16 April Hotel Le Meridien New Delhi Isomalk Technologies for Light Naphtha Isomerization
Naphtha Processing Technology by GTC n-c4 Isomalk-3 i-c4 Light Naphtha Isomalk-2 C5/C6 Isomerate C7 Paraffins Isomalk-4 C7 Isomerate Heavy Naphtha Semi- Regenerative Reforming Reformate 2
Isomerization Technology Requirements Efficiency Low operating temperature (100-150ºС) High octane product (possibility of 92-93 RON) Low H2 consumption and operating costs Long service life (up to 10 years) Environmental Avoidance of acid and alkali wastes Operations and Safety No acid agents Tolerance to catalytic poisons and excursions of feedstock impurities Activity recovery after contaminants removal from the feed Regenerable catalyst 3
Technology Choices Three light gasoline isomerization processes Chlorinated alumina catalysts Reasonable octane increase Regular organochloride additions required Spent caustic disposal also required Extreme measures for H20 and impurity removal Zeolite catalysts High operating temperature Less favorable for formation of high-branched isomers Mixed metal oxide catalysts Advantages of chlorinated alumina plus zeolite, with none of the disadvantages Isomalk-2 leading mixed metal oxide catalyst 4
Temperature Range and Efficiency of Different Isomerization Catalysts 80 70 60 MF 5 (MF 6 )/HF Unstable, disqualified 2.2DMB/ С 6 Н 14, % 50 40 30 SI-2 and Pt/Al 2 O 3 -C l Pt/ZrO 2 -SO 4 First generation, obsolete 20 Pt/zeolite Pt/Al 2 O 3 -F 10 0 0 50 100 150 200 250 300 350 400 450 Temperature C 5
Thermodynamic and Kinetic Limitations equilibrium curve SI-2 curve chlorinated catalyst curve oxide catalyst curve 2,2 DMB/ ΣС 6 Н 14,% zeolite catalyst curve Temperature C 6
Isomerization Comparison Parameter Chlorinated Catalysts Pt/Al 2 O 5 -Cl Zeolite Catalysts Pt/Zeolite Pt/Sulfated Oxides Isomalk-2 Pt/ZrO 2 -M x O y -SO 4 Operating temperature ( C) 120-180 250 280 140-200 120-180 Pressure (kg/cm 2 ) 30 40 20 30 30 35 25 30 H 2 /HC 0.2 0.5 / 1 1 2 / 1 2 3 / 1 2 3 / 1 Octane Number (RON) Once-through 82 85 78 79 80 81 82 85 DIH 86 88 81 82 84 86 88 DIP + DIH 89 90 83 86 86 87 89 90 DIP + DP + DIH 91 93 84 87 89 90 91 93 Trace Contaminant Limits Sulfur (ppm) < 1.0 < 10 < 1.0 < 2.0 Nitrogen (ppm) < 0.5 < 2.0 < 0.5 < 1.0 Water (ppm) < 0.5 < 50 < 3.0 < 10.0 Capability to Regenerate No Yes Yes Yes Water Poisoning Irreversible Recoverable Recoverable Recoverable Isomalk-2 SM is a low-temperature high performance isomerization technology with impressive tolerance to process impurities. 7
High Naphthenic Hydrocarbons - Higher Conversion on SI-2 Naphthenic hydrocarbons conversion to paraffins over chlorinated and SI-2; more benzene allowed in feed. 70 60 Conversion,% 50 40 SI-2 oxide catalyst 30 20 10 Pt/Al 2 O 3 -Cl 0 100 110 120 130 140 150 160 170 180 190 Temperature C 8
Lower C7+ Formation on SI-2 Formation of low-octane С 7+ hydrocarbons in isomerization over chlorinated and SI-2 catalysts; better overall octane 3 2 Yield, C 7+, % Pt/Al 2 O 3 -Cl 1 SI-2 oxide catalyst 0 100 110 120 130 140 150 160 170 180 190 Temperature C 9
Tolerance of the SI-2 Catalyst to Process Impurities 40 SI-2 oxide catalyst 30 Activity, 2,2-DMB/ С 6 Н 14, % 20 Pt/Al 2 O 3 -Cl 10 0 H 2 O, Н 2 S, ppm 0 1 2 3 4 5 6 Minimum risk, high-performance operation; optimized shut-down and start-up procedures 10
SI-2 and Chlorinated Aluminum Operation Cost Comparison Benchmark cost study of the processes over chlorinated and SI-2 catalysts. Chlorinated catalysts - 15% SI-2 catalyst Recycle and product separation Reactor block operation costs Costs of feed water removal and sour gas caustic treatment 11
Isomalk-2 Once-through No Caustic Treatment Block Gas C 1 -C 4 No Perchloroethylene Addition Compressor Dryer Feed Reactor Section Make-up Hydrogen Stabilizer No Feed Dryers Needed Product RON 81-85 RON 82-84 12
Isomalk-2 with Full Recycles Isopentane fraction n-pentane recycle Product Product RON 92-93 RON 91-92 Compressor Reactor Section H 2 Dryer C 1 -C 4 gas H/T feed Deisopentanizer Make-up H 2 Stabilizer Depentanizer Deisohexanizer Low Octane Residue reduced 10 times n-hexane recycle 13 Unwanted Naphthene Recycle minimized
Plant I Case Study, World-Scale Grass-Root Isomalk-2 Unit. 14
Plant I, Case Study, World-Scale Grass Roots Isomalk-2 Unit Full Recycle Capacity, t/y 1,100,000 Isomerate yield, % 99 i-pentane cut, RON 92.0-93.0 Light Isomerate, RON 91.5-92.5 Space velocity in the reactor block, hour -1 2.0-2.5 Start-up year Q4 2010 First World-Scale isomerization unit to use non-chlorinated catalyst and achieve 92.5 RON for final isomerate 15
Plant II Case Study, World-Scale Revamp to Isomalk-2 Unit at BPCL Mumbai 16
Revamp Objectives at BPCL Mumbai Convert existing Semi Regenerative Catalytic Reforming Unit (CRU) to an Isomerization (ISOM) / revamp existing Naphtha Hydro desulfurization (NHDS) unit Increase processing capacity Maximize Isomerate Yield & Octane To produce special products such as Food Grade Hexane (FGH), Special Boiling Point (SBP) Maximize the use of existing equipment 17
Revamp to Isomalk-2 Unit at BPCL Mumbai Revamped existing Naphtha Hydrodesulfurization unit by replacing catalyst to hydrotreat Naphtha streams Revamped existing Reformate Splitter to be used as Naphtha Splitter for splitting hydrotreated naphtha into Top cut as Isomerization Feed Side cut for blending into MS Bottom cut for blending into HSD Revamped existing idle CRU to an Isomerization unit using SI-2 catalyst New DWC combining Deisohexanizer and FGH column to produce Food Grade Hexane product and Isomerate. 18
Plant II Case Study, World-Scale Revamp to Isomalk-2 Unit at BPCL Mumbai Feed from various sources with high x-factor Benzene up to 5% C7 and Naphthenes up to 10% Successfully commissioned with the overall annual capacity of the isomerization section being 680 KTA. Once Through Capacity, t/y 680,000 Isomerate yield, % 97 Stabilized Isomerate, RON 84 Space velocity in the reactor block, hour -1 2.0-2.5 Start-up year Q1 2017 19
Isomalk-2 Applications: Revamp of Other Technologies Company, Year Type of Project Capacity Process Scheme Octane, RON Plant A, 2003 Revamp of Reforming Unit to Isomalk-2 Technology 500 KTA DIH 86-87 Plant B, 2005 Revamp of a Zeolite unit to Isomalk-2 Technology 400 KTA Once-through 82-83 Plant C, 2005 Revamp of a Zeolite Unit to Isomalk-2 Technology 500 KTA Once-through 83-84 Plant D 2005 Revamp of Reforming Unit to Isomalk-2 Technology 400 KTA DIP+DIH 86-87 Plant E, 2006 Revamp of a ZrO 2 based Unit into the Isomalk-2 Technology 180 KTA DIP+DIH 86-87 Plant F, 2008 Revamp of a Zeolite unit to Isomalk-2 Technology 300 KTA DIH 86-88 Plant G, 2009 Revamp of a Zeolite unit to Isomalk-2 Technology 500 KTA DIH 87-88 Plant H, 2015 Revamp of Reforming Unit to Isomalk-2 Technology 300 KTA DIH 86-88 20
Isomalk-2 Highlights Leading low-temperature C 5 -C 6 isomerization technology Based on a use a mixed metal oxide catalyst (non-chlorinated) Low-operating temperatures - high RON, high yields, optimum OPEX There is no need for chlorine injection, off-gas caustic scrubbing, feed dryers Water, Sulfur, Nitrogen specs are significantly relaxed Operation is simple and robust. Minimal start-up, turn-around, shutdown time minimal due to resistance to catalytic poisons >15% CAPEX and OPEX advantage over competing technologies In the last 10 years, Isomalk-2 has been preferred for 30 refinery projects 21
Naphtha Processing Technology by GTC n-c4 Isomalk-3 i-c4 Light Naphtha Isomalk-2 C5/C6 Isomerate C7 Paraffins Isomalk-4 C7 Isomerate Heavy Naphtha Semi- Regenerative Reforming Reformate 22
Isomalk-3 Highlights Isomalk-3 is the leading low-temperature C 4 isomerization technology based on a using a mixed metal oxide catalyst (non-chlorinated) Isomalk-3 was developed as the analogue of Isomalk-2 (C 5 -C 6 ) for C 4 isomerization. A recent award for Isomalk-3 is the first ever non-chlorinated unit in Asia. Operating temperatures of 160-180 o C achieve high conversion, yield and have optimum OPEX The expected catalyst lifetime of Isomalk-3 is 10 years, Pt recovery minimized There is no need for chlorine injection, off-gas caustic scrubbing, only one reactor design. Water, Sulfur, Nitrogen specs are significantly relaxed Operation is simple and robust. Start-up, turn-around, shutdown time are minimal due to resistance to catalytic poisons 23
Isomalk-3 Highlights Process parameter Isomalk-3 Temperature, о С 160-180 Pressure, MPa 1.5-1.8 H2/Feed ratio 0,05-0,1 LHSV, h -1 8-10 N-butane conversion, per pass 50-55 Selectivity for C3+, wt % 98-99 Chlorine injection Off-gas scrubbing no no Life-time of the catalyst, years 8-10 24
Block Flow Diagram for Isomalk-3 No Caustic Treatment Block DA-2/1,2 C-3 Hydrocarbon Gas H 2 gas One Reactor Design RD-3 No Perchloroethylene Addition P-2/A, B DA-2-1/1,2 n-butane fraction P-1/A, B No Additional Trap Beds Required HE-1 R-1 HE-2 SC HE-3 C-4 Stable Isomerate 25
Catalyst Impurity Limits Parameter SI-3 Trace Contaminant Limits Sulfur (ppm) < 2.0 Nitrogen (ppm) < 1.0 Water (ppm) < 10.0 Olefins, wt.% <1.0 Capability to Regenerate Water Poisoning Yes Recoverable Isomalk-3 is a high performance C4 isomerization technology with impressive tolerance to process impurities 26
Isomalk-3 Commercial Units No. Company Process Scheme 1 Liaoning Hualu, China n-butane Isomerization 2 Shandong Sincier, China With propane and butane dehydrogenation unit 3 Haike Ruilin, China n-butane Isomerization 27
Isomalk-3 Summary Based on the use of a non-chlorinated high performance mixed oxide SI-3 catalyst. Offers competitive yield of final product. Significantly reduced CAPEX > 25% excludes chlorine injection equipment and caustic scrubbing, only one-reactor design. Significantly reduced OPEX provides longer catalyst life-time, reliable operation, no need for chloride supply and no corrosion or wastes produced. 28