerization processes.
Hydrogen & Catalyst Hydrogen & Catalyst
Hydrocracking/ Hydrotreating n-BHD Oil and Fat Isomerization Propane/Water
Bio-Gasoline
Bio-Jet
iso-BHD
40 Production of Bio-Jet Fuel
• Collaboration with Petroleum and Petrochemical College • Result: - Bio-jet fuel with freezing point at -46.5C, boiling point of 140-250C and 30% yield
Distillation of bio-jet fuel product Page 41 PHASE II(A): PILOT-SCALE PRODUCTION OF STANDALONE BHD
42 Pilot-scale Production System at PTT-RTI
Hydrotreating Catalyst
Hydrogen Compressor Unit
Hydrotreating Unit 43 Standalone Pilot-Scale Production of BHD
Palm Oil BHD from Palm Hydrotreating Reactors
Jatropha Oil
BHD from Jatropha
Hydrogen Gas
Optimal condition: 320 C, 34 bar, LHSV = 1h-1, H /oil = 1000 NL/L 2 44 Requirements for Diesel Fuels and Analysis Results of BHD Produced by PTT EU’s Thailand’s Thailand’s Palm- Jatropha- Property Unit Paraffinic Diesel Conventional B2 Limit B5 Limit BHD BHD Limit Diesel Limit Class A Class B Cetane number, min - 51 min – 51 50 (2012) 50 (2012) Ongoing Ongoing 70 (1) 66 max (1) Cetane index, min - - 46 50 (2012) 50 (2012) 111.6 - Density at 15°C, min-max kg/m3 770 – 800 800 – 845 810-870 810-870 784 786 (D 4052) Total aromatics, max wt% 1.0 - - - 0 0 Polycyclic aromatics wt% - - 0.1 8 0 0 hydrocarbons (PAH), max (2) (11; 2012) (11; 2012) Total olefin content, max wt% 0.1 - - - - - Sulfur, max (D 4294) 350 350 ppm 5 10 0.31 0.24 (D 2622; 2012) (50; 2012) (50; 2012) Flash point, min (D 93) ⁰C 55 55 52 52 122.5 124 Carbon residue (on 10% distillation residue), max wt% 0.30 0.30 0.05 0.05 0 0 (3)(D 2500)
Ash, max (D 482) wt% 0.01 0.01 0.01 0.01 - -
Heating value (D240) MJ/kg - - 45,968 39,550 47,354 - 45 Requirements for Diesel Fuels and Analysis Results of BHD Produced by PTT (continued) Paraffinic EU’s Thailand’s Thailand’s Palm- Jatropha- Property Unit Diesel Conventional B2 limit B5 Limit BHD BHD Limit Diesel Limit 500 (Water/Sed.) Water, max mg/kg 200 (4) 200 500 70 50 (Water/Sed.) 500 (B100) Total contamination, max mg/kg 24 24 - 24 (B100) - - Copper strip corrosion rating Class 1 Class 1 Class 1 Class 1 1a 1a (3 h at 50⁰C)
FAME (Fatty acid methyl vol% - - ester) content, max - 7 2 5 Oxidation stability, max g/m3 25 25 - 25 - - Lubricity, corrected wear scar diameter (wsd 1.4) at 460 (5) 460 460 460 579 566 60⁰C, max m HFRR (CEC F06-A-96) Viscosity at 40⁰C, min-max mm2/s 2.0-4.5 1.2-4.0 1.8-4.1 1.8-4.1 3.3 3.3 Distillation: T95, max ⁰C 360 360 - - - - E250, max vol% - 65 - - - - E350, max vol% - 85 - - - - 90% recovered (D 86) ⁰C 357 max 357 max 357 max 357 max 302.7 305.1 - clear , Color: 1) Hue - - Yellow Red clear , - water- water-like46 2) Intensity (D1500) - - 4.0 2.0 + red dye like Requirements for Diesel Fuels and Analysis Results of BHD Produced by PTT (continued)
Paraffinic EU’s Thailand’s Thailand’s Palm- Jatropha- Property Unit Diesel Conventional B2 Limit B5 Limit BHD BHD Limit Diesel Limit TAN (D664) mg KOH/g 0.13 0.13 - 0.5 (B100) 0.01-0.05 0.01-0.05 g Iodine/ 3 Iodine value (EN 14111) - - 120 (B100) Nil Nil 100 g (actual value) Cloud point (D5771) C - - - - 22 24 Pour point (D5950) C - - 10 10 20 26 Cold filter plugging point C - - - - 20 23 (D6371) Metal (ICP-OES) ppm Al ppm ------Ni ppm ------Co ppm ------Mo ppm ------Zn ppm ------Monoglyceride (EN - %wt - - 0.80 (B100) Nil Nil 14105) Diglyceride (EN 14105) %wt - - - 0.20 (B100) Nil Nil Triglyceride (EN 14105) %wt - - - 0.20 (B100) Nil Nil
Total glycerin %wt - - - 0.25 (B100) Nil Nil 47 FFA %wt - - - - Nil Nil Properties of BHD Products Compared to Regular Diesel
• Higher cetane number • Higher heat of combustion (MJ/kg) • Higher flash point • Lower density • Poorer lubricity (compared to biodiesel) • Poorer cold flow properties
48 PHASE II(B): PILOT-SCALE PRODUCTION OF CO-PROCESSED BHD
49 Process Diagram for Pilot-scale Co-processing
Collaborated with IRPC, about 5-20% refined palm oil (RPO) have been incorporated to vacuum gas oil (VGO) in pilot-scale demonstration. 50 Co-processing Technology for BHD Production
51 Co-processed BHD Properties
EU’s Co- Paraffinic Thailand’s Thailand’s Property Unit Conventional processe Diesel Limit B2 Limit B5 Limit Diesel Limit d BHD Class A Class B Cetane number, min - 51 min – 66 51 50 (2012) 50 (2012) 66.4 70 (1) max (1) (CFR) Density at 15°C, min-max (D 4052) kg/m3 770 – 800 800 – 845 810-870 810-870 815 Total aromatics, max wt% 1.0 - - - 16.1 Sulfur, max (D 4294, D 2622) ppm 5 10 50 50 6.37 Heating value (D240) J/g - - 45,968 39,550 46,130 500 (Water/Sed.) Water, max mg/kg 200 (4) 200 500 (Water/Sed.) 71 500 (B100) Oxidation stability, max g/m3 25 25 - 25 2 Lubricity, corrected wear scar diameter (wsd m 460 (5) 460 460 460 481 1.4) at 60C, max, HFRR (CEC F06-A-96) Viscosity at 40C, min-max mm2/s 2.0-4.5 1.2-4.0 1.8-4.1 1.8-4.1 4.4 Distillation: 90% recovered (D 86) C 357 max 357 max 357 max 357 max 352 g Iodine/ 3 120 Iodine value (EN 14111) - - Nil 100 g (actual value) (B100) Pour point (D5950) C - - 10 10 3 52 PHASE III(A): PLANT TRIAL OF CO-PROCESSING OF PALM OIL AND REFINERY STREAM
53 IRPC Plant Trial
At existing hydrotreating unit , refined palm oil (RPO) and heavy gas oil (HGO) was incorporated in-situ. 54 Processing and Products
Combined Co-processed Co-processed Feed Product BHD
55 Comparison of Feedstock and Product Properties
Cetane Sulfur Viscosity@40 C T90 (ASTM D86) Item Number (ppm) (cSt) (C)
1. HGO Base 63.4 12300 5.412 369.9
2. RPO ~ 50 3.8 ~ 40 -
3. HGO+RPO 59.6 8600 5.946 348
4. Co-processed Diesel 72.3 1 3.809 350 (Final Product)
Effective removal of oxygen in vegetable oils, sulfur and nitrogen contents in petroleum stream
56 Final Product Properties
Co-processed Test Item ASTM Method Unit Diesel Density @15C D4052 g/ml 0.8190 Flash point D93 C 97.0 Cetane number (CFR) D613 - 74.8 Viscosity@ 40C D445 cSt 3.809 Pour point D5950 C 0 Heating value (Gross) D240 J/g 46,498 Aromatic content in diesel by HPLC IP391 - Mono-aromatic %wt 7.8 - Di-aromatic %wt Nil - Tri-aromatic %wt Nil - PAH %wt Nil - Total aromatic %wt 7.8 High frequency reciprocating rig (HFRR) CEC F06-A-96 µm 504 Sulfur content D2622 %wt 0.0001
57 CONCLUSION AND FUTURE WORKS
58 Conclusion and Future Works
• Seeking for alternative feedstock for BHD production: used cooking oil, palm stearin, PFAD, algae oil tallow, lard, etc. Also solving the problem of feedstock price and supply.
• Sustainable development in own country (in terms of bio-resource and process and catalyst development)
• Source of hydrogen production for sufficient BHD production
• Feasibility study on investment of long-term co-processing and standalone technologies
• Field test and emission test for BHD blended in diesel for PTT’s future diesel product
• Government subsidy and tax incentive for future diesel product
59 Acknowledgements
• PTT Research and Technology Institute
• IRPC
• The Petroleum and Petrochemical College, Chulalongkorn University
• Department of Chemical Engineering, Thammasart University
60 THANK YOU VERY MUCH
Dr.Suchada Butnark
61