New Technologies for cost-efficient Paraxylene Production
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1 New Technologies for cost-efficient Paraxylene Production OLIVIER LARLUS ERNST KÖHLER MATTHIAS WYZYCKI Public Dr. Olivier Larlus Clariant BU Catalysts Petrochemicals th Global Petrochemicals Summit November 14-16, 2016 Lisbon (Portugal)
2 2 Overview Clariant and its Petrochemical Catalysts at a Glance PX Market Fundamentals Zeolites - Indispensable Tool for Aromatics Production Clariant - Full-Scope Partner for Aromatics Production Adsorptive PX Separation Xylene Isomerization TDP & Transalkylation Aromatics Purification The Clariant advantage
3 3 Clariant focuses on creating value through innovation and sustainability Portfolio with leading Market Positions Four Business Areas Clariant in Numbers Care Chemicals 5,807 Sales 2015 (CHF m) from continuing operations 227 Net result 2015 (CHF m) from continuing operations Catalyst former Süd-Chemie Plastics & Coatings 853 EBITDA 2015 (CHF m) before exceptionals 14.7% EBITDA margin 2015 before exceptionals Natural Resources 4 Business Areas 17,213 Employees 2015
4 4 Clariant Focus Areas in Petrochemicals Ethylene Oxide C2 = Oxidation SynDox Epoxidation (HPPO) OxyMax Propylene Oxide Gas Light Naphtha Steam Cracker C2 = /C3 = Selective Hydrogenation OleMax Monomer Purification ActiSorb FCC Offgas Purification OleMax Ethylene Propylene C2= Alkylation EBUF C3= Alkylation PolyMax TransMax EB Dehydrogenation StyroMax Polymerization PolyMax Styrene Monomer Cumene Polyethylene Polypropylene Propane Dehydro (PDH) Catofin Crude Oil Crude Distillation Residue Heavy Naphtha FCCU Methanol Naphtha Reforming Methanol-to-Propylene MTP Aromatization CPA PyGas HDT OleMax BTX Recovery Benzene Toluene Xylenes AROMATICS COMPLEX PX Recovery ZeoSorb PX Transalkylation/ Disproportionation TransMax Xylene Isomerization ISOXYL BTX Purification Tonsil Clays PX Benzene Oxidation TA Purification H2Max PTA Clariant Zeolite Catalysts/Adsorbents
5 PX Market Fundamentals Public Dr. Olivier Larlus Clariant BU Catalysts Petrochemicals
6 6 PX Market Strong Growth in Polyester-based Products MEG (Mono Ethylene Glycol) Growth Rate ,000 kta bn US$ (2014) PTA 7% Polyester Film 4.7% Paraxylene PET Melt Phase 65% Polyester Fibre 4.4% 5.1% DMT 28% PET Resin 6.1% Market Share 2014 Scheme and numbers (w/o formulas and pictures) from ICIS Aromatics in Time of Volatility - Have Fundamentals Changed? May 8, 2015
7 7 PX Market: The Future of Aromatics is bright Long-term ICIS: As a result of mobility, urbanization, environmental and innovation trends: - Benzene consumption: +55% - PX use for polyester: +100% (2014 to ICIS Dec 3, 2015). Global Paraxylene Market Million tons Short/mid-term PX oversupply remains on paper and there may not be enough capacity in 2018 and beyond (HIS - Ashish Pujari 37 th APIC, May 18-20, 2016, Singapore )
8 8 Zeolites Unique Properties Acidity & Shape Selectivity Na + ( K + ) Al 3+ Si 4+ O 2- as synthesized Reactant Shape Selectivity Example: Catalytic Dewaxing Product Shape Selectivity Example: Xylene Isomerization + H + Al 3+ Si 4+ H-Zeolite O 2- + Transition State Shape Selectivity Example: Transalkylation +
9 9 Indispensable Tool for Aromatics Production Clariant has 30 years Experience in Zeolite R&D and Manufacture AEL AFI BEA CHA ERI FAU FER LTA LTL MAZ MEL MFI MOR MTW SOD
10 10 Clariant Catalysts Global Zeolite Catalyst & Adsorbent Operations Bitterfeld (Germany) Louisville, KY (USA) Palo Alto Louisville Needham Little Ferry Bitterfeld Munich Heufeld MoosburgNovara Moscow Severodonetsk Qatar Baroda Daegu Toyama Nanjing Tokyo Panjing Shanghai Jinshan Cochin Vadodara (India) Singapore Suzano Sao Paulo Sasolburg Richards Bay (RSA) Richards Bay Zeolite (Catalyst/Adsorbent) Site Includes JV operations
11 Clariant - A Full-Scope Partner for Aromatics Production Public Dr. Olivier Larlus Clariant BU Catalysts Petrochemicals
12 12 Clariant Products for Aromatics Production C6/C7 Raffinate Benzene Extraction GT-BTX Clay Tonsil Toluene SHU OleMax Reformate Splitter MeOH TA/TDP TransMax Toluene Methyl. TM Benzene Column Toluene Column Catalytic Reformer HDT HDMax Naphtha Pyrolysis Gasoline Clay Tonsil C8+ A Xylene Column OX Column Orthoxylene Heavy Aromatics Column PX Recovery ZeoSorb PX Xylene Isomerization ISOXYL C11+ Clay Tonsil Paraxylene Deheptanizer LE s
13 13 Clariant Products for Aromatics Production Paraxylene Adsorptive Separation ZeoSorb PX-200 Xylene Isomerization (EB Dealkylation) ISOXYL MPH Xylene Isomerization (EB Isomerization) ISOXYL EBI-610 Toluene Disproportionation TransMax 302 Heavy Aromatics Transalkylation TransMax 501 Toluene Methylation TM 101 Aromatics Purification (Clay Treatment) Tonsil CO & APT
14 14 Confidential, TransMax Catalysts for TDP/Transalkylation Clariant Products for Aromatics Production C6/C7 Raffinate Benzene Extraction GT-BTX Clay Tonsil Toluene SHU OleMax Reformate Splitter MeOH TA/TDP TransMax Toluene Methyl. TM Benzene Column Toluene Column Catalytic Reformer HDT HDMax Naphtha Pyrolysis Gasoline Clay Tonsil C8+ A Xylene Column OX Column Orthoxylene Heavy Aromatics Column PX Recovery ZeoSorb PX Xylene Isomerization ISOXYL C11+ Clay Tonsil Paraxylene Deheptanizer LE s
15 15 Paraxylene Adsorptive Separation How it works Large pore zeolite (ø = 7.4 Å) with high adsorption capacity 5.8 Å 6.8 Å 6.8 Å 5.8 Å Preferential adsorption in the pores based on steric hindrance, orientation of isomers and electronic environment Commercial Conditions: Process Simulated Moving Bed (SMB) Adsorbent Size & Shape mm Spheres Operating Temperature [ C] 177 Operating Pressure [barg] 9 Desorbent p-deb 0.5 mm
16 16 Paraxylene Adsorptive Separation ZeoSorb PX-200: Advantage from binderlesszeolite Binderless Zeolite Adsorbent provides 100% active Material, i.e. higher selective pore volume (SPV) and thus higher adsorption capacity than binder-containing adsorbents Clariant proprietary Zeolitization Technology Granule consisting of Zeolite and Binder Carrier before Zeolitization Binder Granule consisting of 100% Zeolite Carrier after Zeolitization Zeolite Crystal Zeolite Crystal
17 17 Paraxylene Adsorptive Separation ZeoSorb PX-200: Key Differentiators 1. PX Selectivity Optimized β values (selectivities of PX over the other C8 aromatics and the solvent) 2. Adsorption Capacity - High selective pore volume (SPV) - Low non-selective pore volume (NSPV) ZeoSorb PX Physical Properties - Bulk crush strength - Attrition - Particle size 4. Mass transfer - Porosity (micro/macro) - Mass transfer coefficient 0.5 mm
18 18 Paraxylene Adsorptive Separation ZeoSorb PX-200 -Performance Testing Available to Clariant Clients to demonstrate PX recovery and purity
19 19 Clariant Products for Aromatics Production C6/C7 Raffinate Benzene Extraction GT-BTX Clay Tonsil Toluene SHU OleMax Reformate Splitter MeOH TA/TDP TransMax Toluene Methyl. TM Benzene Column Toluene Column Catalytic Reformer HDT HDMax Naphtha Pyrolysis Gasoline Clay Tonsil C8+ A Xylene Column OX Column Orthoxylene Heavy Aromatics Column PX Recovery ZeoSorb PX Xylene Isomerization ISOXYL C11+ Clay Tonsil Paraxylene Deheptanizer LE s
20 20 Xylene Isomerization ISOXYL Catalyst Options Mixed Xylenes H + H + Zeolite Zeolite Ethylbenzene (EB) C8 aromatics always contain ethylbenzene (EB) in the range of a few percent up to over 20%. EB can t be separated from xylenes, so it needs to be converted. ISOXYL MPH EB Dealkylation H2 Pt + C 2 H 4 H2 Pt + C 2 H 6 ISOXYL EBI EB Isomerization H2 H + H + H2 Pt Zeolite Zeolite Pt
21 21 Xylene Isomerization / EB Dealkylation ISOXYL MPH - Strong & reliable Performance Careful selection of the zeolite and innovative processing steps Unique manufacturing technology Long-term experience in zeolite R&D and manufacture EB Conversion (EBC): % Xylene Loss (XL): < 1.5 % PXATE: > 100 % Successfully put into commercial operation Expected life time 10 years+
22 22 Xylene Isomerization / EBI Isomerization The all-new ISOXYL EBI-610 Fine balance between protonic sites of the zeolite and the hydrogenation power of the noble metal function results in high EB conversion and excellent selectivity. Less hydraulic load on the PX separation section Improved plant economics by preserving aromatic rings to an excellent level. EB Conversion (EBC) up to 40 % C8 Ring Loss (C8RL) down to 2.0 % ISOXYL EBI-610 incorporates Clariant s vast expertise in zeolite R&D and manufacture PXATE > 92 % EBATE > 60 %
23 23 Clariant Products for Aromatics Production C6/C7 Raffinate Benzene Extraction GT-BTX Clay Tonsil Toluene SHU OleMax Reformate Splitter MeOH TA/TDP TransMax Toluene Methyl. TM Benzene Column Toluene Column Catalytic Reformer HDT HDMax Naphtha Pyrolysis Gasoline Clay Tonsil C8+ A Xylene Column OX Column Orthoxylene Heavy Aromatics Column PX Recovery ZeoSorb PX Xylene Isomerization ISOXYL C11+ Clay Tonsil Paraxylene Deheptanizer LE s
24 24 TDP & Transalkylation TransMax Catalyst Options Toluene-rich Feeds TransMax 302 CH 3 CH 3 CH CH 3 Tol./C9+Aromatics Feeds TransMax 501 CH 3 CH 3 CH 3 CH 3 CH CH 3 CH 3 CH 3
25 25 Transalkylationof C9+A with TransMax Key Reactions in Transalkylation Xylenes Formation Tol + Tol Bz + Xyl Tol + TMB Xyl + Xyl Ethylbenzene Formation ET + Tol EB + Xyl ET + ET EB + EX ET + Tol Xyl + EB EX Xyl + C 2 TMB + TMB TeMB + Xyl Benzene Formation Tol + Tol Bz + Xyl Tol + TMB Bz + TeMB PB Bz + C 3 Toluene Formation ET Tol + C 2 ET + ET Tol + A11 PB Tol + C 2 Heavy Aromatics Formation Tol + ET Bz + A10 ET + ET Tol + A11 ET + ET EB + A10 Tol + TMB Bz + A10 TMB + TMB Xyl + A10 ET + TMB Tol + A11 PB + Tol Bz + A10 PB + Tol ET + Tol
26 26 Transalkylationof C9+A with TransMax Benzene Purity and Aromatics Ring Loss Hydrogenation of aromatic rings is the primary cause for benzene co-boilers and a prerequisite for ring opening/loss TransMax advantage over other catalysts: Less rigorous and more selective hydrogenation function Zeolites have tailored cracking activity to preserve aromatic rings while ensuring maximum activity for TDP, transalkylation and dealkylation TransMax achieves outstanding benzene purity and very low aromatics ring loss
27 27 Transalkylationwith TransMax Challenges & Objectives in TDP/Transalkylation Xylenes Yield Total Conversion Catalyst Life Time TDP/TA Objectives Aromatic Ring Loss Benzene Yield Benzene Purity TransMax catalysts meet all performance objectives in TDP & Transalkylation
28 28 Clariant Products for Aromatics Production C6/C7 Raffinate Benzene Extraction GT-BTX Clay Tonsil Toluene SHU OleMax Reformate Splitter MeOH TA/TDP TransMax Toluene Methyl. TM Benzene Column Toluene Column Catalytic Reformer HDT HDMax Naphtha Pyrolysis Gasoline Clay Tonsil C8+ A Xylene Column OX Column Orthoxylene Heavy Aromatics Column PX Recovery ZeoSorb PX Xylene Isomerization ISOXYL C11+ Clay Tonsil Paraxylene Deheptanizer LE s
29 29 Aromatics Purification Innovative Clay Catalysts -Tonsil APT 800 KTA PX Plant Application Volume [m 3 ] Life Time Increase [months] Total Savings > 1,500,000 per year Tonsil APT Series Higher Activity Longer Service Life Higher Selectivity Faster Start-up (Low Moisture) Tonsil Product Reformate Bottom 2 x APT-MX BT Treatment 2 x APT-BT p-xylene Rerun 4 x APT-PX
30 The Clariant Advantage Public Dr. Olivier Larlus Clariant BU Catalysts Petrochemicals
31 31 The Clariant Advantage Cost Efficiency All catalysts extensively tested by client s against the market leaders Fully commercial conditions with genuine feed All products exceeded or matched the performance of the market leaders Clariant products & services excelled in terms of performance-cost ratio Performance/Cost-Rato 1,8 1,6 1,4 1,2 1 0,8 0,6 0,4 0,2 0 Other Catalyst Clariant
32 32 The Clariant Advantage Technical Service Full-scope service for all aromatics facilities, incl. SMB units, by professionals On-site assistance for loading and start-up Plant optimization Regular technical service visits On-site assistance for trouble-shooting Physical and chemical analysis of used catalyst Process simulation (entire complex) Catalyst testing in pilot plant Adsorbent testing in SMB
33 33 The Clariant Advantage Full-Scope Technology Packages Clariant does not just sell catalysts but provides comprehensive (full-scope) packages of technologies, products and services: Catalysts PX Adsorbent Clays Extract. Design & Engineering Distillation PX Products & Services This offering is peerless in the industry, especially when it comes to cost efficiency Technical Service
34 34 Disclaimer This presentation contains certain statements that are neither reported financial results nor other historical information. This presentation also includes forward-looking statements. Because these forward-looking statements are subject to risks and uncertainties, actual future results may differ materially from those expressed in or implied by the statements. Many of these risks and uncertainties relate to factors that are beyond Clariant s ability to control or estimate precisely, such as future market conditions, currency fluctuations, the behavior of other market participants, the actions of governmental regulators and other risk factors such as: the timing and strength of new product offerings; pricing strategies of competitors; the Company s ability to continue to receive adequate products from its vendors on acceptable terms, or at all, and to continue to obtain sufficient financing to meet its liquidity needs; and changes in the political, social and regulatory framework in which the Company operates or in economic or technological trends or conditions, including currency fluctuations, inflation and consumer confidence, on a global, regional or national basis. Readers are cautioned not to place undue reliance on these forward-looking statements, which speak only as of the date of this document. Clariant does not undertake any obligation to publicly release any revisions to these forward-looking statements to reflect events or circumstances after the date of these materials.
35 35 Thank you for your Attention! Dr. Olivier Larlus Project Leader R&D Clariant Produkte(Deutschland) GmbH Phone: Dr. Ernst Koehler Global Product Manager Aromatics Clariant Produkte(Deutschland) GmbH Phone: Mobile: Matthias Wyzycki Head of Sales EMEA Clariant Produkte(Deutschland) GmbH Phone: Mobile:
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