Venice s Green Refinery: process and products innovation. Giacomo Rispoli

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Venice s Green Refinery: process and products innovation Giacomo Rispoli 1

Highlights Scenario Eni vision Eni/Honeywell UOP Ecofining TM technology Eni Green Refinery in Venice Looking to the future Conclusion 2

Scenario The European refining industry is living a major economic crisis, characterized by very low operating margins, bear fuels market and consequent refining overcapacity installed. This crisis was cracking down on the Venice Refinery in a particular way, due to its simple process scheme made by hydroskimming plus visbreaker/thermal cracker, without any catalytic conversion units. 3

Europe and biofuels EU's Climate Change Package with EU targets by 2020: 20% reduction in greenhouse gas emissions, 20% improvement in energy efficiency, 20% share for renewable in the EU energy mix. EU Directives on biofuels : Renewable Energy Directive RED 2009/28/CE Fuel Quality Directive FQD 2009/30/CE 10% of renewable energy in the transportation sector. Second generation biofuels counted twice. 4

Mb/d Biofuels demand Biofuel consumption by area: 2011 and 2020 UE27: consumption and target 2,2 2,0 1,8 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 Ethanol Ethanol Biodiesel Biodiesel 2011 USA Brasile 2020 UE27 2011 Other countries 2020 etanolo 2011 etanolo 2020 biodiesel 2011 biodiesel 2020 Target Estimated consumption based on current demand 4,8% 10% 7,5% 0,5 Mb/d 2020 forecast 2010 consuntivo 2020 previsioni Source Parpinelli The blending-wall limits biodiesel FAME blending at 7% max. This constraint can be overcome by using new generation renewable Hydrotreated Vegetable Oil (HVO). 5

Eni vision Refining industry crisis Reducing refining overcapacity? EU biofuels scenario ECOFINING TM Technology Biorefinery Reinventing petroleum refinery! 6

Eni approach Eni was able to turn a critical situation into a great opportunity by investing in the innovative Green Refinery project for the conversion of the Venice petroleum refinery into a Biorefinery. The Green Refinery idea is focused on the application of Eni/Honeywell UOP Ecofining TM technology and results from the long term Eni Green Strategy. That s the make option : eni entered the biofuels market, producing a new generation of very high quality biofuels starting from renewable feedstocks. 7

Eni Green Strategy results Eni/Honeywell UOP Ecofining TM patent 2007 Green Refinery Project 2012 2013 Refinery conversion to a biorefinery Eni patent May 2014 Green fuels production starts from Venice Green Refinery 2016 Green fuels production increase in Venice 8

EU and U.S. promote the transition to 2nd generation 1st gen. 2nd gen. 3nd gen. FEEDSTOCKS Agrifood Feedstocks Agricultural nonfood, Agro/Urban waste Feedstocks Non-agricultural High Innovation Feedstocks OPPORTUNITIES large & liquid markets support from the EU and U.S. regulatory targets environmental impact favorable valorization waste materials strong regulatory support Not in competition for use of the land resource high technological added value potentially large yields RISKS strong social and environmental impacts (Food vs fuel) climate risk possible phase-out high legislation production costs and complex logistics climate risk for some productions immature technologies strong investment in R & D required high production costs Diesel Biodiesel FAME Ethanol Gasoline 9

eni/honeywell UOP goal on biofuels Produce real drop-in biofuels, totally hydrocarbon, instead of fuel bio-additives. Focus on path toward new generation feedstocks. Conventional Oxygenated Biofuels Hydrocarbon Biofuels Ethanol Biodiesel Other Oils: Camelina, Jatropha Diesel Jet Gasoline First Generation Advanced Generation Natural oils (vegetables, greases) Lignocellulosic biomass, algae oils 10

BIODIESEL CONVENTIONAL PROCESS: Biofuels process: conventional vs new generation Feed Process Product Methanol Biological feedstocks ECOFINING TM PROCESS : H 2 Biological feedstocks Transesterification Biodiesel HYDROTREATMENT Biodiesel FAME (Fatty Acid Methyl Esters) Glycerine Feed Process Product Green Diesel (HVO) Green Jet (HEFA-SPK) Green Naphtha Green GPL CO 2 /H 2 O LOW QUALITY LOW CAPEX HIGH QUALITY HIGH CAPEX Green Diesel: high quality product obtained by means of hydrotreating (HVO) with paraffinic composition (oxygen free). 11

ECOFINING TM technology Jointly developed by Eni and Honeywell s UOP to produce excellent biofuels, with high quality independent from the renewable feedstocks used, that can be of: 1st generation: edible vegetable oils; 2nd generation: tallow, used cooking oils; 3rd generation: oils from algae and waste. 12

Hydrogen ECOFINING TM technology RENEWABLE FEEDS Vegetable oils Tallow Used cooking oils Oils from algae, waste Light fuels (Green LPG, Green Naphtha) GREEN JET GREEN DIESEL 1st reaction stage 2nd reaction stage Products separation 13

ECOFINING TM : typical yields Feedstock %wt Renewable oils 100 Hydrogen 1,5 3,8 Product %wt %v Propane 4-5 7-9 Naphtha 1-8 1-10 Diesel 75-85 88-98 CO 2 and H 2 O are also produced by the deoxygenation reaction 14

Green Diesel quality Properties Fossil Diesel ULSD Conventional Biodiesel (FAME) ECOFINING TM Green Diesel BIO content 0 100 100 Oxygen, % 0 11 0 Specific gravity 0.840 0.880 0.780 Sulphur, ppm <10 <1 <1 Heating Value, MJ/kg 43 38 44 Cloud Point, C -5 From -5 to +15 Up to-20 Distillation range, C 200-350 340-355 200-320 Polyaromatics, %w 11 0 0 Nox emissions Standard + 10% -10% Cetane 51 50-65 70-90 Oxydation stability Standard Pour Excellent 15

Other uses for Green Diesel: the Green Fleet project eni and the Italian Navy defined an agreement, within the frame of the Navy Green Fleet Project, to formulate and produce a new military ship bio-fuel by means of the Ecofining TM Technology. The new bio-fuel (containing more than 50% of Green Diesel) has been successfully tested for the very first time in Europe on the Italian Military Ship Foscari on last January. 16

Eni Green Refinery The Green Refinery is the result of the first conversion of a petroleum refinery into a biorefinery by mean of the application of Ecofining TM technology. This innovative idea has been patent filed by Eni on September 2012 (n MI2012A001465). Revamping the existing units in Venice significantly reduces the required investment cost, estimated in 1/4 to 1/5 of a new Ecofining TM grass root unit of the same capacity and intensively sped up project timing. 17

Sept. 2012 Aug. 2013 Sep. 2013 May 2014 18

Green Refinery Project: two steps Max throughput 400 kt/y (H2 balance limiting) Former Hydroskimming (H2 from catalytic reforming)) ECOFINING TM H2 Max throughput 560 kt/y (Existing equipment limiting) Steam Reformer & feedstock pretreatment Today, STEP 1: the Ecofining TM is operating in balance with the hydrogen from the refinery hydroskimming section. Tomorrow, STEP 2, on 2016: H 2 production from a new steam reformer will allow to maximize the Ecofining TM capacity. 19

Power Steam Green LPG The Green Refinery today Virgin Naphtha Hydroskimming (Naphtha splitter, Isomerization, Catalytic Reforming) Green Naphtha LPG Euro 5 Gasoline H2 Refined Palm Oil ECOFINING TM Green Diesel Natural gas Power Steam Cogeneration Power More than 300.000 t/a of Green Diesel production and additional conventional products such as EURO 5 gasoline and LPG, integrated with bio-quote of Green Naphtha and Green LPG from the Ecofining TM unit. 20

A technology challenge New feedstock material: different handling due to the poor cold flow properties and organic acidity. Conversion of two existing diesel HDS units into the two reaction stages of the Ecofining TM process. Integrating the Ecofining TM unit into the previous refinery scheme (utilities, ancillaries, etc.). Separating for the 1st step of operation, the derived biological material from the fossil material still running in part of the hydroskimming section of the former petroleum refinery (different blow down, sewers, slop tanks, etc). 21

A technology challenge Corrosion prevention for equipment: Upstream systems: Fatty acids impact on the tracing system selection; Downstream systems: Acidic gases & liquids impact on the metallurgy of the circuit. New acid gas management: CO 2 rich gas, with small amount of H 2 S coming from sulfur injection to Deoxy section; H 2 S recovery from acid gas by amine separation from CO 2 and H 2 S reuse as sulfiding agent in deoxy reactors. 22

The start up: a successful experience The Eni Green Refinery start up in the new configuration was very smooth without any issues; The ECOFINING TM unit successfully started up in May 2014, producing high quality Green Diesel. The unit performance, its operation stability and its response to changes are overcoming expectations. The integration with the hydroskimming section and with the utilities, facilities and offsite of the previous refinery is successful. 23

The update: after 4 months of operation An unplanned shut down of the unit was required after 3 months of operation for high delta P on the reactor guard bed catalyst; A quick turnaround allowed to replace the filtering material inside the first bed of the deoxy reactors; Delta P increase was related to the entrainment of dusty material from existing piping and tanks reused for the revamping; Filtration has been therefore improved. 24

Eni is looking for feeding the Green Refinery with additional advanced biofuel feedstocks: Tallow; Used cooking oils. Next improvement in compliance with the Annex 9 of the Proposal for a directive of the European Parliament and Council, amending the Directive 38/70/EC and 2009/28/EC. Focus on short supply chain: advanced feedstock from the region surroundings for improving the local economy. 25

Looking to the future (eni R&D) New biofuels: a new innovative process is under development for producing new 2nd generation biofuels. Bio-oils from microalgae: eni has a pilot plant operating since 2010 in the Gela refinery, Sicily, constituted by algae farm and oil recovery plant. 26

Conclusions The Venice Green Refinery is the result of the long term eni Green Strategy, made by investment on R&D activities aimed at developing innovative biofuel technology and renewable sources. The Green Refinery shows dual innovation: ON PROCESS 1st conversion in the world of a conventional petroleum refinery into a Biorefinery, by means of the Ecofining TM proprietary technology, which allowed to renew the obsolete Venice Refinery into a high innovative industrial process scheme. ON PRODUCT Launch on the market of new high quality biofuels: Green Diesel, Green jet, Green LPG and Green Naphtha. Green diesel, in particular, will be distinctive of eni Diesel fuel, assuring premium quality for stronger competition. 27

Thank you 28