Motor fuel markets worldwide demand gasoline with lower volatility, olefinicity, and aromaticity, while retaining high octane ratings. Chemical reaction and reactor design begins with a discussion of chemical reactions, emphasizing chemical equilibrium and rate of reaction and proceeds to the theory and practice of heat and mass transfer, and important considerations in the design of chemical reactors. Performance of alkylation process a schematic diagram of the alkylation process is shown in figure below the feed to the reactor consists of olefin v1 bpd and a fresh acid makeup of m. How do we prevent the hf alkylation reactor from corrosion at. Petroleum refining design and applications handbook wiley. For the conversion of a gravityflow hf alkylation unit, the existing vertical acid settler will be retrofitted with proprietary internals for mixing and will perform the function of an alkylation reactor, acid. The major riskrelated differences of sulfuric acid and hf as a catalyst in the alkylation unit lies in each compounds volatility. Hf alkylation unit components feed system hf alkylation reactor acid regeneration acid dump system fractionation product treating key controlled and operating variables feed flow control feed drying isobutane toolefin ratio acid strength water in acid phase. Simulation on alkylation reactor sulfuric alkylation posted in chemical process simulation. Hf alkylation and selective hydrogenation process uop inc. Ic4 is one of the two main alkylation ingredients, supplied to the reactor in great excess and must be evaporated into the isostripper accumulator to be recycled to the reactor.
Refineries without alkylation capabilities are becoming rarer and typically can only produce conventional gasoline, i. Furthermore, there is always the risk of leaving something full of acid in a large, complex system like an entire hf alkylation unit. Uop hf alkylation the uop hf alkylation direct alkylation process catalytically combines light olefins such as propylene, butylene or amylene with isobutane to increase their value and make an environmentally sound alkylate product for highoctane gasoline blending. In hf alkylation units, hydroflouric acid is used as the catalyst. The typical hydrofluoric acid hf alkylation unit requires far less acid than a sulfuric acid unit to achieve the same volume of alkylate. Simulation on alkylation reactor sulfuric alkylation. A unique solidacid catalyst that converts light hydrocarbons into alkylates and 2. Low temperature alkylation maximizes selectivity, octane value, and yield 1,2. The effect of operating conditions on corrosion in hf. Low temperature alkylationmaximizes selectivity, octane value, and.
The hazop technique is a structured process hazards. Modelling and simulation of benzene alkylation process reactors for production of ethylbenzene article pdf available in petroleum and coal 461 january 2004 with 5,582 reads. Pdf modelling and simulation of benzene alkylation process. Phillips is a major licensor of hf alkylation technology and numerous other technologies. Once in the alkylation unit, the alkenes react to the isobutane while in the presence of a catalyst, causing the two substances to combine, creating the alkylates. Design of the chemical reactor critical manifoldsdistance to the critical. Materials performance in hfalkylation units book osti. A process for removing polymeric byproduct aso acid soluble oil from the circulating hf alkylation acid in an hf alkylation unit used for the production of gasoline boiling range alkylate product by alkylation of an isoparaffin with an olefin, which comprises. The worldwide capacity for alkylate production by these two processes over the past 50 years has shown a decline in hf alkylation since 1990 beall et al. Williams at marathon ashland petroleum llc, and david l. Hf alkylation conversion is finally within reachpart 1.
Alkylate is a premium gasoline blending component alkylation capacity steadily increased annually since 1980s due to gasoline specifications high octane number isooctane 100 low vapor pressure less volatile. Concentrated hydrofluoric acid hf is then mixed in and fed to the reactor. In the meantime, existing alkylation units can and must be made safer. Materials selection in hfalkylation units is mostly based on long time experience. Commit to ending the use of hf alkylation an d replacing it with safer alternatives as soon as possible. Hydrofluoric acid alkylation conversion and expansion. May 28, 2014 the publication recommends that access to an hf alkylation unit be restricted due to the potential hazards of hf. Superior refinery hf alkylation unit animation duration.
No similar specification was recommended for sulfuric acid alkylation. By true sac we mean that the catalytic acid function is intrinsic to the solid itself rather than being a separate species, such as an immobilized liquid deposited on a solid substrate. The second conversion option using a novel reactor design is also suitable for both gravityflow and pumpedflow hf alkylation units. Alkylation reactions are catalyzed by strong acids i. Materials selection in hf alkylation units is mostly based on long time experience. The design is intended to resemble the new liquidphase eb process offered by lummus crest, which uses a zeolite catalyst developed by unocal. Alkylation and dealkylation in industrial processes reactor engineering class 148. These compounds are fed into a reactor, where, under the influence of a sulfuricacid or. Olefin and isobutane feed streams are dried to remove water before they are mixed with the isobutane recycle stream. Otherwise the light ends will require venting of the hf alkylation unit with resulting hf acid losses. Revap is compatible with existing hf alkylation reactor systems, which are used to meet increasing demand for alkylate as a clean highoctane blending component in reformulated gasoline. The most widely used material in the station units is standard carbon steel, because it is capable to form a thick protective fefsub 2 layer in concentrated or anhydrous hydrofluoric acid. Uop approved hf1, hf10, hf2, hf20, hf4, hf40, hf5, hf50.
The alkyclean process employs a zeolite catalyst coupled with a novel reactor. Application of hazop, lopa and sil to the alkylation unit. A method of converting an hf alkylation process into a solid catalyst alkylation process is disclosed. Because of the chemical burn hazard present with hf, refineries have incorporated many or all of the following engineering controls at hf alkylation units. Exelus has developed an innovative isoparaffin alkylation technology exsact, as an economically viable alternative to hf h2so4 processes. The equipment is a stack of 3 aeu exchangers, with the stripper feed in the tubes. Louisiana refining division if applicable hf alkylation unit training. The alkylation reaction takes place combining the olefins with the isobutane to form the. Results of alkylation unit hazard, operability study are.
The two main principles involved in establishing conditions for performing a reaction are chemical kinetics and thermodynamics. Triple offset valve tov formally approved by uop in august 2015 for hf alkylation service. Procedia chemistry 10 2014 547 a 554 551 as each har molecule can deactivate 2 moles of acid, catalyst relative activity dependence on har content in the reactor is linear and is written as follows. The light hydrocarbons consist of olefins such as propylene and butylene and isoparaffins such as isobutane. Finally, acid cleanings leave carbon steel surfaces in.
When combining a selective hydrogenation process with an hf alkylation process, it is necessary to remove light gases such as ethane, methane, and hydrogen from the hydrogenation unit effluent before it is charged to the alkylation unit. Hf alkylation process with internal acid regeneration. Mar 11, 2015 alkylation and dealkylation in industrial processes reactor engineering class 148. Dobis, materials and corrosion director at the equity engineering group, inc. In this method, an hf alkylation unit having an hf stripper downstream of the hf alkylation reactor is modified to a benzene rectifier. A novel fixedbed reactor that is designed to enhance the performance of this. Cenco refining licenses phillips revap alkylation technology. Through lecture, exercises, and discussion, participants will gain an understanding of the hf alkylation process and. Inherently safer than liquid acid technologies, particularly hf. As of december 2006, the online acid analysis system is installed in almost 20 hf alkylation units worldwide and has a combined operating history of process collaboration hydrofluoric acid alkylation. Invistigation on alkylation process sust repository.
Develop reactor internals for optimizing reactor design. The uop hf alkylation process, created in 1941, catalytically combines light olefins propylene, butylenes and amylenes with. Kellogg corporation cascade reactor were bubbled up through liquid hf. Alkylation processes alkylation is catalysed by a strong acid, either sulphuric h2so4 orhydrofluoric hf. An improved reactor for an hf alkylation unit of the shellandtube heat exchanger type has an axial tube bundle to provide cooling for the reactor and a centrallylocated axial sparger system for injecting and dispersing the hydrocarbon reactants into the flow path in the reactor. Our hf based detergent alkylation unit uop design always has a steady increase in dp on the hf stripper feed preheater due to hf scale.
Alkylate is the reactor product, isooctane or isoheptane to be separated as the isostripper bottom product. Sep 27, 1988 when combining a selective hydrogenation process with an hf alkylation process, it is necessary to remove light gases such as ethane, methane, and hydrogen from the hydrogenation unit effluent before it is charged to the alkylation unit. Construction of concrete containment curbs around reactor and hf storage vessels. Thermodynamics is an engineering fundamental having various applications for the chemical reactor design. Solidacid alkylation process development is at a crucial stage osti. Chemical kinetics is the study of rate and mechanism by which one chemical species is converted to another. Exelus has developed an innovative isoparaffin alkylation technology exsact, as an economically viable alternative to hfh2so4 processes.
Shutting down a sulfuric acid alkylation unit reactor. The two most commonly used reactor systems which grew out of the reactor development work for h2so4 alkylation are the stratford engineering companys stratco contactor and the m. Reactor performance depends on important parameters such as reaction kinetics and thermodynamics, reactor. Vice president operations jonathan bayhi 225 7479565 email protected learn more. Reactorregenerator system joint work optimization in benzene. The effect of operating conditions on corrosion in hf alkylation units part 1 by jonathan d. Fouling in hf alkylation units chemical plant design. Hf alkylation unit developed fel2fel3 packages and the bid package for detailed engineering for uop alkylation unit retrofitted with split olefin feed technology soft reactor for a revamp project to handle increased capacity and to handle a shift in the reactor feed composition. Alkylation, in petroleum refining, chemical process in which light, gaseous hydrocarbons are combined to produce highoctane components of gasoline. The failure of even a small piece of piping is a big problem when the unit is started up. In the liquidphase process the alkylation reactor operates at higher pressure but lower temperature than the vaporphase alkylation process.
After prescreening of potential candidates in a laboratory alkylation microreactor, a true sac was selected as the preferred prototype. Fundamentals of petroleum refining pages 251 300 text. The publication recommends that access to an hf alkylation unit be restricted due to the potential hazards of hf. Our team our dedicated team of professionals are on a mission to provide the highest level of service and support to hf units worldwide. The alkylation process itself generates a significant amount of heat. By careful selection of the operating conditions, a high proportion of products can fall in the gasoline boiling range with motor octane. The hf process only creates a small amount of organofluorine side products which are continuously removed from the reactor and the consumed hf is replenished. Apr 22, 2020 after prescreening of potential candidates in a laboratory alkylation micro reactor, a true sac was selected as the preferred prototype. This is especially true for the hf alkylation process.
The conversion options for the reaction section include. Hi guys, i am trying to simulate a sulfuric acid alkylation reactor unit in hysys but the current available reactor model is not robust enough based on the complexity of the sulfuric alkylation reaction it. Fundamentals hf alkylation process implementation seminar course overview course number. The mixture is fed to the reactor, where it is highly dispersed into an incoming stream of acid catalyst. The louisiana refining division requires hf alkylation unit training for personnel engaged in entering the refinerys hydrofluoric acid alkylation unit hf alky unit and performing work in affiliation with equipment in hf service. Hf alkylation unit components feed system hf alkylation reactor acid regeneration acid dump system fractionation product treating key controlled and operating variables feed flow control feed drying isobutane toolefin ratio acid strength water in acid phase reactor temperature contact time. Installation of segregated sewer systems designed to contain spills and runoff from hf acid areas. A case study of the alkylation unit at the delaware city refining company dcrc involving equipment maintenance incident petroleum refining design and applications handbook, volume 1.
The sparger comprises an axiallyextensive tube with outlet nozzles for the hydrocarbon reactants arranged around. Alkylation and dealkylation in industrial processes. Low temperature cd alky breaks the lowtemperature barrier through innovative reactor design. Thus i wanna give it a shot to simulate this reactor using aspen custom modeler but i have to. Cdalky breaks the lowtemperature barrier through innovative reactor design. Isoalky technology is commercially viable alternative. The uop hf alkylation process is used in more than 150 refineries worldwide. How do we prevent the hf alkylation reactor from corrosion at the design stage.
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