Innovative Solutions for Optimizing Refining & Petrochemicals Synergies. Jean-Paul Margotin

Transcription

1 Innovative Solutions for Optimizing Refining & Petrochemicals Synergies Jean-Paul Margotin 1

2 Agenda Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production R&P synergies for aromatics 2

3 Refining & Petrochemical Flow Exchanges Refining Technology Petrochemicals Final Unsaturated ROG Products FCC C 3 cut FCC C 4 -C 5 cuts Coker C 3 -C 4 cuts Saturated ROG Excess of C 3, C 4 SR Naphtha Cracked Naphtha CCR Reformate Gas Oil HC bleed VGO AR/VR PRU Conversion to C 3 = Purification Dehydrogenation H 2, C 4, Pygas HDT & Splitter to Aromatics to SC to SC or PetChem FCC PetChem RFCC Gasoline Pool Bases Raffin. Steam Cracker Aromatics Complex ParamaX Pygas (C 3 = ) PP (C 2 = ) PE, PVC (C 3 = ) PP (Styrene) PS Polyethylene terephthalate PET 3

4 Agenda Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production R&P synergies for aromatics 4

5 Propylene Production Forecast by Source 36% 2010 Production ~ 75 Million tons (Mt) 12% From Refineries (DCC/RFCC/FCC) From Steam crackers On purpose production Metathesis Olefins cracking MeOH to propylene C 3 dehydrogenation 52% Additional Propylene Production by Process Technology Mt/y Basis Global Additional Demand : ~ 20 Mt Average annual growth rate: ~ 4.5% Additional propylene production from refineries > 4 Mt Source: Axens (2011) 5

6 Propylene Production from Refinery LPG Naphtha Steam Cracker Complex C 4 -C 5 cut Olefins cracking Olicrack >8 wt% C 2 = >30 wt% C 3 = Resid Coker C 4 -C 5 cut On-purpose C 3 = unit VGO Resid FCC High Propylene FCC HS-FCC Resid to Propylene C 4 -C 5 cut C 3 = 8 to 20 wt% C 4 -C 5 Olefins Recovery or C 3 = Alternative Fuel units Fischer-Tropsch C 4 -C 5 cut FlexEne or Unique integration With FCC for flexibility Gasoline /Distillate 6

7 Comparative Yields HDT VGO Feed Yields, wt % 100% 80% 60% 1% 1% 17% 6% 2% 1% 20% 11% 2% 4% 22% 20% Fuel Gas Ethylene C3s + C4s Propylene 40% 55% 48% 33% Gasoline LCO 20% 0% 11% 4% 4% FCC 9% 3% 6% High Propylene FCC 8% 5% 6% HS-FCC Slurry Coke 7

8 High Propylene FCC Technology Location: Al Jubail, Saudi Arabia HP FCC Technology 33,000 bpsd Start-up in 2013 >10%wt Propylene production LCN recycle before feed injection Feed: Deeply hydrotreated VGO 3 other recent similar units in Middle East Source: Google Earth 8

9 HP FCC Technology Riser separator RS² Stripper / Packing Regenerator Bathtub catalyst distributor C C/O = 10 ZSM-5 content 10-20% (40% crystal) Feed LCN recycle 9

10 High Severity Fluidized Catalytic Cracking HS-FCC A worldwide cooperation Saudi Aramco (Saudi Arabia) JX (Japan) Shaw (United States) Axens (France) Feed injection Downflow reactor Catalyst down flow Regenerator Catalyst / Product separator Catalyst up flow Stripper using structured packing HS-FCC Yields, wt.% Ethylene = 4% Propylene = 20% 10

11 Resid to Propylene FCC Technology Ruwais refinery, Abu Dhabi Resid to Propylene Technology (R2P) 127,000 bpsd R2R technology, >12 wt% Propylene PetroRiser recycling LCN Atm. Residue, API=21, CCR=4 to 6, S = 1.7 wt% Source: Google Earth 11

12 Resid to Propylene Process Scheme & Technology Fuel Gas Fractionator & Gas Recovery C3 C4 LPG Treatment & Separation C3 Splitter Propylene PG Propane Naphtha Splitter Raw C 4 HCN LCO C 550 C C/O C C/O 12 Slurry/CLO FEED R2R Risers & Regenerators 660 C LCN Recycle R2R Unit Main Riser Resid PetroRiser LCN 12

13 Propylene Production from Refinery LPG Naphtha Steam Cracker Complex C 4 -C 5 cut Olicrack >8wt% C 2 = >30wt% C 3 = Resid Coker C 4 -C 5 cut On-purpose C 3 = unit VGO Resid FCC High Propylene FCC HS-FCC Resid to Propylene C 4 -C 5 cut C 3 = 8 to 20 wt% C 4 -C 5 Olefins Recovery or C 3 = Alternative Fuel units Fischer-Tropsch C 4 -C 5 cut FlexEne or Unique integration With FCC for flexibility Gasoline /Distillate 13

14 FlexEne TM - Flow Scheme Sweetening Sulfrex TM Gas Recovery Polymer Grade Propylene Propane Recycle Gasoline Distillate Raffinate C 4 -C 5 cut Polynaphtha TM Gasoline Distillate MF Pool FCC Feed Recycle Oligomers from Polynaphtha to FCC riser to maximize C 3 = Or Valorize Polynaphtha Gasoline or Distillate to Motor Fuel to adjust Gasoline/Diesel ratio 14

15 FlexEne & Polynaphtha FlexEne enables: The addition of 3-6% wt. of propylene yield, over and above the effect of ZSM-5 The increase of the desired Motor Fuels by flexible recycle selection Polynaphtha: is an Oligomerization unit Using a solid acidic catalyst 15

16 Petron Bataan Refinery Location: Petron, Philippines High Propylene FCC (HP FCC) 34,000 bpsd 250 kt/y of Propylene FlexEne TM, Gasoline & Propylene mode Feed: VGO + Hydrotreated Coker Gasoil Source: Google Earth 16

17 Propylene Production from Refinery LPG Naphtha Steam Cracker Complex C 4 -C 5 cut Olicrack >8 wt% C 2 = >30 wt% C 3 = Resid Coker C 4 -C 5 cut On-purpose C 3 = unit C 3 = / C 2 = ratio > 3-4 VGO Resid FCC High Propylene FCC HS-FCC Resid to Propylene C 4 -C 5 cut C 3 = 8 to 20 wt% C 4 -C 5 Olefins Recovery or C 3 = Alternative Fuel units Fischer-Tropsch C 4 -C 5 cut FlexEne or Unique integration With FCC for flexibility Gasoline /Distillate 17

18 Operability Continuous Catalyst Regeneration is based on Axens CCR experience > 100 Octanizing & Aromizing references Iso-5 Process Flexible and easy to operate regenerator 18

19 Agenda Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production R&P synergies for aromatics 19

20 Axens Technologies for Olefins Upgrading Steam Cracker C 3 = C 4 Ethylene C 2 LPG C 5 - C 10 Pygas MAPD Selective Hydrogenation Maximum Butadiene C4 C4 Acetylenes Selective Hydrogenation Maximum Butenes Butadiene Selective Selective Hydrogenation Hydrogenation C 4 /C 5 C 4 /C 4 /C 5 5 Olefins Hydrogenation C 5 Pygas Selective Hydrogenation GHU1 Purification Multibed Butadiene Extraction C 4 Etherification Catacol Skeletal Isomerization Iso -- 5 C 6 - C 10 Dimerization AlphaButol Max B=1 Super - Hydrogenation Fractionation Max Max B=2 B=2 IB= Purification Hydrogenation Isopure C 5 5 Etherification Catacol Advanced Advanced Pygas Pygas Upgrading Upgrading APU C 6 - C 10 Pygas Hydrodesulfurization GHU2 Removal of Arsenic & Mercury RAM II C 5 = Oligomerization Selectopol Polynaphtha C 9 - C 10 C 6 - C 8 Oligomerization Oligomerization AlphaSelect/ α - Select/ AlphaHexol α - Hexol 2 - Butenes Hydration Dimerization Dimersol-X Extraction Sulfolane Morphylane Dehydro. Olefins Hydrogenation Sulfur Removal OATS 1 - Hexene Lin. α - Olefins Propylene Butadiene 1 - Butene Isobutane Isobutylene Octenes n - Butane MEK MTBE, ETBE Solvents TAME, TAEE Benzene Toluene C 8 Aromatics to Aro. Complex To Motor Gasoline Pool Condensates 20

21 AlphaHexol Key Features Selective ethylene trimerization mechanism (Cr catalyst) L n M+ M = Metal L n = Ligand 1-Hexene 3 C 2 H 4 Recently born process, similar to AlphaButol, strongly backed up by extensive industrial experience in homogeneous catalysis Polymer grade 1-hexene suitable for LLDPE & HPDE Efficient ethylene feed use Process simplicity and ease of operation High flexibility Mild operating temperature and pressure Liquid phase Carbon steel equipment Ethylene Feed L n M Catalyst Preparation and Storage Reactor Recycle Column Catalyst 2 Removal Heavy Ends with spent Catalyst Separation section 1-Hexene C 8 + Cut Solvent Recycle 21

22 Agenda Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production R&P synergies for aromatics 22

23 Aromatic Complex Blocks Functions ParamaX Suite 23

24 Refinery with HCK, HP FCC + ParamaX CDU SR Naphtha Naphtha Naphtha Aromatic Complex ParamaX H 2 Benzene Paraxylene Toluene rich cut, A8+ A9+, raffinate, light naphtha Gasoline Pool Kero VDU VGO HCK Bleed HP FCC Gasoline Diesel Propylene Delayed Coker HCGO LPG Coke Refinery production 400,000 bbl/d Benzene: 140 kt/y Aromatics production Paraxylene: 700 kt/y (2.5% of 2009 PX world production) 24

25 Existing Refinery with Steam Cracker + ParamaX Heavy Naphtha Aromatic Complex ParamaX Benzene Paraxylene Gasoline H 2 export Existing refinery Kero Diesel Residue C 2, LPG, raffinate Pygas Propylene Light Naphtha SC Ethylene Existing Refinery production Aromatics production 400,000 bbl/d Paraxylene: 1,400 kt/y (5% of 2009 PX world production) Benzene: 650 kt/y 25

26 Conclusion Refining & Petrochemicals integration is achievable through: Full range of innovative technologies from residue conversion to olefins / aromatics maximization Full range of associated services: consulting (configuration studies), tech service. Full range of products: catalysts & adsorbents 26

27 Innovative Solutions for Optimizing Refining & Petrochemicals Synergies 27