Zeolite Catalyst. Methanol. Propylene. Petrochemical Research & Technology پژوهش و فناوري پتروشیمی

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NPC-RT Propylene via Methanol Technology Methanol Zeolite Catalyst December 2016 Propylene ١

Natural Gas Value Chain Methanol Demand & Supply Methanol and Propylene Price Overview of NPC-RT PVM Technology ٢

Natural Gas Methanol Plant Methanol PVM Plant Propylene Propylene Processing Propylene Derivatives $ $$ $$$$ $$$$$ PP Acrylic Acid ٣

٤

UOP/Hydro MTO Fluidized bed Reactor SAPO-34 Catalyst 400 o C, 1 atm Lurgi/NPC-RT, PVM Fixed bed Reactor ZSM-5 Catalyst 460 o C, 1.5 atm Easier Operation (more Convenient) Lower Fix.Cap. Inv. More Propylene Production Iran Olefin Cracking Plants for Ethylene Production ٥

MeOH HP Steam Steam System MeOH, DME Reaction Gas Separation Compression Purification LPG Regeneration HP Condensate Cold Water System HC DM Water Refr. System Flare Nitrogen, Plant Air, Instrument Air, Electrical Power, Fuel, LPG for startup, etc. C3= Gasoline Water ٦

شرکت ملی صنایع پتروشیمی National Petrochemical Company DME Reactor Methanol 457 kt/a Reaction section Quench and Compression section Products selectivity (dry basis) PVM Reactors (2 operating + 1 reg.) Olefin Recycle Water Recycle Propylene Fuel Gas (for internal use) Process Water (for internal use) Gasoline Product Fractionation optional Ethylene Propylene 120 kt/a LPG 18 kt/a Gasoline 49 kt/a Separation section LPG C 2 61.73% 24.5% 9.27% 4.5% ٧

شرکت ملی صنایع پتروشیمی National Petrochemical Company Catalyst and Chemical Summary List Catalysts and support Material ٨ Filling or Consumption Life-time DME Catalyst (for 01-R-0111) 32700 kg 2 years Inert balls for DME Reactor ( ½ / ¼ ) 2000/2000 kg 2 years PVM Catalyst (for 01-R-0151 AB/C) 124820 kg 12000hrs ( 3 reactor) Inert balls for DME Reactor (½ /¼ /½ ) 32700 / 33000 / 65300 kg 2 years Adsorbents and Support Material Molecular sieve for drying of olefinic product streams (01-D-0491 A/B / 01-D-0492 A/B) Molecular sieve for CO2-Adsorption ( for 01-D-0532 A/B) Adsorbent for DME (Guard bed) (for 01-D-0533 A/B) 48000 kg 2 3 years 98560 kg ) 2 3 years 20480 kg 2 3 years Inert Balls for Adsorbers (1 / ¼ / ½ ) 8000/4200/3920 kg 2-3 years Ion Exchanger Methanol polisher (for 01-D-0611) 9900kg Approx. 5 years Chemicals Caustic Soda (28%) Approx. 50 kg/h - Gasoline Stabilizer (44% solution) 15 kg/h - Corrosion Inhibitor (cooling water) Biocide in coolig water NaOCI solution (12 wt%cl) 1.5 kg/h 17 kg/h In 10000 m3/h water circulation (norm. op)

Utility Electrical Power Consumption High Pressure Steam Consumption (39.5 barg) Boiler Feed Water Consumption (HP) Cooling Water Consumption Instrument Air Consumption Unit Demand KWh Electricity / t propylene 372 thp steam / t Propylene 4.81 t Boiler Feed Water / t Propylene 2.47 M 3 Circulating Water, T=10 C / t Propylene 887 Nm 3 Instrument air/ t Propylene 50 ٩

شرکت ملی صنایع پتروشیمی National Petrochemical Company Acetone and Aldehydes Acetone Acidity (as acetic acid) Alkalinity (as ammonia) Appearance Carbonizable impurities, Color Color Distillation range at 760 mm Hg, maximum Pure Methanol Specification Grade AA Ethanol, percent by weight, maximum 0.001 Non-volatile content, g per 100 ml, maximum Odour Permanganate fading time 0.003 percent by weight, maximum 0.002 percent by weight, maximum 0.003 percent by weight, maximum 0.003 percent by weight, maximum Free of opalescence, suspended matter and sediment (clear-colorless) Not darker than color standard No. 30 of ASTM D 1209, platinum cobalt scale Not darker than color standard No. 5 of ASTM D 1209, platinum cobalt scale 1.0 C (and shall incl. 64.6 C ± 0.1 C) 0.0010 Specific gravity at 20, maximum 0.7928 Water, percent by weight, maximum 0.10 Methanol, percent by weight, minimum 99.85 Characteristics: non-residual No discharge of color in 50 min. ١٠

شرکت ملی صنایع پتروشیمی National Petrochemical Company Propylene Methane, ethane, ethylene, propane Propylene (Polymer Grade) Other paraffines, olefins, naphthenes, aromatics Other components (see below) Hydrogen Carbon Monoxide Carbon Dioxide Oxygen Water Acetylene Methyl acetylene Propadiene Butadienes Dimethylether (DME) Acetone Methanol Cyclopentadiene 99.60 percent by weight, minimum 0.40 percent by weight, maximum 200 ppm by weight, maximum 40 ppm by weight, maximum 5 ppm by weight, maximum 0.03 ppm by weight, maximum 3 ppm by weight, maximum 5 ppm by weight, maximum 5 ppm by weight, maximum 2 ppm by weight, maximum 2 ppm by weight, maximum 1 ppm by weight, maximum 3 ppm by weight, maximum 5 ppm by weight, maximum 3 ppm by weight, maximum 5 ppm by weight, maximum 0.05 ppm by weight, maximum ١١

LPG (Liquefied Petroleum Gas) C 2 - Hydrocarbons 0.2 percent by weight, maximum C 3 Hydrocarbons 10 25 percent by weight C 4 Hydrocarbons 75 90 percent by weight C + 5 Hydrocarbons 2.0 percent by weight, maximum Total Sulfur Components 5 ppm by weight, maximum Gasoline Density @ 15 C 740 790 kg/m³ Equivalent Dry Vapour Pressure (DVPE, EN 13016-1) 0.45 0.70 bar Research Octane Number (RON) 90 95 Composition Paraffins and Naphthenes 45 65 percent by weight Olefins 20 25 percent by weight Aromatics 15 30 percent by weight Benzene 1.0 percent by volume, maximum Total Sulfur Components 5 ppm by weight, maximum ١٢

High propylene yield (~62%, on C basis) Simple process (low-cost propylene production) Simple fixed-bed adiabatic reactor system Simple well-known purification section Moderate operating condition Valuable by-products (LPG, Gasoline) ١٣

Several microrecator setups with online analyzers Lab and pilot scale catalyst production setups 4 100 gr catatest setup (parallel beds) 1500 gr catalyst pilot plant with main separation units PVM Demo plant with complete comercial features (world s first demonstration PVM plant) Complete analytical facilities Expert research and engineering team ١٤

PVM Microrecator setup (up to 50 gr catalyst) Fixed bed reactor Reaction in adiabatic conditions Steam generation Catalyst testing Modification of reaction conditions ١٥

PVM Pilot Plant (1.5 kg) Six adiabatic PVM reactors with DME pre-reactors compressor (23 bar) continuous C4/C5 recycle DME removal column In-depth & long-term investigation of recycle effects Data acquisition for process design ١٦

DEMO Plant unit Six stage adiabatic PVM reactor DME adiabatic reactor Capacity: Propylene 1 ton/day LPG 165 kg/day Gasoline 295 kg/day Complete separation to achieve pure propylene (Polymer grade) Complete recycle system to increase the propylene production Compatibility with commercial unit DEMO Unit ١٧

شرکت ملی صنایع پتروشیمی National Petrochemical Company Lab. Scales 4 100 gr 1.5 kg 180 kg 1.5 kg/hr MeOH 150 kg/hr MeOH Commercial Scales 0.3 kg/hr MeOH 5 100 120 470 ١٨ Up to (3 ) 29000 kg/hr MeOH

More than 24000 hour-on-stream pilot plant run More than 7000 hour-on-stream DEMO plant run Development of a new catalyst with great performance Preparing PVM basic design package (120 kta) Kimya garan sabzevar co. and Fanavaran petrochemical co. ١٩

Modification in reactor control loops in demo plant and modify of basic engineering industrial documents ٢٠

Modification in reactor control loops in demo plant and modify of basic engineering industrial documents Replace the main reactor preheater, steam super heater and recycle streams preheater by gas furnace,(redesign industrial furnace and the recycle streams preheater is removed. ٢١

Modification in reactor control loops in demo plant and modify of basic engineering industrial documents Replace the main reactor preheater, steam super heater and recycle streams preheater by gas furnace,(redesign industrial furnace and the recycle streams preheater is removed. Modification the catalyst regeneration recipe and decreasing the nitrogen consumption over than 60%. Modification in lines, isometrics and also type of insulation to decrease heat lost. The operating manual is modified for good operation practice. i.e. separation unit. ٢٢

NPC-RT PVM catalyst NPC-RT PVM Catalyst Pilot Test Reaction: T= 480 C, WHSV=0.9h -1 P= 1 atm, MeOH/ H 2 O = 1/1 wt % ٢٣

Title Filling date Assignee Preparation of solid catalyst for DME synthesis in fixed bed reactor 2007 NPC Methanol Conversion to Propylene by Catalyst base on Aluminosilicate 2008 NPC Conversion of methanol to propylene on modified mordenite catalyst 2008 NPC Preparation of nanocatalyst H-ZSM-5 for methanol to propylene process 2009 NPC MFI Catalyst Preparation in atmospheric Pressure for Methanol Conversion to Light Olefines 2009 NPC Preparation of Aluminosilicate catalyst for DME synthesis 2010 NPC Propylene Production via Methanol and DME Process 2011 NPC Aluminosilicate Catalyst for Preparation Propylene via Methanol 2013 NPC Increasing Propylene Production via Methanol by Recycle Stream 2015 NPC ٢٤

Thank you for your kind attention Q / A? PVM Demo Unit