Sarthak Urankar Adsorbent Purification Solutions for Refining and Petrochemicals 19 February 2018 Honeywell UOP ME-TECH Seminar Dubai, UAE UOP 8080C-0 2018 UOP LLC. A Honeywell Company All rights reserved.
Why Remove the Trace Contaminants? Get better yields from your expensive catalysts Nobel metal catalysts (isomerization, reforming, selective hydrogenation, complete saturation) prevent sulfur compound poisoning Polymerization catalysts (Ziegler Natta, Metallocene) Meet or exceed product specifications Polymer grade olefins water, arsine and mercury, COS, CO 2, CO and O 2 and other oxygenates Copper strip product specifications sulfur compounds Productivity, g/g Active Metal 4,000,000 3,500,000 Catalyst Activity 3,000,000 2,500,000 2,000,000 1,500,000 1,000,000 500,000 0 Mercury attack Contaminant Specifications 150,000 Catalyst Activity 300,000 Catalysts 600,000 1 1 4,000,000 Protect equipment (plant and pipelines) Chloride removal to minimize corrosion Mercury attack of equipment and cold boxes Environmental toxicity and for emission controls (Increased toxicity awareness, Tighter TLV limits / tighter emission standards) Mercury, sulfur compounds Equipment fouling Equipment Damage UOP 8080C-1
Contaminants of Concern In Petroleum Refineries 2 2 Gas Concentration Amine Guard H 2 Plant Polybed PSA From FCC LPG Light Straight Run Hydrotreating From FCC Light Naphtha Isomerization Propylene Crude Distillation Naphtha Hydrotreating Catalytic Reforming Gasoline Desalted Crude Oil Kerosene Middle Distillate Atmospheric Gas Oil Hydrotreating Catalytic Condensation C 4 Isomerization Kerosene Jet Fuel Diesel Legend Mercury Fluorides Vacuum Distillation FCC SHP Alkylation Arsine Oxygenates Chlorides Water Sulfur Compounds UOP 8080C-2
UOP Purification Solutions 3 3 UOP continues to develop new technology solutions to meet industry demands Catalytic Reforming Net Gas Chloride Adsorbents + CLR-304 Metal Oxide Sulfur Guard Beds ADS-120 Specialty Hybrid Adsorbents AZ-300/AZ-400 for purification of reactive streams Metal Sulfides Mercury Guard Beds GB-347 UOP 7879H-3 UOP Can Help You Meet Your Future Technology Needs
Chloride Management for Catalytic Reforming Reactor Section 8 4 Catalyst Regenerator Stacked Reactor Naphtha Feed from Treating Combined Feed Exchanger Recycle Gas Compressor Net Gas Compressor Recovery Section Preferred location Net H 2 Rich Gas Fuel Gas Separator Fresh Catalyst H H H H Fired Heaters Stabilizer Light Ends Spent Catalyst Possible locations for chloride gas or LPG Treaters Possible location for stabilizer liquid chloride Treaters Preferred location Reformate to: Gasoline Pool, or Aromatics Recovery UOP Addresses Corrosion and Plant Safety in the Entire Reforming Process
UOP Chloride Management Portfolio 5 UOP is the Supplier that Manufactures the major types of chloride adsorbent, including promoted aluminas, molecular sieves and mixed metal oxides Provides an unbiased recommendation of single or combination products to most cost effectively address your technical needs UOP Product CLR-204 CLR-304 CLR-454 Base Material Service Green oil Formation Promoted Alumina Net Gas and LPG Very low Mixed Metal Oxide Net Gas Negligible Molecular Sieve Net gas Reduces green oil and removes organic chloride PCL-100/ PCL-200 Molecular Sieve Stabilizer Feed, Liquid Phase N/A Are not only adsorbent experts but also have extensive knowledge of the Catalytic Reforming process and catalyst itself Adsorption capacity Preferred product for HCl & reduces organic chloride formation Excellent capacity for HCl, does not make organic chlorides Good for HCl & preferred for organic chlorides Good for HCl & for organic chlorides UOP Offers Products, Services and Field Expertise for Catalytic Reforming
Net Gas Chloride Treaters Two Case Studies & Key Technical Issues CLR-204 vs Promoted Alumina Feed: H 2 gas Operating temperature: 40 C Operating pressure: 1,200 KPa Start-up mid 2009 2 ppmv HCl CLR-204 vs Mixed Metal Oxide Feed: : H 2 gas (MW ~7.5) Operating temperature: 35 C Residence time: 20 seconds Start-up mid 2010 6 4 ppmv HCl Competitive alumina product experience - 4 months lifetime Severe green / red oil problem CLR-204 Mixed metal oxide ~5.5 months lifetime (~ 50% of stoichiometric capacity) CLR-204 CLR-204-7.5 months lifetime* No green oil problem CLR-204 6 months lifetime No green oil problem * Adsorbent change-out due to turnaround Not All The Promoted Aluminas Perform The Same Every Treater Is Unique 0.1 ppmv HCl Theoretical Adsorption Capacity Capacity Commercially Achieved < 1 ppmv HCl Product Performance Can Vary Tremendously Depending Upon Operating Conditions
Mixed Metal Oxide, CLR-304 Chloride Adsorbent for Net Gas 7 Chloride on Spent Adsorbent in Dynamic Lab testing 120 Oligomerization Reactivity Comparison % HCl Capacity CLR-304 CLR-204 100 80 60 40 20 Inlet 25% 50% 75% Distance into Adsorbent Bed Outlet 0 Commercial std. promoted alumina CLR-204 CLR-304 Green Oil UOP CLR-304 is UOP s Highest Chloride Capacity and Lowest Green Oil Production Product UOP 6570H-7
UOP Purification Solutions 8 8 UOP continues to develop new technology solutions to meet industry demands Catalytic Reforming Net Gas Chloride Adsorbents + CLR-304 Metal Oxide Sulfur Guard Beds ADS-120 Specialty Hybrid Adsorbents AZ-300/AZ-400 for purification of reactive streams Metal Sulfides Mercury Guard Beds GB-347 UOP 7879H-8 UOP Can Help You Meet Your Future Technology Needs
Sulfur Removal Adsorbents: Non-Regenerative 9 9 For C 5 + hydrocarbons sulfur compound removal, hydrotreating and /or Adsorbent sulfur guard beds are used NON-regenerative adsorbents are used to achieve ultra low sulfur levels UOP offers all major options and helps our customers select the product best suited to their specific needs ADS-11L (Nickel) ADS-120 and ADS-130 (Copper) ADS-280 (Zinc) Simplified sulfur guard bed chemistry M + H 2 S MS + H 2 O MO + H 2 S MS + H 2 O MO = metal oxide, MS = metal sulfide Metal oxide metal sulfide UOP 7879H-9 UOP Offers a Complete Portfolio of Sulfur Guard Beds Including Copper, Nickel and Zinc Products
Sulfur Guard Bed for Paraffin Isomerization Unit A Case Study 10 N. American Refinery: Sulfur Guard Bed; upstream of UOP Paraffin Isomerization Product Installed: ADS-120 Feed Rate: 100 m 3 /hr Operating temperature: 118 C Feed sulfur design: 1 ppmw ADS-120 handled an unexpected NHT upset extremely well The refiner claimed a 1 day NHT upset and estimated feed sulfur at ~ 70 ppmw Spent samples (10 samples from various parts) were tested - EVERY SAMPLE had achieved stoichiometric sulfur capacity during the upset Back calculated the feed sulfur was 350 ppmw if upset only lasted for 1 day 5x times vs. customer estimation and 350 X design feed sulfur! The ADS-120 bed had captured all the sulfur; previous experience with other products were NOT so good Customer reordered ADS-120 as a recharge in addition to replacement for a Catalytic Reformer Sulfur Guard Bed as well 1 ppmw Sulfur ADS-120 0.1 ppmw Sulfur Robust Product Performance is Critical in Order to Handle Process Upsets
UOP Purification Solutions 11 11 UOP continues to develop new technology solutions to meet industry demands Catalytic Reforming Net Gas Chloride Adsorbents + CLR-304 Metal Oxide Sulfur Guard Beds ADS-120 Specialty Hybrid Adsorbents AZ-300/AZ-400 for purification of reactive streams Metal Sulfides Mercury Guard Beds GB-347 UOP 7879H-11 UOP Can Help You Meet Your Future Technology Needs
Olefin Treating: Challenges 12 12 Removal of impurities from olefins, using adsorption, is significantly more difficult than from paraffins Adsorbent reactivity can impact operational safety and performance Strong olefin adsorption on molecular sieves can release sufficient heat to start a dangerous polymerization reaction + + Olefin Treating: Solutions Some Strategies to overcome these problems and reduce the concerns: Adsorbent selection to exclude the reactive olefin stream (ODG-442) Use of hybrid adsorbents (AZ-300/ AZ-400) that have a low heat of adsorption, are not reactive towards the process stream and has adequate contaminant capacity Use of chemisorbents such as low reactivity promoted aluminas or metal oxides to selectively scavenge targeted contaminants (COS, mercury, arsine) Purification of Reactive Streams, Such as Those Containing Olefins, Is Challenging
13 Low Catalytic Reactivity Adsorbents are a Must Have for Sensitive Olefin Purification Applications 13 UOP 7435G-13 Adsorbent Reactivity, Should be a Key Factor in Product Selection
UOP High Capacity Hybrid Adsorbent: AZ-400 14 14 AZ-400 is UOP s Highest Capacity Hybrid Adsorbent for Olefin Containing Streams Butene-1 Comonomer Treaters for LLDPE/ HDPE Plant % Capacity Improvement Over AZ-300 50 40 30 20 10 0 Diethyl Sulfide C3 Mercaptan Acetone T-Butanol Bed on Adsorption AZ- 400 ODG- 442 Treated Butene-1 to Polymerization Reactor CH 3 OH, Carbonyls, MTBE, Peroxides H 2 O N 2 at 240 C Bed on Regeneration AZ-400 hybrid adsorbent is especially effective, for the hard to remove, less polar contaminants Feed Butene-1 UOP 7435G-14 AZ-400 is UOP s Highest Capacity Hybrid Adsorbent for Demanding Olefin Purification Applications
UOP Purification Solutions 15 15 UOP continues to develop new technology solutions to meet industry demands Catalytic Reforming Net Gas Chloride Adsorbents + CLR-304 Metal Oxide Sulfur Guard Beds ADS-120 Specialty Hybrid Adsorbents AZ-300/AZ-400 for purification of reactive streams Metal Sulfides Mercury Guard Beds GB-347 UOP 7879H-15 UOP Can Help You Meet Your Future Technology Needs
Mercury in the Hydrocarbon Chain 16 Upstream Midstream Downstream Exploring, drilling and producing crude oil and natural gas Processing, storage and transportation Refining oil and gas into fuels and chemicals Difficult to Mitigate Close to Wellhead Processing Technology and Materials Available in Natural Gas Processing Advanced Hg Removal Technologies Developed Amalgamation versus chemical reaction two different Hg removal pathways: regenerative and non-regenerative UOP can provide both regenerable and non-regenerable adsorbents for R&P applications, which allows for flexible flow sheet location choices, and sometimes used in combination to provide an economical MRU solution 1. UOP Regenerable HgSIV adsorbents: amalgam formation Ag o + Hg o = HgAg 2. UOP GB non-regenerable adsorbents metal sulfide products for liquid applications (GB-346S, GB-346HPS, GB-347) and 500 series products for gas phase (unsulfided options are also available) 2CuS + Hg = HgS + Cu 2 S UOP 8080C-16
Adsorbent Purification Solutions for Refining and Petrochemicals 17 17 UOP adsorbents are an effective, and economical, method for purification of process streams in Refineries, Petrochemical processes and Natural Gas Conditioning Factors to consider in adsorbent selection Adsorbent capacity and selectivity Adsorbent reactivity Process reliability and safety Continuous Product and Process Innovation World-wide Tech service support Multiple manufacturing facilities located world-wide to satisfy our customers needs UOP Modular solutions for timely, guaranteed performance CLR-204/304 PCL-100/200 P-188 HgSiv-3 GB-3465 Chloride Flourides GB-238 3A-EPG ODG-442 AZ-400 AZ-300 CG-731 GB-620 GB-622 SG-731 GB-217 AZ-400 AZ-300 Single Point Responsibility (Adsorbents & Services) Similar to Managing Licensor Concept Hg AsH 3 / PH 3 / SbH 3 H 2 O MolSiv Alumina Hybrid Metal Oxide Oxygenates CO 2 O 2 /CO H 2 S/COS/ Mercaptans/ CS 2 NH 3 /RSH AZ-400 AZ-300
UOP 8080C-18 18
UOP Offers a Complete Range of Contaminant Removal Solutions 19 19 Molecular Sieves Use of a small pore zeolite enables exclusion of reactive species and is very effective for dehydration Other contaminants may need a larger pore (such as a 4A, 5A, or 13X type) which may adsorb a reactive carrier stream thus a preload step may be required Careful selection of base material helps control high surface energy and active sites to meet adsorption requirements in reactive streams Hybrid Adsorbents Engineered homogenous combination of a promoted alumina and a large pore zeolite Combines high selectivity for light acid gases with low olefin reactivity (low heat of adsorption of hydrocarbons) and high capacity for polar molecules makes these products ideally suited for purification of olefinic streams Promoted Aluminas Activated aluminas are synthetic transitional phase aluminas with a tailored pore structure to facilitate rapid chemisorption, resulting in a short mass transfer zone Low affinity for reactive hydrocarbons, thus a preload step not needed Light acid gases such as CO 2, H 2 S & COS are removed by chemisorption to very low concentrations Metal Oxides & Sulfides Critical applications for hydrocarbon streams Trace arsine and phosphine removal from hydrocarbon streams to protect sensitive noble metal or polymerization catalysts Specialty applications - such as mercury & sulfur compound removal Trace CO, O 2 scavenging from ethylene and N 2 UOP 8080C-19
UOP HPG-300 MOLSIV Adsorbent for Improved Paraffin Isomerization Feed Treating 23 HPG-300 offers increased capacity for contaminants compared to current generation Butamer and Penex adsorbents. Key customer benefits include: Ability to increase throughput in existing feed driers by as much as 30% without contaminant breakthrough Ability to tolerate higher feedstock impurities and help olefin content Less frequent regenerations in existing vessels will save operating costs and result in longer adsorbent life UOP HPG-300 Adsorbent has Higher Contaminant Capacity & Ability to Tolerate Higher Feed Olefins
Arsine Adsorbent Performance: Lab and Commercial Tests 25 25 Non-UOP arsine guard adsorbent produces high boiling residue at 30 C UOP GB-238 arsine guard is non-reactive at a higher temperature (50 C) C 8 -C 20 + Oligomers 100 80 60 40 20 Arsine Adsorbent Lab Testing UOP GB-238 Arsine Guard at 50 C Non-UOP Arsine Guard at 30 C Arsine Adsorbent Accelerated Commercial Test 22 Days on Stream at 40 hr-1 LHSV 0 0 5 10 15 20 Time, hours Arsenic on Bed 0 UOP GB-238 Arsine Guard non-uop Arsine Guard 10 20 30 40 50 A combination of enhanced porosity along with lower reactivity enable the GB-238 to outperform a typical non-uop adsorbent with a similar metal content, helping achieve Safer operation and longer life Bed Depth, Inches UOP 8080C-25
Innovative CS 2 Removal from Petrochemical Naphtha 26 Petrochemical grade naphtha requires reduced CS 2 in order to reduce poisoning of pygas hydrotreating catalysts and equipment corrosion in ethylene Plants There is an increased global attention on CS 2 content of petrochemical naphtha UOP CS2-100 is a unique molecular sieve adsorbent which features: High CS 2 adsorption capacity Regenerability for long term usage A thermal swing adsorption (TSA) system with CS2-100: Has much lower capital cost versus a traditional Hydrotreating unit Is able to remove CS 2 to very low levels (e.g. <1 ppm) Petrochemical grade naphtha with < 1 ppm CS 2 UOP MOLSIV CS2-100 Hot Regenerant Bed on Regeneration Straight run naphtha contaminated with CS 2 and sulfur compounds New UOP Adsorption Solution for CS 2 Removal From Petrochemical Grade Naphtha
Modular CS 2 Removal Solution: Certainty in All Aspects 27 Low operating cost Consistently low CS 2 in product Optimize cycle time based on feed Does not depend on liquid feed composition Trouble-free operation Thermal swing adsorption (TSA) concept is proven commercially Modular fabrication and supply Quality via controlled environment Quick and certain delivery schedule Turnaround schedule Cost Guaranteed Performance CS 2 = <1.0 wppm; Adsorbent Life = 2 to 5 years Honeywell UOP s Modular TSA UOP 7879H-27 Modular Supply Equals On-Time, On-Budget, No Surprises
CS 2 in Petrochemical Naphtha Ethylene Plant Implications 28 Limits on CS 2 in Petrochemical naphtha date back to 2014 when naphtha industry agreed to report CS 2 level particularly influenced by Japanese isoprene producers 4 Issues with CS 2 in regard to the pygas hydrogenation unit were reported as far back as the 10th Ethylene Producers Conference in 1998 1 CS 2 passes through the cracking furnaces largely unaffected It passes through the traditional alkali wash process in ethylene crackers, which Is used to remove sulfur specifies from these processes CS 2 concentrates in the C 5 + pyrolysis gasoline Further processing options in the ethylene plant: Send C 5 + to pygas hydrogenation 2 Extract C 5 s from pygas (isoprene extraction unit there have been reports of polymerization catalyst deactivation, as well as severe CS 2 corrosion in such units) Hydrogenate the C 5 s for recycle cracking CS 2 Impacts Pygas Hydrogenation and Isoprene Extraction Units
29 29 Refinery & Petrochemicals Purification of Trace Contaminants Case Studies: Catalytic Reforming Net Gas Chloride removal Sulfur Guard beds for Paraffin Isomerization, Benzene Saturation and Catalytic Reforming Purification of Reactive Olefin Streams UOP 8080C-29
Ethylene Plant Cracked Gas and Cracked Liquid Solutions 30 30 EPG-2 3A-EPG EPG-N UOP HgSIV Adsorbent EPG-2 Dehydration Break-up resistant Low reactivity 3A-EPG Dehydration Superior mass transfer EPG-N Ammonia removal UOP HgSIV TM Mercury removal Same dryer size Existing and New Units Adsorbent Capabilities Use Layers of Multiple MOLSIV Adsorbents to Remove Multiple Contaminants