Catalysts & Catalytic Processes in Petrochemical Industry Part-1 Basic chemicals 10 th Orientation Course in Catalysis for Research Scholars 28 th November to 16 th December,2009 Dr.K.R.Krishnamurthy National Centre for Catalysis Research (NCCR) Indian Institute of Technology Chennai-600036 INDIA

Contents Chemical industry & Catalysis Origin of Petrochemicals Basic / Building block chemicals Basic chemicals to Petrochemicals Petrochemical processes & catalysts Ethylene, Propylene & Butadiene by thermal cracking Alternative routes for Basic chemicals

Chemical Industry-The Fact Sheet 70000 products 10 Million direct employees 50 Million indirect employees Wide range of products/processes / feed-stocks Enabling better quality of life Annual growth rate 2.4 % Global enterprise valued at $2.2 Trillion …… and growing

Catalysis in Chemical Industry Catalysts- Motors of Chemical Industry

Chemical Industry-The challenges Constraints in feedstock with respect to availability, quality & cost Eco friendly processes & products: stringent emission levels- Preserving the environment Need for conserving energy Waste minimization/effective treatment Catalysts with higher efficacy: activity/selectivity/ life / Max.atom efficiency Process improvements: milder conditions/fewer steps Ever-increasing demand for niche /specialty products at affordable prices New catalysts /processes: Reduction in discovery & process development cycle time Catalysis provides innovative solutions

Catalysis- Key to process innovations Catalysis: The science behind sustainable energy & chemicals

Target ( <10ppm S) achieved through scientific pursuits How Science responds to the technological challenges ? Production Ultra Low Sulfur Diesel requires ultra high active HDS catalysts Target ( <10ppm S) achieved through scientific pursuits Science takes on the demands from the environment

Global Catalyst Market Major market segments Petroleum Refining Polymerization Petrochemicals / Chemicals Environmental Market Projections- 2012 Growth rate 6.3 % Market value 16.5 Bill.US$ Global Catalyst market: $ 12.9 Bill (up to 2007). Catalysts for Energy & Environment to grow faster

Chemical Industry- Products pattern Petrochemicals-37% Chemicals- Intricately woven with our day to day life

Petroleum Refining- The Mother Industry C R U D E O I L 5-6%

Product Slates Petrochemical feed-stocks Petroleum Fuels C2-C3 gas Hydrogen Lubricants Syngas Sulfur Petrochemical feed-stocks C2-C3 gas LPG C4 stream Naphtha for light olefins Naphtha for aromatics Kerosene Gas oil for cracking

Ethylene, Propylene, 1.3-Butadiene & BTX, Petrochemicals- The Origin CRUDE OIL REFINARY FEEDSTOCKS Gas, Naphtha, Gas Oil, Kerosene PETROCHEMICAL INDUSTRY BASIC CHEMICALS Ethylene, Propylene, 1.3-Butadiene & BTX, PETROCHEMICALS PE,PP,PVC,PS,PBR,MEG,LAB,ACN, AF, PTA, PHA, MA,CPL

Basic/Building block Chemicals Ethylene Propylene Butadiene (1,3) Benzene Toulene Xylenes

Petrochemicals from Ethylene

Petrochemicals from Propylene

Petrochemicals from Butadiene Polybutadiene Rubber PBR Styrene-Butadiene Rubber SBR Acrylonitrile- Butadiene -Styrene ABS Adiponitrile ADN Specialty Polymers / Chemicals

Petrochemicals from Benzene

Petrochemicals from Toluene Benzene Xylenes Specialty/ Functionalized chemicals

Petrochemicals from Xylenes O-Xylene m-Xylene p-Xylene Phthalic anhydride Terephthalic acid PTA Iso-phthalic acid Plasticizers PET Polyesters

Table.3. Major petrochemical processes & catalysts Catalysts/Processes Aromatics Naphtha reforming- Production of Gasoline & BTX Pt-Re/Al2O3, Pt-Sn/Al2O3, Semi-regenerative/ CCR UOP/Axens/Criterion/Chevron/IPCL/RIL Xylene Isomerization- Towards maximization of p-Xylene- EB Conversion/ EB dealkylation prcesses ZSM-5 Composite UOP, Axens, Exxon-Mobil Zeolyst , IPCL/RIL C7+C9 Aromatics Transalkylation- Upgradation of low value C7& C9 streams, towards maximization of p-Xylene UOP, Axens, Exxon-Mobil,SK Corpn  Toluene Disproportionation- Up gradation of low value C7 stream- Value added products- Benzene & p- Xylene UOP, Axens, Exxon-Mobil,  Alkylation of Toluene/ Ethylbenzne- Value added products- p-Xylene & PDEB Pore regulated ZSM-5  IPCL/RIL, UOP

Dehydrogenation C3 ,C4 paraffins to Olefins- Monomers- Propylene, Iso-butene Cr2 O3/Al2O3, Pt-Sn/Al2O3,  UOP, CATOFIN, Phillips, Linde C10-C13 paraffins to Mono olefins- For alkylation with Benzene to Linear Alkyl Benzene (LAB) Pt-Sn/Al2O3, UOP, IFP,IPCL/RIL   Ethyl benzene to Styrene Fe-K/Al2O3 UOP

Hydrogenation Acetylenics in C2/C3/C4 hydrocarbon streams- Purification of monomers Pd/Ni supported on alumina with promoters Axens, Sud-Chemie, BASF Benzene to Cyclohexane- For caprolactum production Ni/Alumina, Pt/Alumina Axens, SC,UOP Hydrogenation of Oils/Fats Ni/Alumina Purification of PTA- removal of 4-CBA Pd/Carbon BASF, Sud-Chemie,Chemit Hydrogenation of unsaturated organic compounds Supported Ni/Pd with promoters

Oxidation /Epoxidation /Oxychlrination / Ammoxidation Ethylene to Ethylene oxide Promoted Ag/Alumina, DOW,Shell,Sci.Design Ethylene to Acetic acid Supported Pd Ethylene+ HCl to Ethylene dichloride CuCl2- KCl/Alumina BASF, KNF, Oxyvinyl Propylene to Acrylonitrile Molybdates of Bi,Fe,Ni/Silica  Ineos Propylene to Acrylic acid V-P-O,Ineos Propylene to Propylene oxide Supported Mo Oxides/Au O-Xylene to Phthalic anhydride Vanadia/TiO2 P-Xylene to Purified Terephthalic acid (PTA) Co-Mn fatty acids   Butane to Maleic anhydride V-P-O, Ineos

Syngas conversions CO+2H2→ CH3OH ZnO-CuO-Chromia   CO+2H2→ CH3OH ZnO-CuO-Chromia CO+H2→ n-Paraffins (Fischer-Tropsch) Supported Co/Fe with promoters CO + CH3OH→ Acetic acid Rh-,Ir-Iodide promoted

Polymer Processes Ethylene to Polyethylene LDPE, LLDPE, HDPE   Ethylene to Polyethylene LDPE, LLDPE, HDPE High pressure tubular process (LDPE) Chevron-Phillips slurry process Basell Spherilene process ( LLDPE/HDPE) NOVA- Sclairtech process ( LLDPE/HDPE) Propylene to Polypropylene PP, PE Copolymers Basell Spheripol PP process Dow UNIPOL PP process Borstar PP process Vinyl chloride to Polyvinyl chloride PVC Innovyl Suspension PVC UHDE, Goodrich process

Polymer Processes Ethylene to Polyethylene LDPE, LLDPE, HDPE   Ethylene to Polyethylene LDPE, LLDPE, HDPE High pressure tubular process (LDPE) Chevron-Phillips slurry process Basell Spherilene process ( LLDPE/HDPE) NOVA- Sclairtech process ( LLDPE/HDPE) Propylene to Polypropylene PP, PE Copolymers Basell Spheripol PP process Dow UNIPOL PP process Borstar PP process Vinyl chloride to Polyvinyl chloride PVC Innovyl Suspension PVC UHDE, Goodrich process

(SRT-Heaters) S as DMDS is injected to control CO & Coke

Selective hydrogenation of C2,C3 & C4 acetylenes in olefinic streams are the critical processes to get pure C2,C3 & C4 olefins

Propylene: Supply-Demand gap

Depends on relative costs of ethylene & propylene Olefin metathesis C2H4 + C4H8  2 C3H6 Can be a stand alone unit or integrated with cracker/FCC unit Low investment, less energy intensive, attractive returns High propylene/ethylene yield ratios, varying from 0.5 to 1.1 Use of low cost C4 stream Process technologies META-4 ® (Axens – IFP Group Technologies) OCT ® Olefins Conversion Technology (ABB Lummus) UOP’s process Depends on relative costs of ethylene & propylene

Metathesis- Catalysts & Process conditions

Alternative routes to Propylene Olefin Inter conversion Processes Catalytic cracking of C4- C5 streams or the light naphtha streams in a fixed or fluidized bed reactor Compatible with crackers and FCC units Unlike metathesis, do not consume ethylene. Process technologies Olefin Cracking Process (UOP-ATOFINA) Propylur (Lurgi) PCC process (Exxon –Mobil) SUPERFLEX ® (Lyondell/Kellogg) Mobil’s Olefin Inter conversion Process (MOI)