Pressure swing adsorption-rapid cycle www. Shell Global Solutions has approximately 5, staff located in an extensive network of offices around the world, with primary commercial and technical centres operating in the USA, Europe and Asia Pacific. Outside of the Shell Group, the company successfully services refining, chemicals, gas, metals, pulp and paper and motor-sport customers worldwide.
Since then, UOP engineers have generated thousands of patents, leading to a complete portfolio of licensed processes, catalysts, molecular sieve adsorbents and key mechanical equipment that support the quality, efficiency and profitability needs of customers around the globe.
These products are backed by a broad array of engineering and technical services that facilitate successful installation and operations. For more information, visit UOP online at www. Deasphalting - KBR www.
Olefins-butenes extractive distillation - Uhde GmbH Olefins-dehydrogenation of light paraffins to olefins - Uhde GmbH Refinery offgas-purification and olefins recovery - Shaw www. SO2 removal, regenerative - Belco Technologies Corp. Dewaxing - Bechtel Corp. White oil and wax hydrotreating - Uhde GmbH www. By using isobutylene as the sole olefin source, the CDAlkyPlus technology allows for the profitable conversion of isobutylene and isobutane into high-value motor fuel alkylate.
This combination provides significant benefits over direct alkylation of isobutylene as well as other isobutylene upgrading processes such is isooctene production.
Because isobutane and isobutylene are incorporated together to produce a high-value alkylate product, the CDAlkyPlus process produces two times the volume of gasoline blendstock compared with isooctene production. This process is ideal for use downstream of an isobutane dehydrogentation process. This technology also provides a unique opportunity for revamping an existing dehydrogenation unit-based methyl tertiary butyl ether MTBE plant to produce alkylate. For these retrofit cases, the isobutane recycle around the dehydrogenation unit is essentially eliminated.
This means the nbutane capacity of the complex can be doubled without expanding the existing dehydrogenation unit. Propane product 5 6 Products: Branched chain hydrocarbons for use in high-octane motor 2 3 1 n-Butane product 4 fuel and aviation gasoline.
Description: Plants are designed to process a mixture of propylene, butylenes and amylenes. The liquid contents of the Contactor reactor are circulated at high velocities and an extremely large amount of interfacial area is exposed between the reacting hydrocarbons and the acid catalyst from the acid settler 2. Contactor reactor products pass through a flash drum 3 and deisobutanizer 4. The refrigeration section consists of a compressor 5 and depropanizer 6. The overhead from the deisobutanizer 4 and effluent refrigerant recycle 6 constitutes the total isobutane recycle to the reaction zone.
This total quantity of isobutane and all other hydrocarbons is maintained in the liquid phase throughout the Contactor reactor, thereby serving to promote the alkylation reaction. Onsite acid regeneration technology is also available. When processing straight butylenes, the debutanized total alkylate has RON as high as 98 clear.
Reference: Hydrocarbon Processing, Vol. Licensor: DuPont. The AlkyClean process uses a true solid acid catalyst to produce alkylate, eliminating the safety and environmental hazards associated with liquid acid technologies. Simultaneously, reactors are undergoing a mild liquid-phase regeneration using isobutane and hydrogen and, periodically, a reactor undergoes a higher temperature vapor phase hydrogen strip 2. The reactor and mild regeneration effluent is sent to the product-fractionation section, which produces n-butane and alkylate products, while also recycling isobutane and recovering hydrogen used in regeneration for reuse in other refinery hydroprocessing units 3.
The AlkyClean process does not produce any acid soluble oils ASO or require post treatment of the reactor effluent or final products. Gieseman, E. This eductor mixing device is more cost-effective than other devices being used or proposed.
It is maintenance free and does not require replacement every two to three years. This mixing device can be a retrofit replacement for existing contactors.
In addition, the auto refrigeration vapor can be condensed by enhancing pressure and then easily absorbed in hydrocarbon liquid, without revamping the compressor. The mixture is pumped to the reactor 1 to the eductor suction port. The motive fluid is sent to the eductor nozzle from the bottom of reactor, which is essentially sulfuric acid, through pumps to mix the reactants with the sulfuric-acid catalyst.
The mixing is vigorous to move the reaction to completion. The makeup acid and acid-soluble oil ASO is removed from the pump discharge. The process has provisions to install a static mixer at the pump discharge. Some feed can be injected here to provide higher OSV, which is required for C3 alkylation.
The coalescers are being used by conventional process to reduce the acid in the hydrocarbon phase to 7—15 wppm. After the coalescer, the hydrocarbon phase is heated and flashed increasing the alkylate concentration in the hydrocarbon, which is sent through the finishing coalescer 4 where essentially all of the remaining acid is removed. The butane is sent to offsites or can be converted back to isobutane for processing units requirements.
The isothermal condition lowers acid consumption and yields higher octane product due to improved selectivity of 2,4,4 trimethylpentane. Some liquid is sent to depropanizer 6 ; propane and light ends are removed. The bottoms are recycled to C4 system and sent to the reactor. The major advances of RHT process are threefold: eductor mixing device, advance coalescer system to remove acid from hydrocarbon dry system , and C4 autorefrigeration vapors recovery by absorption, making compressor redundant.
References: US patent 5, US Patent 4, Kranz, K. Branzaru, J. Nelson, Handbook of Refining. Meyers, R. Description: The additive stripper sends acid, water and light-acid soluble oils overhead and on to the acid regenerator. Heavy acid soluble oils and the concentrated HF-additive complex are sent to the additive stripper bottoms separator.
From this separator the polymer is sent to neutralization, and the HF-additive complex is recycled to the reactor section. The acid regenerator removes water and light-acid soluble oils from the additive stripper overhead stream.
There is no expected increase in the need for operator manpower. Maintenance requirements are similar to equipment currently in standard operation in an HF alkylation unit in similar service.
Three are in operation. Licensor: UOP. Description: The InAlk process makes premium alkylate using a combination of commercially proven technologies. The resulting mixture of higher molecular weight iso-olefins may then be hydrogenated to form a high-octane paraffinic gasoline blendstock that is similar to alkylate, but usually higher in octane, or it may be left as an olefinic high-octane gasoline blending component. Either resin or solid phosphoric acid SPA catalysts are used to polymerize the olefins.
Resin catalyst primarily converts iso-butene. SPA catalyst also converts n-butenes. The saturation section uses either a base-metal or noble-metal catalyst.
Typical feeds include FCC-derived light olefins, steam-cracker olefins and iC4 dehydrogenation olefins. UOP has licensed and designed more than catalytic condensation units for the production of polygasoline and petrochemical olefins and more than hydrogenation units of various types. Currently, 10 InAlk units are in operation. Description: The CDAlky low-temperature sulfuric acid alkylation technology reacts light olefin streams from refinery sources such as fluid catalytic cracking units or from steam-cracking units with isoparaffins to produce motor fuel alkylate.
The CDAlky process is available for license to the petroleum refining and petrochemical industries. The process flow diagram shows the basic configuration to process a mixed-C4 olefin feed and produce a high-octane motor fuel alkylate, without the need for a reactor effluent alkaline water wash.
The CDAlky process yields a higher quality product while consuming significantly less acid than conventional sulfuric acid-based technologies. The flow scheme is also less complex than conventional designs, which reduces capital and operating costs. Conventional sulfuric acid alkylation units use mechanical mixing in their contactors, which are characterized by their high acid consumption.
In addition, they are unable to take full benefit of operating at very low temperature, which substantially improves alkylate quality and reduces acid consumption. This scalable, vertical reactor also reduces capital costs and plot space requirements.
This process has also eliminated the need for reactor effluent alkaline water wash, thus reducing caustic waste. In addition, this dry fractionation section reduces the potential for downstream corrosion and thereby reducing overall maintenance costs.
Technology can be installed rassroots or retrofit into existing alkylation facilities. Refrigerant Products: A low-sulfur, low-Rvp, highly isoparaffinic, high-octane especially MON gasoline blendstock is produced from this alkylation process.
Description: Olefin feed and recycled isobutane are introduced into the stirred, autorefrigerated reactor 1. Mixers provide intimate contact between the reactants and acid catalyst. Highly efficient autorefrigeration removes heat of reaction heat from the reactor. Hydrocarbons, vaporized from the reactor to provide cooling, are compressed 2 and returned to the reactor. A depropanizer 3 , which is fed by a slipstream from the refrigeration section, is designed to remove any propane introduced to the plant with the feeds.
Hydrocarbon products are separated from the acid in the settler containing proprietary internals 4. In the deisobutanizer 5 , isobutane is recovered and recycled along with makeup isobutane to the reactor. Butane is removed from alkylate in the debutanizer 6 to produce a low-Rvp, high-octane alkylate product.
A small acid stream containing acid soluble oil byproducts is removed from the unit and is either regenerated on site or sent to an off-site sulfuric acid regeneration facility to recover acid strength.
Yields: Alkylate yield 1. Unit capacities currently range from 2, bpsd to 30, bpsd. Another licensed unit is in the design phase with a capacity of 16, bpsd. Economic advantages: Better economy of scale—Reactor system is simple and easily expandable with 10, bpsd single train capacities easily achievable Reference: Lerner, H.
Meyers, Ed. Alkylation takes place in the presence of HF catalyst under conditions selected to maximize alkylate yield and quality. UOP offers two configurations. Both ensure efficient contacting and mixing of hydrocarbon feed with the acid catalyst. Our gravity flow design provides good mixing without the need for a catalyst circulation pump. The forced circulation design reduces acid inventory and reaction vessel elevations.
Acid regeneration occurs in the acid regenerator or via a patented internal-acid-regeneration method. Internal regeneration allows the refiner to shutdown the acid regenerator, thereby realizing a utility savings as well as reducing acid consumption and eliminating polymer disposal. Feed: Alkylation feedstocks are typically treated to remove sulfur and water. Selective hydrogenation of butylene feedstock is recommended to reduce acid regeneration requirements, catalyst acid consumption and increase alkylate octane by isomerizing 1-butene to 2-butene.
Saturate feed Olefin feed Recycle i-C4 n-C4 product Forced circulation design Propane product Alkylate Efficiency: HF Alkylation remains the most economically viable method for the production of alkylate. And unlike sulfuric alkylation units, HF Alkylation does not require refrigeration equipment to maintain a low reactor temperature. Installations: Since , UOP has licensed alkylation units. The feedstocks can be either pygas C8 or reformer C8 streams.
The technology features a proprietary catalyst with high activity, low ring loss and superior long catalyst cycle length. This technology is partnered with Toray Industries, Inc. Offgas Light ends Reactor Description: The technology encompasses two main processing areas: reactor section and product distillation section. In this process, C8 aromatics feed stream is first mixed with hydrogen.
The mixed stream is then heated against reactor effluent and sent through a process furnace. The heated mixture is fed into the DX reaction unit, where EB is de-alkylated at very high conversion and xylenes are isomerized to equilibrium.
The reactor effluent is cooled and flows to the separator, where the hydrogen-rich vapor phase is separated from the liquid stream. A small portion of the vapor phase is purged to control the recycle hydrogen purity. The recycle hydrogen is then compressed, mixed with makeup hydrogen and returned to the reactor. The liquid stream from the separator is pumped to the deheptanizer to remove light hydrocarbons. The liquid stream from the deheptanizer overhead contains benzene and toluene and is sent to distillation section to produce high-purity benzene and toluene products.
This liquid stream is sent to the PX recovery section. Licensor: GTC Technology. The technology features a proprietary catalyst with high activity and selectivity toward paraxylene. Fuel gas H2 Separator Description: The technology encompasses three main processing areas: reactor section, product distillation and paraxylene PX recovery.
Fresh toluene and recycled toluene from the product distillation area are mixed with hydrogen. The hydrogen-to-toluene ratio is about 1 to 1.
The mixed stream is heated against reactor effluent and through a process furnace. The heated vapor stream flows to the reactor, which produces the benzene and xylenes. The toluene disproportionation reactions are mildly exothermic.
A small portion of the vapor phase is purged to control recycle hydrogen purity. The liquid stream from the separator is pumped to the stripper to remove light hydrocarbons. The technology features a proprietary catalyst and can accommodate varying ratios of feedstock while maintaining high activity and selectivity.
Process description: The technology encompasses three main processing areas: splitter, reactor and stabilizer sections. The splitter bottoms are exchanged with other streams for heat recovery before leaving the system. The aromatic product is mixed with toluene and hydrogen, vaporized and fed to the reactor. The reactor gaseous product is primarily unreacted hydrogen, which is recycled to the reactor. The liquid product stream is subsequently stabilized to remove light components.
The resulting aromatics are routed to product fractionation to produce the final benzene and xylene products. The reactor is charged with zeolite catalyst, which exhibits both long life and good flexibility to feed stream variations including substantial C10 aromatics. Installation: Two commercial licenses. The vapor pressure of the aromatics is lowered more than that of the less soluble nonaromatics. Bottom product of the ED column is fed to the stripper to separate pure aromatics from the solvent.
After intensive heat exchange, the lean solvent is recycled to the ED column. NFM perfectly satisfies the necessary solvent properties needed for this process including high selectivity, thermal stability and a suitable boiling point. It represents a superior process option in terms of investment and operating cost. The first single-column Morphylane unit went onstream in References: Diehl, T. Kolbe and H. Ranke and H. Licensor: Uhde GmbH. With lower capital and operating costs, simplicity of operation, and range of feedstock and solvent performance, extractive distillation is superior to conventional liquid-liquid extraction processes.
Flexibility of design allows use for grassroots aromatics recovery units, debottlenecking or expansion of conventional extraction systems. Raffinate Lean solvent Extractive distillation column EDC Hydrocarbon feed Solvent recovery column Aromatics to downstream fractionation Description: Hydrocarbon feed is preheated with hot circulating solvent and fed at a midpoint into the extractive distillation column EDC.
The nonaromatic hydrocarbons exit the top of the column and pass through a condenser. A portion of the overhead stream is returned to the top of the column as reflux to wash out any entrained solvent. The balance of the overhead stream is raffinate product and does not require further treatment. Rich solvent from the bottom of the EDC is routed to the solventrecovery column SRC , where the aromatics are stripped overhead.
Stripping steam from a closed-loop water circuit facilitates hydrocarbon stripping. The SRC is operated under a vacuum to reduce the boiling point at the base of the column. A small portion of the lean circulating solvent is processed in a solvent regeneration step to remove heavy decomposition products.
The SRC overhead mixed aromatics product is routed to the purification section, where it is fractionated to produce chemical-grade benzene, toluene and xylenes. Benzene saturation is applied when the logistics of benzene recovery and production are unfavorable, or where the economy of scale for benzene production is not sufficient. Description: GT-BenZap process features a reliable traditional design paired with a proven nickel-based catalyst.
The process consists of hydrotreating a narrow-cut C6 fraction, which is separated from the full-range reformate to saturate the benzene component into cyclohexane. The C6 olefins present in the C6 cut are also hydrogenated to paraffins, while the C5— olefins removed at the top of the splitter are not, thus preserving the octane number.
The hydrogenated C6 fraction from the reactor outlet is sent to a stabilizer column where the remaining hydrogen and lights are removed overhead. The C5— cut, produced from the splitter overhead, is recombined with the hydrogenated C6 cut within the GT-BenZap process in a unique manner that reduces energy consumption and capital equipment cost.
GTC also offers a modular construction option and the possibility to reuse existing equipment. Installation: Technology available for license. The process can be applied in a singlestage for concentrated PX feedstock or in two stages for equilibrium xylenes feed.
The technology has fewer pieces of equipment, simplified flow schemes and a more reliable operation compared to traditional crystallization methods. The technology uses an optimized arrangement of equipment to obtain the required recovery and product purity. Washing the PX crystal with the final product in a high efficiency pusher-centrifuge system produces the PX product. When PX content in the feed is enriched above equilibrium, such as streams originating from selective toluene conversion processes, the proprietary crystallization process technology is even more economical to produce high-purity PX product at high recoveries.
The process technology takes advantage of recent advances in crystallization techniques and improvements in equipment to create this cost-effective method for paraxylene recovery and purification. The design uses only crystallizers and centrifuges in the primary operation.
This simplicity of equipment promotes low maintenance costs, easy incremental expansions and controlled flexibility. High-purity PX is produced in the front section of the process at warm temperatures, taking advantage of the high concentration of PX already in the feed. At the back end of the process, high PX recovery is obtained by operating the crystallizers at colder temperatures.
This scheme minimizes recycling excessive amounts of filtrate, thus reducing total energy requirements. The produced styrene is high purity and suitable for polymerization at a very attractive cost compared to conventional styrene production routes.
If desired, the mixed xylenes can also be extracted from the pygas, upgrading their value as a chemical feedstock. The process is economically attractive for pygas feeds containing more than 15, tpy styrene. The resulting styrene concentrate is fed to an ED column and mixed with a selective solvent, which extracts the styrene to the tower bottoms. The rich solvent mixture is routed to a solvent recovery column SRC , which recycles the lean solvent back to the ED column and recovers the styrene overhead.
A final purification step produces a The ED column overhead can be further processed to recover a highquality mixed-xylene stream. A typical world-scale cracker can produce approximately 25, tpy styrene and 75, tpy mixed xylenes from pyrolysis gasoline. Both versions gain high ethylbenzene EB conversion rates while producing equilibrium mixed xylenes. Catalysts that exhibit superior physical activity and stability are the key to this technology.
The technology and catalysts are used commercially in several applications. Offgas Light ends Reactor Description: For an EB dealkylation type of isomerization, the technology encompasses two main processing areas: reactor section and product distillation section. In this process, paraxylene PX -depleted feed stream is first mixed with hydrogen. The mixed stream is then heated against reactor effluent and through a process furnace.
The heated mixture is fed into isomerization reaction unit, where m-xylene,o-xylene and PX are isomerized to equilibrium and EB is de-alkylated to benzene. The liquid stream from the deheptanizer overhead contains benzene and toluene and is sent to the distillation section to produce high-purity benzene and toluene products.
This liquid stream is returned to the PX recovery section. To counter this trend, there is a global strong emphasis on regenerative energy such as biofuels to effectively reduce or avoid such emissions. Reactor 1 Transesterification Oil Description: The Lurgi biodiesel process is centered on the transesterification of different raw materials to methyl ester using methanol in the presence of a catalyst. Transesterification is based on the chemical reaction of triglycerides with methanol to methyl ester and glycerine in the presence of an alkaline catalyst.
The reaction occurs in two mixer-settler units. The actual conversion occurs in the mixers. The separation of methyl ester as the light phase and glycerine water as the heavy phase occurs in the settlers due to the insolubility of both products and the difference in density. Byproduct components are removed from the methyl ester in the downstream washing stage, which operates in a counter-current mode.
After a final drying step under vacuum, the biodiesel is ready for use. Any residual methanol contained in the glycerine water is removed in a rectification column. In this unit operation, the methanol has a purity, which is suitable for recycling back to process.
Economics: The approximate consumption figures—without glycerine distillation and bleaching—stated below are valid for the production of one ton of rapeseed methyl ester at continuous operation and nominal capacity. Only in the last five years, Lurgi has contracted more than 40 plants for the production of biodiesel with capacities ranging from 30, to , tpy.
Licensors: Lurgi GmbH. The lack of sulfur in the biodiesel enables complying with many international fuel specifications. The biodiesel is comparable to petroleum-based diesel. Triglycerides are reacted with methanol, ethanol or higher alcohols to yield biodiesel within the acceptable boiling range.
Methanol is most commonly used for the biodiesel production since it is the most cost-effective of alcohols, and it can provide better economics for the biodiesel producers. Biodiesel is produced by reacting vegetable oils and animal fats triglycerides with methanol in the presence of highly alkaline heterogeneous catalyst at moderate pressure and temperature.
Pretreatment may be required if the vegetable oil has a high free-fatty acids content to optimize methyl esters yield. If free fatty acids are present in the feed, first step is esterfication of the free-fatty acid with methanol. However if the free-fatty acids concentrations are low, then this step can be deleted. The triglycerides and methanol are converted by transesterfication reaction to yield methyl esters of the oils and fats, and glycerine is produced as a byproduct.
The glycerine is separated from the methyl esters biodiesel by phase separation via gravity settling. The methyl esters and glycerine are purified to meet the product specifications.
The feed is heated to the reaction temperature and is sent to esterification reactor. The reactor contains an acid catalyst for this reaction and can remove Note: the pretreatment is only required when the feed contains free-fatty acids; otherwise, this step can be omitted. The biodiesel product is taken from the top of the separator, and is water washed. The washed biodiesel product is taken from the top of the drum. Author : Taras Y.
Author : John J. Dave; Review: Design process of nanomaterials; ; J. Of Material Science; , 48, Author : Carl L. This volume covers inorganic compounds and elements. Mixed - base crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks usually consist of mixtures of two or more different crude oils. This extensively updated second edition of the already valuable reference targets research chemists and engineers who have chosen a career in the complex and essential petroleum industry, as well as other professionals just entering the industry who seek a comprehensive and accessible resource on petroleum processing.
The handbook describes and discusses the key components and processes that make up the petroleum refining industry. Beginning with the basics of crude oils and their nature, it continues with the commercial products derived from refining and with related issues concerning their environmental impact.
At its core is a complete overview of the processes that make up a modern refinery, plus a brief history of the development of processes.
Also described in detail are design techniques, operations and in the case of catalytic units, the chemistry of the reaction routes. The handbook also covers off-sites and utilities, as well as environmental and safety aspects relevant to the industry.
The chapter on refinery planning covers both operational planning and the decision making procedures for new or revamped processes. This page requires that javascript be enabled for some elements to function correctly. Description Besides covering topics like catalytic cracking, hydrocracking, and alkylation, this volume has chapters on waste water treatment and the economics of managing or commissioning the design of a petroleum refinery. Found only in this volume is material on operating a jointly owned and operated refinery.
Over the last decade, the ownership of many refineries has shifted to small companies, from the large, integrated companies.
Because of this shift, many refineries are now jointly owned and operated.
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