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Gas Processing Technologies Recent Advances
Dr. N V ChoudaryScientist Emeritus
Hindustan Petroleum Corpn. Ltd.
Outline …
➢ About HPCL
➢ Gas processing
➢ HiGAS technology
➢ H2PSA Technology
About Hindustan Petroleum Corpn. Ltd.
❖ HPCL is Global Fortune 500 and Forbes 2000 company.
❖ Sales turnover about USD 30 billion during 2015-16.
❖ 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.
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.
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.
Pilot Plant Facility
Analytical Facility
Gas Processing in Petroleum and
Petrochemical Industry
Gas Processing
❖ Gas processing is important in refining & upstream oil platforms.
❖ The major applications:
Acid gas (H2S/ CO2) removal from various hydrocarbon streams
such as natural gas, refinery fuel gas, etc.
H2 purification from Reformer off-gases and steam reformers
H2S removal from H2 recycle gas (e.g. Hydrotreating units)
Off-shore Gas purification Processes
Syngas purification (removal of H2S, CO2, SOx and NOx)
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
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.
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.
Commercial Absorption Technologies
Process Licensor Sorbent Reference
Chemical Absorption
Econamine Fluor Diglycolamine, mono-ethanolamine www.fluor.com
ADIP-X Shell MDAE+accelerator www.shell.com
aMDEA® BASF MDEA www.basf.de
GAS/SPEC Ineos MDEA www.gasspec.com
UCARSOL DOW MDEA www.oilandgas.dow.com
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)
www.catcarb.com
Flexsorb HP Exxon Mobil Potassium carbonate (+steric amine) www.exxonmobil.com
Process Licensor Sorbent Reference
Physical Absorption
Fluor Solvent Fluor Dry propylene carbonate www.fluor.com
Selexol UOP/DOW Mixed polyethylene glycol dimethyl
ethers
www.uop.com
Purisol Lurgi 2-Methyl-2-pyrrolidone www.lurgi.com
Rectisol Lurgi Chilled methanol www.lurgi.com
Ifpexol IFP Chilled methanol Larue et., al., Oil Gas Sci. Tech., 1996,
51(5), 653-668
Mixed-solvent process
Sulfinol-D Shell Sulfolane + DIPA + Water www.shell.com
Amisol Lurgi Methanol + Sec. amine + Water Kohl and Nielsen., Gas Purification, Gulf
Pub.
Commercial Absorption Technologies - Contd….
HPCL’s Novel gas processing Technology
HP-HiGas Technology
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 ~50-
100 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.
Schematic Operation
Casing
Packing elements
Motor ShaftLiquid Distributor
Liquid In
Gas In
Gas Out
Liquid Out
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 H2S
from Fuel Gas. The unit was commissioned in Sept, 2014.
❖ The unit is designed for treating 14 Tons/hour of Refinery Fuel gas for
reducing H2S 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.
HiGAS Unit at HPCL Vizag Refinery
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 13960 4.71
Sweet Gas 13020 100 ppm
Lean Amine 28750 0.24
Rich Amine 29680 2.44
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).
Adsorption Process
H2 PSA Technology
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.
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 2015.
❖ 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.
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
Operation & Performance
❖ Operating at 110% of design thru’put with intended H2 purity.
❖Meeting Hydrogen (H2) demand of one of the HPCL
Refineries.
Unit at HPCL Vizag Refinery
Future? ❖ Novel adsorbents with high CO2 adsorption capacity
References:
1) HPCL data; 2) S Himenoa, et al., J Chem. Eng. Data 2005, 50, 369-376; 3) Z. Liang, et al., Micro & Meso Mat., 2010, 132, 305-310;
4) J R Karra and K S Walton, J. Phys. Chem, C, 2010; 5) P L Llewellyn, et al., Langmjuir 2008, 24, 7245-7250;
6) A R Millward, et al., J. Am. Chem. Soc., 2005, 127, 17998-17999; 7) S Bourrelly, et al., J. Am. Chem. Soc., 2005, 127, 13519-13521
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 A1 1100 2.6 5.2 2.6
AC B1 1200 2 4.6 2.6
AC C2 1400 2.3 4.8 2.5
Zn/DABCO3 1725 2.2 10 7.8
Ni/DABCO3 1705 2.1 9 6.9
Cu-BTC4 1500 5.6 12.1 6.5
MIL-1015 2700 2.3 6.4 4.1
IRMOF-66 2506 1.1 5.1 4
MOF-56 2833 0.9 4.7 3.8
MIL-477 2674 2.5 6.4 3.9
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.
