Gas Processing Technologies Recent Advances. Dr. N V Choudary Scientist Emeritus Hindustan Petroleum Corpn. Ltd.

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1 Gas Processing Technologies Recent Advances Dr. N V Choudary Scientist Emeritus Hindustan Petroleum Corpn. Ltd.

2 Outline About HPCL Gas processing HiGAS technology H2PSA Technology

3 About Hindustan Petroleum Corpn. Ltd. HPCL is Global Fortune 500 and Forbes 2000 company. Sales turnover about USD 30 billion during Owns & operates 2 major refineries producing a wide variety of petroleum fuels & specialties. Cumulative refining capacity ~24 MMTPA (including JV refinery). Largest Lube producer in India. Over 300+ grades of Lubes, Specialties and Greases.

4 Brief HP Green R&D Centre HPCL has set-up HP Green R&D Centre at Bengaluru in a campus of 104 acres, with an objective to develop innovative technologies and products. The phase-i is set-up with an initial investment of over USD 75 millions. Currently we have a dedicated team of about 80 scientific staff with an average age of 32 years. Developed and demonstrated 8 products/process during the last four years. Filed over 60 patents.

5 Products & Processes developed & demonstrated HP-HiGAS: Revolutionary technology for gas processing with significant size reduction. H2 PSA: Technology for hydrogen purification with enhanced regeneration capability. Cat-Visbreaking: Distillate yield improvement using novel soluble catalyst HP Spraymax: Improved feed nozzles for FCC units. HP-DUCER: Chemical for pressure drop reduction in fixed bed reactors. HP-FurnOcare: Furnace tubes online cleaning for performance enhancement. HP CoSol: Co-solvent system for increasing Lube base oil yield. HP-BioActiva: Microbial additive for improvement of refinery effluent characteristics.

6 Pilot Plant Facility

7 Analytical Facility

8 Gas Processing in Petroleum and Petrochemical Industry

9 Gas Processing Gas processing is important in refining & upstream oil platforms. The major applications: Acid gas (H 2 S/ CO 2 ) removal from various hydrocarbon streams such as natural gas, refinery fuel gas, etc. H2 purification from Reformer off-gases and steam reformers H 2 S removal from H 2 recycle gas (e.g. Hydrotreating units) Off-shore Gas purification Processes Syngas purification (removal of H2S, CO2, SOx and NOx)

10 Methods for Gas Processing Absorption process using a solvent: Trayed columns Adsorption process using a solid adsorbent: Pressure Swing Adsorption (PSA) Temperature Swing Adsorption (TSA) Membrane process using a membrane

11 Separation by Absorption Conventional trayed absorption columns are most widely used. Solvent counter-currently contacts feed gas & absorbs impure gases. Treatment columns have limitations particularly in space-constrained locations like off-shore platforms and on-ship LNG plants.

12 Solvents for Absorption Monoethanolamine (MEA), H2NCH2CH2OH Diethanolamine (DEA), HN(CH2CH2OH)2 Methyldiethanolamine (MDEA), CH3N(CH2CH2OH)2 Activated methyldiethanolamine (amdea) Di-2-propanolamine (DIPA), HN(CH2CH(CH3)OH)2 Diglycolamine (DGA), H2N-CH2CH2OCH2CH2OH Sterically hindered amine e.g., AMP (2-amino-2-methyl-1-propanol) (CH3)2C(NH2)CH2OH. Has high equilibrium loading capacity.

13 Commercial Absorption Technologies Process Licensor Sorbent Reference Chemical Absorption Econamine Fluor Diglycolamine, mono-ethanolamine ADIP-X Shell MDAE+accelerator amdea BASF MDEA GAS/SPEC Ineos MDEA UCARSOL DOW MDEA KM CDR Mitsubishi KS-1 hindered amine Mimura et al., Ene. Con. Manage, 1995, 36(6-9), 397 Benfield UOP Potassium carbonate UOP overview of gas processin Catacarb Eickmeter and Associates Potassium carbonate (+Organic additive) Flexsorb HP Exxon Mobil Potassium carbonate (+steric amine)

14 Commercial Absorption Technologies - Contd. Process Licensor Sorbent Reference Physical Absorption Fluor Solvent Fluor Dry propylene carbonate Selexol UOP/DOW Mixed polyethylene glycol dimethyl ethers Purisol Lurgi 2-Methyl-2-pyrrolidone Rectisol Lurgi Chilled methanol Ifpexol IFP Chilled methanol Larue et., al., Oil Gas Sci. Tech., 1996, 51(5), Mixed-solvent process Sulfinol-D Shell Sulfolane + DIPA + Water Amisol Lurgi Methanol + Sec. amine + Water Kohl and Nielsen., Gas Purification, Gulf Pub.

15 HPCL s Novel gas processing Technology HP-HiGas Technology

16 HP-HiGAS Technology Technology is based on the concept of process intensification. HP-HiGAS technology, having compact design & low foot print can be a revolutionary alternative to trayed absorption process. Utilizes high centrifugal force which improves the mass transfer rate & reduces the Height Equivalent to Theoretical Plate (HETP) by ~ times resulting in significant size reduction. A Rotating Packed Bed is used having porous packing elements with high surface area providing space for gas-liquid mass transfer.

17 Schematic Operation Gas In Liquid In Gas Out Motor Shaft Liquid Distributor Casing Packing elements Liquid Out

18 HP-HiGAS Technology HP-HiGAS reduces the footprint of equipment resulting in lower capital cost. The first commercial unit was set-up at HPCL Refinery for the removal of H 2 S from Fuel Gas. The unit was commissioned in Sept, The unit is designed for treating 14 Tons/hour of Refinery Fuel gas for reducing H 2 S content over 4 wt% (40000 ppm) to <100 ppm. Plant size reduction achieved by 10 times, i.e., a 2.5 mts. HP-HiGAS vs the existing conventional FGAAU column of 23 mts.

19 HiGAS Unit at HPCL Vizag Refinery

20 HP HiGAS unit performance Commercial HiGAS unit at HPCL processes feed gas with H2S content of about 4 to 5 wt% and achieves <100 ppm which is better than the design. Mechanical performance as well as process performance (absorption efficiency) of HiGAS unit is highly satisfactory. Flow Rate (Kg/hr) H2S Content (wt%) Sour Gas Sweet Gas ppm Lean Amine Rich Amine

21 Benefits Smaller equipment / Lower footprint. Lower Capital Cost (25% savings). Safer process (low hydrocarbon hold-up). Ease of maintenance. Can overcome limitations of conventional off-shore units (swaying effect on tray liquid level, weight).

22 Adsorption Process H2 PSA Technology

23 Hydrogen PSA Technology Demand for H2 is ever increasing due to the growth of Hydroprocessing technology in refineries which require huge amounts of H2. PSA Technology is widely used for H2 purification. There are very few process licensors offering PSA technology.

24 H2 PSA Unit HPCL developed H2 PSA technology using multiple adsorbents. The first 6-bed commercial PSA unit was set-up at HPCL Refinery for the purification of H2 from CCR off-gas. The unit was commissioned in May The PSA unit is designed for 99.5 mol% H2 purity & 88% recovery. Unique Feature: Capacity enhancement possibility by 40-50% by incorporating Vacuum blower without any other major hardware changes.

25 Design Information Description Value Capacity (Nm3/hr) 36,000 Feed Composition (vol%) H2 = 93.5 CH4 = 2.5; C2H6 = 2.3 C3H8 = 1.5; C4+ = 0.2 Pressure (Kg/cm2g) 23.0 Temperature (deg C) 40 Source CCR Product Composition (vol%) H2 = 99.5; CH4 = 0.5 Product Recovery (%) 88 Tail Gas Pressure (Kg/cm2g) 0.5

26 Operation & Performance Operating at 110% of design thru put with intended H2 purity. Meeting Hydrogen (H2) demand of one of the HPCL Refineries.

27 Unit at HPCL Vizag Refinery

28 Future? Novel adsorbents with high CO 2 adsorption capacity Adsorbent BET SA (m2 g-1) CO2 Ads Cap at 1 bar/298k (mol kg-1) CO2 Ads Cap at 5 bar/298k (mol kg-1) CO2 working cap (mol kg-1) AC A AC B AC C Zn/DABCO Ni/DABCO Cu-BTC MIL IRMOF MOF MIL References: 1) HPCL data; 2) S Himenoa, et al., J Chem. Eng. Data 2005, 50, ; 3) Z. Liang, et al., Micro & Meso Mat., 2010, 132, ; 4) J R Karra and K S Walton, J. Phys. Chem, C, 2010; 5) P L Llewellyn, et al., Langmjuir 2008, 24, ; 6) A R Millward, et al., J. Am. Chem. Soc., 2005, 127, ; 7) S Bourrelly, et al., J. Am. Chem. Soc., 2005, 127,

29 Conclusions Gas processing in Oil & Gas sector is witnessing significant technological changes. HP-HiGAS Technology is a major path-breaking and disruptive technology which can change the landscape of gas processing in refining and upstream industry. HP H2PSA technology has unique advantage as it can use vacuum desorption resulting in higher plant capacity.