Source: HANDBOOK OF PETROLEUM REFINING PROCESSES P ● A ● R ● T ● ALKYLATION AND POLYMERIZATION Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website ALKYLATION AND POLYMERIZATION Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website Source: HANDBOOK OF PETROLEUM REFINING PROCESSES CHAPTER 1.1 NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION Ronald Birkhoff Kellogg Brown & Root, Inc (KBR) Matti Nurminen Fortum Oil and Gas Oy INTRODUCTION Environmental issues are threatening the future use of MTBE (methyl-tert-butyl ether) in gasoline in the United States Since the late 1990s, concerns have arisen over ground and drinking water contamination with MTBE due to leaking of gasoline from underground storage tanks and the exhaust from two-cycle engines In California a number of cases of drinking water pollution with MTBE have occurred As a result, the elimination of MTBE in gasoline in California was mandated, and legislation is now set to go in effect by the end of 2003 The U.S Senate has similar law under preparation, which would eliminate MTBE in the 2006 to 2010 time frame With an MTBE phase-out imminent, U.S refiners are faced with the challenge of replacing the lost volume and octane value of MTBE in the gasoline pool In addition, utilization of idled MTBE facilities and the isobutylene feedstock result in pressing problems of unrecovered and/or underutilized capital for the MTBE producers Isooctane has been identified as a cost-effective alternative to MTBE It utilizes the same isobutylene feeds used in MTBE production and offers excellent blending value Furthermore, isooctane production can be achieved in a low-cost revamp of an existing MTBE plant However, since isooctane is not an oxygenate, it does not replace MTBE to meet the oxygen requirement currently in effect for reformulated gasoline The NExOCTANE technology was developed for the production of isooctane In the process, isobutylene is dimerized to produce isooctene, which can subsequently be hydrogenated to produce isooctane Both products are excellent gasoline blend stocks with significantly higher product value than alkylate or polymerization gasoline 1.3 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION 1.4 ALKYLATION AND POLYMERIZATION HISTORY OF MTBE During the 1990s, MTBE was the oxygenate of choice for refiners to meet increasingly stringent gasoline specifications In the United States and in a limited number of Asian countries, the use of oxygenates in gasoline was mandated to promote cleaner-burning fuels In addition, lead phase-down programs in other parts of the world have resulted in an increased demand for high-octane blend stock All this resulted in a strong demand for high-octane fuel ethers, and significant MTBE production capacity has been installed since 1990 Today, the United States is the largest consumer of MTBE The consumption increased dramatically with the amendment of the Clean Air Act in 1990 which incorporated the percent oxygen mandate The MTBE production capacity more than doubled in the 5-year period from 1991 to 1995 By 1998, the MTBE demand growth had leveled off, and it has since tracked the demand growth for reformulated gasoline (RFG) The United States consumes about 300,000 BPD of MTBE, of which over 100,000 BPD is consumed in California The U.S MTBE consumption is about 60 percent of the total world demand MTBE is produced from isobutylene and methanol Three sources of isobutylene are used for MTBE production: ● ● ● On-purpose butane isomerization and dehydrogenation Fluid catalytic cracker (FCC) derived mixed C4 fraction Steam cracker derived C4 fraction The majority of the MTBE production is based on FCC and butane dehydrogenation derived feeds NExOCTANE BACKGROUND Fortum Oil and Gas Oy, through its subsidiary Neste Engineering, has developed the NExOCTANE technology for the production of isooctane NExOCTANE is an extension of Fortum’s experience in the development and licensing of etherification technologies Kellogg Brown & Root, Inc (KBR) is the exclusive licenser of NExOCTANE The technology licensing and process design services are offered through a partnership between Fortum and KBR The technology development program was initialized in 1997 in Fortum’s Research and Development Center in Porvoo, Finland, for the purpose of producing high-purity isooctene, for use as a chemical intermediate With the emergence of the MTBE pollution issue and the pending MTBE phase-out, the focus in the development was shifted in 1998 to the conversion of existing MTBE units to produce isooctene and isooctane for gasoline blending The technology development has been based on an extensive experimental research program in order to build a fundamental understanding of the reaction kinetics and key product separation steps in the process This research has resulted in an advanced kinetic modeling capability, which is used in the design of the process for licensees The process has undergone extensive pilot testing, utilizing a full range of commercial feeds The first commercial NExOCTANE unit started operation in the third quarter of 2002 PROCESS CHEMISTRY The primary reaction in the NExOCTANE process is the dimerization of isobutylene over acidic ion-exchange resin catalyst This dimerization reaction forms two isomers of Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION 1.5 NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PROCUCTION trimethylpentene (TMP), or isooctene, namely, 2,4,4-TMP-1 and 2,4,4-TMP-2, according to the following reactions: TMP further reacts with isobutylene to form trimers, tetramers, etc Formation of these oligomers is inhibited by oxygen-containing polar components in the reaction mixture In the CH3 CH3 CH2 = C - CH2 - C - CH3 CH3 CH3 2,4,4 TMP-1 CH2= C - CH3 CH3 Isobutylene CH3 CH2 - C = CH2 - C - CH3 CH3 2,4,4 TMP-2 NExOCTANE process, water and alcohol are used as inhibitors These polar components block acidic sites on the ion-exchange resin, thereby controlling the catalyst activity and increasing the selectivity to the formation of dimers The process conditions in the dimerization reactions are optimized to maximize the yield of high-quality isooctene product A small quantity of C7 and C9 components plus other C8 isomers will be formed when other olefin components such as propylene, n-butenes, and isoamylene are present in the reaction mixture In the NExOCTANE process, these reactions are much slower than the isobutylene dimerization reaction, and therefore only a small fraction of these components is converted Isooctene can be hydrogenated to produce isooctane, according to the following reaction: CH3 CH3 CH2 = C – CH2 – C – CH3 + H2 CH3 Isooctene CH3 CH3 CH2 – C – CH2 – C – CH3 CH3 Isooctane NExOCTANE PROCESS DESCRIPTION The NExOCTANE process consists of two independent sections Isooctene is produced by dimerization of isobutylene in the dimerization section, and subsequently, the isooctene can be hydrogenated to produce isooctane in the hydrogenation section Dimerization and hydrogenation are independently operating sections Figure 1.1.1 shows a simplified flow diagram for the process The isobutylene dimerization takes place in the liquid phase in adiabatic reactors over fixed beds of acidic ion-exchange resin catalyst The product quality, specifically the distri- Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION 1.6 ALKYLATION AND POLYMERIZATION C4 Raffinate Isooctene Isobutylene Dimerization Product Recovery Hydrogen Hydrogenation Reaction Fuel Gas Isooctane Stabilizer Alcohol Recycle DIMERIZATION SECTION HYDROGENATION SECTION FIGURE 1.1.1 NExOCTANE process bution of dimers and oligomers, is controlled by recirculating alcohol from the product recovery section to the reactors Alcohol is formed in the dimerization reactors through the reaction of a small amount of water with olefin present in the feed The alcohol content in the reactor feed is typically kept at a sufficient level so that the isooctene product contains less than 10 percent oligomers The dimerization product recovery step separates the isooctene product from the unreacted fraction of the feed (C4 raffinate) and also produces a concentrated alcohol stream for recycle to the dimerization reaction The C4 raffinate is free of oxygenates and suitable for further processing in an alkylation unit or a dehydrogenation plant Isooctene produced in the dimerization section is further processed in a hydrogenation unit to produce the saturated isooctane product In addition to saturating the olefins, this unit can be designed to reduce sulfur content in the product The hydrogenation section consists of trickle-bed hydrogenation reactor(s) and a product stabilizer The purpose of the stabilizer is to remove unreacted hydrogen and lighter components in order to yield a product with a specified vapor pressure The integration of the NExOCTANE process into a refinery or butane dehydrogenation complex is similar to that of the MTBE process NExOCTANE selectively reacts isobutylene and produces a C4 raffinate which is suitable for direct processing in an alkylation or dehydrogenation unit A typical refinery integration is shown in Fig 1.1.2, and an integration into a dehydrogenation complex is shown in Fig 1.1.3 NExOCTANE PRODUCT PROPERTIES The NExOCTANE process offers excellent selectivity and yield of isooctane (2,2,4trimethylpentane) Both the isooctene and isooctane are excellent gasoline blending components Isooctene offers substantially better octane blending value than isooctane However, the olefin content of the resulting gasoline pool may be prohibitive for some refiners The characteristics of the products are dependent on the type of feedstock used Table 1.1.1 presents the product properties of isooctene and isooctane for products produced from FCC derived feeds as well as isooctane from a butane dehydrogenation feed The measured blending octane numbers for isooctene and isooctane as produced from FCC derived feedstock are presented in Table 1.1.2 The base gasoline used in this analyDownloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION 1.7 NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PROCUCTION C4 C4 Raffinate DIMERIZATION ALKYLATION FCC Isooctene Hydrogen HYDROGENATION Isooctane NExOCTANE FIGURE 1.1.2 Typical integration in refinery NExOCTANE Isooctene iC4= DEHYDRO Butane DIB DIMERIZATION HYDROGEN TREATMENT RECYCLE TREATMENT HYDROGENATION Isooctane Hydrogen C4 Raffinate ISOMERIZATION FIGURE 1.1.3 Integration in a typical dehydrogenation complex sis is similar to nonoxygenated CARB base gasoline Table 1.1.2 demonstrates the significant blending value for the unsaturated isooctene product, compared to isooctane PRODUCT YIELD An overall material balance for the process based on FCC and butane dehydrogenation derived isobutylene feedstocks is shown in Table 1.1.3 In the dehydrogenation case, an isobutylene feed content of 50 wt % has been assumed, with the remainder of the feed Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION 1.8 ALKYLATION AND POLYMERIZATION TABLE 1.1.1 NExOCTANE Product Properties FCC C4 Butane dehydrogenation Isooctane Isooctene Isooctane 0.704 99.1 96.3 97.7 1.8 0.729 101.1 85.7 93.4 1.8 0.701 100.5 98.3 99.4 1.8 Specific gravity RONC MONC (R ϩ M) / RVP, lb/in2 absolute TABLE 1.1.2 Blending Octane Number in CARB Base Gasoline (FCC Derived) Isooctene Isooctane Blending volume, % BRON BMON (R ϩ M) / BRON 10 20 100 124.0 122.0 101.1 99.1 95.1 85.7 111.0 109.0 93.4 99.1 100.1 99.1 TABLE 1.1.3 BMON 96.1 95.1 96.3 (R ϩ M) / 97.6 97.6 97.7 Sample Material Balance for NExOCTANE Unit Material balance Dimerization section: Hydrocarbon feed Isobutylene contained Isooctene product C4 raffinate Hydrogenation section: Isooctene feed Hydrogen feed Isooctane product Fuel gas product FCC C4 feed, lb/h (BPD) 137,523 30,614 30,714 107,183 (16,000) (3,500) (2,885) (12,470) 30,714 (2,885) 581 30,569 (2,973) 726 Butane dehydrogenation, lb/h (BPD) 340,000 170,000 172,890 168,710 (39,315) (19,653) (16,375) (19,510) 172,890 (16,375) 3752 175,550 (17,146) 1092 mostly consisting of isobutane For the FCC feed an isobutylene content of 22 wt % has been used In each case the C4 raffinate quality is suitable for either direct processing in a refinery alkylation unit or recycle to isomerization or dehydrogenation step in the dehydrogenation complex Note that the isooctene and isooctane product rates are dependent on the content of isobutylene in the feedstock UTILITY REQUIREMENTS The utilities required for the NExOCTANE process are summarized in Table 1.1.4 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PROCUCTION 1.9 TABLE 1.1.4 Typical Utility Requirements Utility requirements FCC C4 per BPD of product Butane dehydrogenation per BPD of product 13 0.2 0.2 6.4 0.6 0.03 Dimerization section: Steam, 1000 lb/h Cooling water, gal/min Power, kWh Hydrogenation section: Steam, 1000 lb/h Cooling water, gal/min Power, kWh 1.5 0.03 0.03 0.6 0.03 0.1 NExOCTANE TECHNOLOGY ADVANTAGES Long-Life Dimerization Catalyst The NExOCTANE process utilizes a proprietary acidic ion-exchange resin catalyst This catalyst is exclusively offered for the NExOCTANE technology Based on Fortum’s extensive catalyst trials, the expected catalyst life of this exclusive dimerization catalyst is at least double that of standard resin catalysts Low-Cost Plant Design In the dimerization process, the reaction takes place in nonproprietary fixed-bed reactors The existing MTBE reactors can typically be reused without modifications Product recovery is achieved by utilizing standard fractionation equipment The configuration of the recovery section is optimized to make maximum use of the existing MTBE product recovery equipment High Product Quality The combination of a selective ion-exchange resin catalyst and optimized conditions in the dimerization reaction results in the highest product quality Specifically, octane rating and specific gravity are better than those in product produced with alternative catalyst systems or competing technologies State-of-the-Art Hydrogenation Technology The NExOCTANE process provides a very cost-effective hydrogenation technology The trickle-bed reactor design requires low capital investment, due to a compact design plus once-through flow of hydrogen, which avoids the need for a recirculation compressor Commercially available hydrogenation catalysts are used Commercial Experience The NExOCTANE technology is in commercial operation in North America in the world’s largest isooctane production facility based on butane dehydrogenation The project includes a grassroots isooctene hydrogenation unit Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website NExOCTANE™ TECHNOLOGY FOR ISOOCTANE PRODUCTION Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.26 GAS-TO-LIQUIDS TECHNOLOGIES Global demand: Methanol 30 million TPA LNG 100 million TPA SMDS product slate 2,000 million TPA 20% 4% million TPA million TPA 0.2% 600 million SCF/day TCF over project life million TPA FIGURE 15.3.1 Market impact of NG-derived products technology offers a new way to produce middle distillates without coproduction of refinery residuals The first commercial SMDS project was approved in 1989; the plant was constructed in Bintulu, Sarawak, Malaysia (Fig 15.3.2) Production started in 1993, some 20 years after first research efforts were initiated by Shell PROCESS DESCRIPTION The basic conversions of SMDS involve partial oxidation of methane into synthesis gas and subsequent Fischer-Tropsch conversion to paraffins The theoretical thermal efficiency of this route is 78 percent on the basis of NG LHV: CH4 ϩ 1⁄2O2 → 2H2 ϩ CO 803 MJ/kmol 100% 767 MJ/kmol 96% 2H2 ϩ CO → -(CH2)- ϩ H2O 767 MJ/kmol 100% 96% 621 MJ/kmol 81% 78% The three main process stages are shown schematically in Fig 15.3.3 In the SMDS process, these stages are identified as syngas manufacture, heavy paraffin synthesis (HPS, the Fischer Tropsch synthesis), and heavy paraffin conversion (HPC) These stages will be described here Several support and utility blocks are added Syngas Manufacture (SGP, Shell Gasification Process) Synthesis gas, a mixture of hydrogen and carbon monoxide, is one of the most versatile feedstocks for a wide range of (chemical) processes In GTL technology, the conversion Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.27 SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS FIGURE 15.3.2 SMDS Bintulu, Malaysia ASU Offgas Offgas to fuel O2 NG SGP – CH2 – Syngas HPS Debutanizer (C3+) C3+ H2O HSR H2 Steam HPC + workup Middle Distillates, LPG Utilities Utilities ASU = Air Separation Unit SGP = Shell Gasification Process HSR = Hydrocarbon Steam Reforming HPS = Heavy Paraffin Synthesis (FT) HPC = Heavy Paraffin Conversion Optional: • Specialties • Power Export • Sea water Desalination FIGURE 15.3.3 Shell Middle Distillate Synthesis process scheme trajectory from methane to liquid hydrocarbons uses syngas as an intermediate Direct conversion of methane to hydrocarbon chains with economic selectivity and conversion is not (yet) possible Syngas manufacture in SMDS is relatively expensive; between 50 and 60 percent of total process capital costs are related to syngas production Within the syngas manufacturDownloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.28 GAS-TO-LIQUIDS TECHNOLOGIES ing section, it is the air separation units (ASUs) which account for a substantial part of the cost of syngas produced In developing the SMDS technology it was established that a combination of commercially proven technologies was most suitable: ● ● Partial oxidation (POX) of natural gas with pure oxygen, using the proprietary Shell Gasification Process (SGP) A hydrogen-manufacturing unit (HMU) based on hydrogen steam reforming (HSR), to adjust the syngas H2/CO ratio Pure oxygen is obtained from an air separation unit SGP is based on direct partial oxidation without the need for a catalyst (Fig 15.3.4) The feedstock, natural gas, is converted in an empty, refractory lined vessel The conversion equilibrium is advantageous due to the high temperature More than 95 percent of NG carbon is converted to CO Oxidation heat is recovered on a high temperature level as high-pressure steam The syngas effluent cooler (SEC) is a dedicated design, with several features for the operating conditions Steam superheating FIGURE 15.3.4 Shell Gasification Process (SGP): gasifier and syngas effluent cooler Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.29 can be integrated Secondary heat recovery is by a boiler feedwater economizer downstream of the SEC Part of the steam is used for preheat of feed gas and oxygen The remainder is utilized to drive compressors in the air separation unit(s) Trace components in the cooled raw syngas are removed in a water scrubber and in guard beds prior to transfer to the synthesis section Since the 1950s, SGP has been developed into a highly reliable and cost-effective process for syngas production from NG, liquid hydrocarbons, and coal The process has proved its robustness and reliability in a remote location during the years of operation of SMDS Bintulu Substantial scale-up from present unit capacities can be done to exploit economies of scale without changes to the process Scale-up of NG SGP does benefit from developments in oil and coal gasification that have been realized meanwhile For Fischer-Tropsch conversion of synthesis gas derived from natural gas, the H2/CO ratio of the gas leaving the SGP requires some adjustment SGP produces synthesis gas with an H2/CO ratio close to 1.7 By nature of the synthesis process, the consumption ratio in the synthesis step is approximately The hydrogen-manufacturing unit (HMU) provides additional hydrogen ● ● ● To adjust the H2/CO ratio of feed gas supplied to the synthesis section As a feed gas for the heavy paraffin cracking unit of the SMDS plant For desulfurization of the NG feed Based on hydrogen steam reforming, the HMU produces raw hydrogen and pure hydrogen (pressure swing unit) depending on the quality required by various consumers Alternative syngas manufacturing technologies can be considered, e.g., autothermal reforming (ATR) Studies indicate that ATR could compete with SGP HMU of SMDS at very low steam/carbon ratio and by recycling CO2 This would require development beyond the industrially proven window for ATR SGP HSR is still the preferred option for next-generation SMDS plants Heavy Paraffin Synthesis The heavy paraffin synthesis section is the heart of the SMDS process This section entails the conversion of the synthesis gas with a low-temperature cobalt-based FT catalyst to produce paraffinic hydrocarbons (and an equivalent amount of water) Low-temperature cobalt-based FT synthesis is most suitable for natural gas–derived syngas Since the FT synthesis is highly exothermic, temperature control and heat removal are major parameters in design of the reactor Moreover, the performance of the synthesis step is a key parameter for the economics of a GTL plant Newer catalysts provide a very high chain growth probability, to promote formation of long paraffinic chains and to minimize production of undesired light products (Fig 15.3.5) The ensuing hydroconversion of the long paraffinic chains provides the SMDS product slate flexibility to fit market conditions The hydrocarbon synthesis process, and performance of the FT-catalyst in particular, is crucial for commercial viability of a GTL process Traditional high-temperature FT processes have been used extensively for conversion of syngas from coal High-temperature FT processes are best suited to production of motor gasoline and other light products Obtaining high yields of middle distillates from NG-derived syngas, however, requires a far higher probability of hydrocarbon chain growth than provided by classical Fe and Co catalysts The low-temperature Co catalysts developed for SMDS are most suitable for production of long paraffinic hydrocarbon chains from NG-derived syngas with high selectivity This contributes to high overall thermal and carbon efficiency Figure 15.3.6 shows the distribution of products, obtained from NG-derived syngas, as a function of chain growth probability Yield of light fuel components is minimized at high chain growth probability Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.30 GAS-TO-LIQUIDS TECHNOLOGIES 100 Liquid Selectivity (%w) 95 90 85 80 Relative Fixed Bed Volumetric Productivity FIGURE 15.3.5 Potential of fixed-bed heavy paraffin catalyst Fixed-bed FT operating window with R&D pilot plant data % mass 100 C1-2 Fuel gas 80 C3-4 LPG 60 C5-12 Tops/Naphtha 40 C12-19 Diesel 20 C20+ Wax 0.75 0.80 0.85 Co (Classical) 0.90 0.95 Probability of chain growth Fe (Classical) NEW CATALYSTS FIGURE 15.3.6 Fischer-Tropsch product distribution Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.31 The desired middle-distillate product slates are obtained in the third stage, the selective cracking and isomerization of the heavy paraffins (wax) The combination of selective conversion of synthesis gas into heavy paraffins, followed by selective hydrocracking and isomerization into marketable products, is the key to the high thermal/carbon efficiency as well as to the product flexibility of SMDS Heavy Paraffin Synthesis Reactor Technology Various types of reactor technology can be considered for the synthesis stage, in view of the high chain growth probability of the Shell proprietary class of synthesis catalysts, identified as heavy paraffin synthesis: ● ● ● Gas-solid fluidized bed Three-phase slurry Fixed bed The Fischer-Tropsch synthesis is a highly exothermic process with an enthalpy change of Ϫ146 MJ/kmol CO and operates within a relatively narrow temperature range Heat removal, thermal stability, and temperature control are key parameters in HPS reactor design Gas-Solid Fluidized-Bed Technology For the highly exothermic and catalyst pore-diffusion-limited synthesis reaction, gas-solid fluidized-bed reactor technology seems attractive Heat-transfer coefficients are high, and mass-transfer limitations are avoided with the small catalyst particles Operational restrictions apply, however As long as hydrocarbon product resides within the catalyst pores due to capillary condensation, the particles will behave as dry ones Once hydrocarbon components start to condense on the external surface of the catalyst particles— a condition characterized by the hydrocarbon dew point—particle agglomeration and poor fluidization will occur The window for troublefree operation of a fluid-bed FT reactor is governed by the (Andersen-Flory-Schulz) chain growth probability ␣, by syngas conversion, by operating pressure, by operating temperature, and by paraffin vaporization energy depending on chain length Fluid-bed FT is possible at high temperatures, low operating pressure, and low conversions and will produce relatively light products This is confirmed by the operating conditions of the Sasol Synthol reactors and of the Hydrocol plant by Hydrocarbon Research Inc., which was operated in the 1950s For production of heavy wax, a stationary, nonregenerative fluid-bed FT reactor is not suitable The heavy paraffin synthesis aims at producing long, heavy hydrocarbon chains at high selectivity and conversion levels Thermodynamics dictate that this benefits from low operating temperature and high operating pressure Hence, gas-solid catalyst fluidized-bed technology has not been considered for SMDS Slurry Technology Slurry technology relies on small catalyst particles, suspended in liquid product hydrocarbons The synthesis gas is bubbled through the hydrocarbon/catalyst slurry The catalyst particles are small to enable suspension in the liquid product fraction With the small catalyst particle size (range of 10 to 200 m) there is no mass transport limitation within the catalyst particles Long-chain, heavier hydrocarbons will reside in the Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.32 GAS-TO-LIQUIDS TECHNOLOGIES liquid phase whereas the lighter products will leave the reactor with the vapor phase Temperature control and heat removal from the reactor, most conveniently by immersed cooling tubes carrying boiling water, are in principle favorable in comparison to fixed-bed technology Process side pressure drop is low Large unit capacities can be realized Several companies have selected and developed slurry reactor technology for FT synthesis in GTL Slurry FT synthesis involves several distinct engineering challenges The design of large slurry reactors involves three-phase hydrodynamics on a large scale Too high a catalyst holdup in the liquid phase, in particular with very small particles, increases the apparent slurry viscosity This affects the favorable mixing, heat removal, gas dispersion, and mass-transfer properties of the three-phase system Dedicated filtration systems must be installed for separation of liquid product from the catalysts/wax mixture and from the overhead vapor/offgas, after cooling and condensation Slurry catalyst must be mechanically robust to avoid catalyst breakage and fines formation, which might cause losses and product contamination Fixed Bed The SMDS synthesis section (HPS) uses fixed-bed reactor technology (Fig 15.3.7) The syngas passes through multiple tubes containing the FT catalyst Reaction heat is removed by boiling water in the reactor shell to produce medium-pressure (MP) steam This MP steam is the main utility to generate electricity and to drive compressors Multitubular reactor technology has matured to a high degree of sophistication with a productivity potential of 10,000 to 15,000 bbl/day per reactor Today’s Shell proprietary fixed-bed FT catalysts provide activity, selectivity, and stability for a unit capacity range of 7000 to 10,000 BPD HPS syngas conversion can be as high as 96 percent with liquid (C5ϩ) selectivity better than 90 percent (Fig 15.3.5) The catalyst is loaded into a large number of tubes Specific heat-transfer surface is high FT fixed-bed reactors are heavier than fluid-bed/slurry reactors for the same unit capacity Multitubular reactor (MTR) technology has a number of attractive features compared to two- or three-phase fluidized-bed reactors: ● ● ● ● ● The design of a commercial MTR is straightforward by multiplication of the performance of an individual tube, which can be assessed accurately in a pilot plant Fixed-bed catalyst provides intrinsic and absolute separation of the products, with zero contamination by catalyst This is important with several of the products or derivatives having FDA approval By nature of the MTR design, axial catalyst distribution is uniform irrespective of operating conditions In situ catalyst (re-) activation, which is done typically once per year, is easy and effective Conditions are independent of normal operating conditions and are fully controlled A multitubular reactor arrives at the construction site as a fully integrated unit ready for erection and tie-in This is an advantage for a remote location Auxiliaries are the thermosyphon cooling system and a shared gas loop utility for catalyst (re-) activation The pressure drop over a fixed-bed reactor, operated at a high performance level, is high in comparison to two- or three-phase fluidized systems Since the FT synthesis provides ample steam to provide compressor shaft power, this aspect has little effect on capital expenditure or operating costs Selection of fixed-bed FT catalyst size and shape is a balancing act Heat removal and control of temperature gradients in the fixed bed rely on the effective heat conductivity of the packed catalyst particles, which benefits from high gas velocities and larger particles Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.33 FIGURE 15.3.7 Fixed-bed multitubular (FT) reactors of SMDS Bintulu, Malaysia Larger particles also reduce pressure drop In high-performance FT catalyst particles a few millimeters in size, intraparticle diffusion limitations will prevail Catalyst utilization imposes an upper limit to particle size Hence, catalyst size, shape, and reactor tube diameter are carefully optimized with regard to reaction kinetics, heat transfer, pressure drop, catalyst, and hardware costs Bintulu SMDS experience has confirmed the easy operation of fixed-bed MTRs, including start-up, shutdown, and other transient operating modes Restart of Bintulu FT reactors, after a long standstill, also appeared straightforward: heat up to melt the solidified wax, start up according to standard procedure, and there is no need for inspection or reactivation Loading of catalyst is foreseen for every multitubular HPS reactor typically every years Experience with the efficiency of automated loading, including preparation and check procedures, is impressive and has turned this into a routine activity With further development of SMDS technology, and high-performance FT catalysts being available, it was established that fixed-bed technology remains attractive in comparison Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.34 GAS-TO-LIQUIDS TECHNOLOGIES to alternative reactor technology for a GTL plant on a remote location The upward potential of MTR technology will be further utilized with new generations of catalyst becoming available Heavy Paraffin Cracking Fischer-Tropsch synthesis alone cannot produce high yields of paraffins of specified carbon number, with adequate cold flow properties SMDS consists of separate steps: selective production of heavy paraffins (HPS) with subsequent selective cracking and isomerization (HPC) into the desired middle distillates In the third stage of the SMDS process, the raw synthesized hydrocarbons consisting mainly of high-molecular-weight paraffins are hydrocracked A dedicated hydrocracking process using a proprietary catalyst under relatively mild conditions, typically 30- to 50-bar total pressure and at a temperature of about 300 to 350°C, has been developed to achieve this The layout of the HPC section is very similar to that of a conventional gas oil hydrotreater The output is subsequently fractionated HPC removes any oxygenated components; long paraffin chains are broken and isomerized to produce middle distillates The HPC stage has four functions: ● ● ● ● Preferential hydrocracking of heavy paraffins into fragments in a specified length/boiling range Sufficient hydroisomerization of the resulting cracked components to meet cold flow specifications Hydrogenation of olefins in the HPS product Removal of small amounts of oxygenates, mainly primary alcohols The example of Fig 15.3.8 shows that very little methane and ethane are formed, and propane is at a very low level The small fraction of light hydrocarbons is rerouted as feedstock and fuel for the hydrogen-manufacturing unit The middle-distillate yield is better than 85 percent Products with an intermediate carbon number are formed in significant quantities; the boundaries of the distribution are remarkably sharp The distribution of Fig 15.3.8 is 14 12 mol % 10 2 Carbon number 10 11 12 13 14 15 FIGURE 15.3.8 Selectivity of heavy paraffin cracking Molar product distribution after hydrocracking an FT fraction (88% n-C16, 12% n-C17) over a bifunctional acid/metal catalyst Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.35 indicative for primary cracking; scission of internally located C-C bonds of the paraffin chains is favored above terminal (␣) or near-terminal (ß, ␥) positions Another factor contributing to preferential cracking of the heavy paraffin chains is the vaporization of the lighter hydrocarbons, reducing residence time and the probability of further cracking Varying the hydrocracking severity provides SMDS product slate flexibility, to vary the distribution over gas oil, kerosene, and naphtha, as shown in Figs 15.3.9 and Fig 15.3.10; 60 to 75 percent gas oil yield can be achieved Selectivity toward the desired product range can be achieved by HPC severity The HPC effluent is separated by conventional distillation In the kerosene mode, kerosene yield is some 50 percent of total liquid product whereas a gas oil mode yields some 60 percent gas oil The theoretical maximum thermal efficiency of the basic SMDS scheme CH4 ϩ 1⁄2O2 → 2H2 ϩ CO → -(CH2)- ϩ H2O is 78 percent based on LHV The thermal efficiency of SMDS, which can be actually achieved, is typically 63 percent, that is, 80 percent of the Kerosene 25% Gas oil 60% Tops/naphtha 15% FIGURE 15.3.9 Product distribution in gas oil mode Gas oil 25% Kerosene 50% Tops/naphtha 25% FIGURE 15.3.10 Product distribution in kerosene mode Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.36 GAS-TO-LIQUIDS TECHNOLOGIES thermodynamic maximum The carbon efficiency is 78 to 82 percent Considering the number of process steps and trims, this is a remarkable achievement It should be realized that the efficiency number is affected by the quality of the feed gas, by the environmental conditions, as well as by investment optimization considerations Thermal efficiency will be raised further with new generations of HPS and HPC catalyst becoming available, which offer better activity and selectivity of synthesis, and by more favorable operating conditions QUALITY OF THE PRODUCTS By their nature, products synthesized from carbon monoxide and hydrogen are extremely clean They contain no sulfur, no nitrogen, and no aromatics The SMDS products have impurities that are several orders of magnitude lower than highly refined crude oil–derived products The highly paraffinic nature of SMDS products makes them stand apart from crude oil–derived distillates in terms of density, combustion characteristics, and chemical composition Although the first SMDS plant at Bintulu, Malaysia, produces several hydrocarbon products, an interesting and profitable group of products is the FDA-approved, food-grade waxes The waxes are ultimately used in chewing gum, cosmetics, medicines, cup coatings, and a host of other products Prices obtained for these products are high and contribute substantially to plant economics Here, we focus on the middle-distillate fuel qualities (Table 15.3.1) Naphtha The naphtha fraction is completely paraffinic and therefore makes an excellent ethylene cracker feedstock, giving a higher yield of ethylene and propylene in comparison to petroleum-derived naphtha feedstock Kerosene SMDS kerosene is a clean-burning fuel for domestic heating It can also be used to upgrade kerosene fractions that have a low smoke point and high aromatics It may offer possibilities as a jet fuel component However, it has not yet been approved TABLE 15.3.1 Property Density @ 15°C Saybolt color Distillation range IBP FBP Sulfur Cetane index Smoke point Flash point Aromatics Typical Middle Distillate Properties Unit Naphtha Kerosene Method kg/m 690 ϩ29 738 ϩ30 ASTM D1298 ASTM D156 ASTM D86 °C °C ppm 43 166 Ͻ3 n/a n/a n/a 155 191 Ͻ10 58 Ͼ50 42 Ͻ0.1 mm °C %v ASTM D1266 ASTM D976 ASTM D1322 ASTM D93 ASTM D5186 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.37 SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS Moreover there are attractive solvent/chemical applications for SMDS kerosene It can be tailored to a solvent of high purity, which together with its low odor and water-clear appearance makes it particularly attractive in applications such as dry cleaning and other “speciality solvent” applications SMDS kerosene is also suitable as a trimming agent for heavy gas oils that need to be upgraded to specification diesel, for example, winter diesel for automotive use in cold climates SMDS Diesel/Gas Oil The GTL product with the brightest future seems diesel for use as transportation fuel SMDS produces an exceptional quality of synthetic fuel that can be used directly (after including a lubricity additive) in diesel engines or as a blendstock to upgrade refinery diesel Independent studies with SMDS gas oil have shown the significant reduction in emissions (NOx, SOx, HC, CO, and particulates) SMDS diesel has a cetane index (CI) of 76, no detectable sulfur even on the ppm level It is virtually paraffinic (with a high proportion of straight-chain paraffins) and contains almost no aromatic, cycloparaffinic, or polar species The SMDS diesel responds well to commercial lubricity additives, allowing it to meet the given lubricity specification Compatibility of the fuel with elastomeric seals in fuel injection equipment (FIE) may need some consideration Table 15.3.2 details the properties of SMDS and comparable automotive gas oil (AGO) samples, i.e., an EU reference CEN (Comité Européen de Normalisation) fuel (typical 1998 quality) and a Swedish Class I (a very low sulfur content fuel) The forthcoming EU specifications for diesel fuel, which require a maximum sulfur content of 50 ppm mass, could ideally use SMDS gas oil as a blending component Alternatively the products could well on a market where premium specifications are desired to meet local requirements, for example, the California Air Resources Board (CARB) specifications, a maximum of TABLE 15.3.2 Typical SMDS and AGO Sample Analyses Property CEN (1998 quality) Density* @ 15°C kg/m Distillation, °C† IBP 10% 50% 90% FBP Cetane number Cetane index‡ Viscosity @ 40°C Cst§ Sulfur, %m Aromatics, %m¶ Mono Di Tri Total Swedish Class I SMDS 837 814 776 201 219 269 326 368 50 52.2 2.823 0.05 197 213 231 269 293 58 50.4 1.903 0.001 184 — 275 340 357 81 76 2.702 Ͻ0.0002 25 2.1 1.2 28 9.7 0.1 Ͻ0.05 10 Ͻ0.05 Ͻ0.05 Ͻ0.05 Ͻ0.05 *IP160/ASTM D1298 †IP123/ASTM D86 ‡IP380/94 §IP71/ASTM D445 ¶HPLC, IP391 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.38 GAS-TO-LIQUIDS TECHNOLOGIES 500 ppm sulfur and maximum 10 vol % aromatics SMDS gas oil with zero aromatics, zero sulphur, and cetane index of 76 can be used in blends to meet these severe CARB regulations Since 1995, SMDS diesel has been sold to refiners and blenders who used it to upgrade its mineral diesel to CARB specification to Californian market Another attractive characteristic of SMDS gas oil is that the material is fully biodegradable For certain applications this is of prime importance (e.g., where spills into environment could occur); this feature is expected to gain momentum in the near future COMPLEX INTEGRATION GTL involves large energy streams Partial oxidation of NG (SGP) and Fischer-Tropsch synthesis are highly exothermic processes Plant utilities are integrated such that all requirements, including these of the air separation units, are generated from the complex energy streams Produced steam is utilized for direct or indirect drive (via electricity generation) of compressors, including those needed for air separation Light hydrocarbons are recycled for utility generation or as fuel for hydrogen manufacturing If commercially attractive outlets are available, export of nitrogen, steam, and/or electricity is an option as shifting the internal balance of the SMDS complex could produce these WASTES AND EMISSIONS The SMDS system offers major gains in air quality compared to the refinery system, thanks to its significantly lower emissions of hydrocarbons, nitrogen oxides, sulfur oxides, and waste Nor these gains in air quality result in a greenhouse gas penalty, since its carbon emissions are in the same range as those of a conventional refinery system Process water and condensate can be reused in the plant Most of the oxygen feed to the plant ends as water Note that the Fischer-Tropsch synthesis alone produces some 1.3 tons of water per ton of hydrocarbons Wastewater is biotreated to the extent that it can be discharged as surface water In areas of water scarcity, production of clean water is an option Light hydrocarbon gaseous by-products, which are produced in small quantities by different process units, are recycled or used for utility generation Flue gases emitted to air are almost free from sulfur, meeting most stringent specifications worldwide Catalysts used in several process units (synthesis, cracking, hydrogen manufacture) have a lifetime of several years Spent catalyst, the only solid waste of the process, is returned to the manufacturer for metals recovery FUTURE PROSPECTS The economic viability of gas-to-liquids projects today and in the near future depends on several key economic factors: the availability of low-cost gas, crude prices, capital and operating costs, site-specific factors, and the fiscal regime of the host country Low-cost gas as well as fiscal friendly regimes are of the utmost importance to make a gas-to-liquids project viable If natural gas is priced at 0.50 U.S $/millionBtu, then the feedstock cost element in the product is about U.S.$5/bbl The total selling price further includes a capital charge which depends on numerous factors, including fiscal regimes, local incentives, debt/equity ratio, type of loans, and corporate return requirements Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.39 SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS Another important factor is whether the products are for domestic use or export For countries with sufficient gas but needing to import oil or oil products to meet local demand, SMDS products manufactured in that country should realize at least import parity values For such countries, therefore, the national benefit of the SMDS process can be substantial In addition to these factors, the capacity of the plant is of great importance Especially for remote locations, where self-sufficiency of the plant is essential, larger plants in the range of 75,000 bbl/day benefit from the economy of scale SMDS (Malaysia) Sdn Bhd has demonstrated the commercial viability of the SMDS process Further developments have reduced the specific capital cost, such as ● ● ● Equipment scale-up, notably in the synthesis gas manufacturing plant, which accounts for more than 50 percent of the total process capital cost Further catalyst improvements A second-generation catalyst, which yields significantly more liquids than the catalyst originally implemented in Bintulu, has been developed and is ready for application in the next plant General process integration within the project Operational experience, coupled with technological improvements, has resulted in specific capital costs of around U.S $20,000/bbl, as shown in Fig 15.3.11 The successful application of GTL technology at SMDS Bintulu represents an important advance in the commercialization of that technology and is an asset in Shell’s portfolio of technologies for making natural gas transportable It provides exciting opportunities in terms of marketing hydrocarbon products of a quality ideally suited for a business environment requiring increasingly high-performance standards REFERENCES S T Sie, M M G Senden, and H M W van Wechem, “Conversion of Natural Gas to Transportation Fuels via the Shell Middle Distillate Process (SMDS),” Catalysis Today, 8: 371–394, 1991 Unit capital expense, U.S $ thousand/BPD 50 Bintulu Economy of scale 35 Second generation 20 Year 1987 1996 2000 FIGURE 15.3.11 Reduction of specific costs of SMDS Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website SHELL MIDDLE DISTILLATE SYNTHESIS (SMDS) PROCESS 15.40 GAS-TO-LIQUIDS TECHNOLOGIES M M G Senden, S T Sie, M F M Post, and J Ansorge, “Engineering Aspects of the Conversion of Natural Gas into Middle Distillates,” Paper presented at NATO Advanced Study Institute Conference at University of West Ontario, Canada, Aug 25–Sept 4, 1991 R H Clark and J F Unsworth, “The Performance of Diesel Fuel Manufactured by the Shell Middle Distillate Synthesis Process,” Proceedings of Second Int Colloquium “Fuels,” Tech Akad Esslingen, Ostfildern, Germany, Jan 20–21, 1999 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website [...]... out the operation of existing polymerization plants The importance of the HF Alkylation process in the refining situation of the 2000s has been increased even further by the scheduled phase-out of MTBE and the increased *Trademark and/or service mark of UOP 1.33 Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All... Controlling Olegin Ratios Patent 6,194,625, issued 2/01 Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website Source: HANDBOOK OF PETROLEUM REFINING PROCESSES CHAPTER 1.3 UOP ALKYLENE™ PROCESS FOR MOTOR FUEL ALKYLATION Cara Roeseler UOP LLC Des... Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website UOP ALKYLENE™ PROCESS FOR MOTOR FUEL ALKYLATION Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved... operation of reaction zones in autorefrigerated reactors Reliability One of the primary factors affecting the reliability of an alkylation unit is the number and type of mechanical seals required in the reaction zone Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of. .. of the alkylate, a large portion of the n-butane and isopentane must be removed Low C5ϩ content of the n-butane product is difficult to meet with a vapor side draw on the DIB and Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website STRATCO... to that of the product obtained from liquid acid technologies ALKYLENE PROCESS Olefins react with isobutane on the surface of the HAL-100 catalyst to form a complex mixture of isoalkanes called alkylate The major constituents of alkylate are highly branched trimethylpentanes (TMP) that have high-octane blend values of approximately 1.25 Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com)... of various molecular weights These fragments can then undergo further alkylation Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website UOP HF ALKYLATION TECHNOLOGY 1.36 ALKYLATION AND POLYMERATION TABLE 1.4.1 Feedstocks Compositions of. .. Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website STRATCO EFFLUENT REFRIGERATED H2SO4 ALKYLATION PROCESS STRATCO EFFLUENT REFRIGERATED H2SO4 ALKYLATION PROCESS 1.21 nology can improve product quality compared to alkylation of the same olefins mixed together... effluent stream in the feed/effluent exchangers FIGURE 1.2.1 Block flow diagram of STRATCO Inc effluent refrigerated alkylation process Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website STRATCO EFFLUENT REFRIGERATED H2SO4 ALKYLATION... catalyst are maintained in the liquid phase The hydrocarbon effluent flows from the top of the acid settler to the tube bundle in the Downloaded from Digital Engineering Library @ McGraw- Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw- Hill Companies All rights reserved Any use is subject to the Terms of Use as given at the website STRATCO EFFLUENT REFRIGERATED H2SO4 ALKYLATION PROCESS