The product alkylate contains a mixture of highoctane, branchedchain paraffinic hydrocarbons. Pdf environmental assessment of hf alkylation process using. It is based upon a rigorous and highfidelity mathematical process model to provide a realistic dynamic response of a process unit. Corrosion and fouling in hf alkylation units are closely linked to feed quality and operating conditions. Capital and production costs are estimated for the plant. Alkylation process alkylation is the process of producing gasoline range material light olefins primarily propylene and butylene with isobutane in the presence of a highly acidic catalyst, either sulfuric acid or hydrofluoric acid. This is the base case for direct alkylation, using a straight run ironbased high temperature fischertropsch fehtft c4 feed. A process design is developed for the plant incorporating the inventions with the design based on the results of a detailed process simulation. New alkylation technology for increasing gasoline octane. In this work, computer aided tools as process simulation and graphical user interfase environmental evaluation were used for analysis of an alkylation unit using hydrofluoric acid hf as acidic. Environmental assessment of hf alkylation process using war. Fundamentals hf alkylation process implementation seminar course. Referring to the system diagram below, the invensys system consists of a.
New process schemes, retrofits, fine tune alkylation. Then, the normal paraffins are dehydrogenated to corresponding monoolefins over a highly selective and active catalyst. Operations process engineer on the hf alkylation unit in conocophillips companys sweeny refinery. The refinery, operating a phillips petroleum hf alkylation process, was looking for a significant improvement from gate and plug valves commonly used. Mei maverick engineering, a wholly owned subsidiary of triple 5 worldwide, can be of assistance with your alkylation projects. The message is simple we specialize in supporting your companys uop and phillips hf alkylation technology with highlyexperienced, industryleading consultants and engineers who are ready to assist in a moments notice. Superior refinery hf alkylation unit animation husky energy. Online monitoring allows to increase octane number in alkylate, optimize water contents and improve catalyst regeneration process. An overview of the progress some of these companies have made will give refiners an update on the status of these new schemes. Overviewofalkylation process solutions guide refining crudeandvacuum distillation dela yedcok er fluidizedbed catalyticcracker fcc a lk ation hydrotreating hydrog n plant blending.
Propane is further treated through the propane splitter to remove any dissolved hf and finally treated with alumina to remove fluorinated organics, and then caustic koh to neutralize any remaining acid. The alkyclean process challenges with hf alkylation units. Emersons enhanced software enables refiners to better. Apc hf alkylation specific application for hf alkylation units. The hf alkylation advanced control package uses axens horizon latest generation multivariable controller mvac. Early commercial units used h 2 so 4, but more recently, hf alkylation has been used more commonly in petroleum refineries. Due to the severity of the process, all testing procedures are strictly adhered to per licensors requirements. Figure 2 is a simplified process flow diagram for the uop alkyplustm process. The alkylation process combines an unsaturated contains double carbon bonds light hydrocarbon, usually propylene propene or butylene butane with isobutane. Successful operation of the first alkyclean solid acid.
The uop hf alkylation process, created in 1941, catalytically combines light olefins propylene, butylenes and amylenes with isobutane to produce a premium gasoline blending component. May 28, 2014 the publication recommends that access to an hf alkylation unit be restricted due to the potential hazards of hf. Flow diagrams of direct and indirect alkylation process. 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. Important operating variables include acid strength, reaction. The method employs nearinfrared spectroscopy coupled with chemometric data analysis. Hydrofluoric acid alkylation hfu unit optimization the use of. It is used to convert isobutane and lowmolecularweight alkenes primarily a mixture of propene and butene into alkylate, a high octane gasoline component. Alkylation continues to be a very important process to refiners continued growth in alkylation capa 1 methodology cont. Prior to the development of the alkylation process, these lowmolecular weight hydrocarbons were essentially waste. Alkylation and dealkylation in industrial processes. Process solutions guide refining crudeandvacuum distillation dela yedcok er fluidizedbed catalyticcracker fcc a lk ation hydrotreating hydrog n.
This powerful tool analyzes the nearir absorption spectrum of a mixture and. Optimization of refining alkylation process unit using. Process optimization of a butanebutene alkylation plant 73 streams are not pure. Alkylation continues to be a very important process to refiners. Micromotionhighlyaccuratedensity measurementscanbecorrelatedtotheacidstrength. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion or a carbene or their equivalents. Hf alkylation simulation and tutorial simulation gses envision simulation is a realtime dynamic process simulation program used for operator training. 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 from the process sets the quality standard for environmentally friendly gasoline. Environmental impacts assessment using war algorithm the war methodology was implemented through graphical user interphase environmental evaluation for analysis of an alkylation unit towards process assessment and improvement. Motor fuel alkylation using liquid hydrofluoric hf or sulfuric acids h2so4 is one of the oldest catalytic processes used in the petroleum refinery operations. No similar specification was recommended for sulfuric acid alkylation. The hf alkylation unit processes olefin feed and isobutane to create highvalue alkylate product.
Hf can be more easily regenerated than h 2 so 4 in the alkylation process, and hf alkylation is less sensitive to temperature fluctuations than h 2 so 4 alkylation 3. They contain high amounts of inert components such as. C alkylation is a process for the formation of carboncarbon bonds. In 1991, 16,000 tons of hf were consumed in alkylation catalysis in the u. Application of hazop, lopa and sil to the alkylation unit. Appendix ix also includes the type of hf alkylation process phillips or uop used at each refinery. The resulting product is referred to as alkylate, and is usually a seven or eightbranched carbon molecule. Show full abstract alkylation desulfurization process, which could reduce the sulfuric compounds to hydrogen sulfide by catalytic alkylation with olefins and distillation followed by. The overheads consist mostly of hf acid fumes and propane gas. The purpose of this bulletin is to alert field personnel to the potential safety and health risks posed by hydrofluoric acid hf used in hf alkylation units and to present the control measures implemented by industry to reduce workers exposure, and pertinent osha requirements. The typical hydrofluoric acid hf alkylation unit requires far less acid than a sulfuric acid unit to achieve the same volume of alkylate.
The mixture is fed to the reactor, where it is highly dispersed into an incoming stream of acid catalyst. Responsible for the daytoday operations and midterm optimization of. Alkylation creates additives that boost the octane of gasoline. In an hf alkylation process wherein a preselected amount of acid soluble oils is described to be maintained in the alkylation system hf catalyst the improvement comprises returning a stream comprising acid soluble oils recovered from an hf rerun column and isobutane to the hf alkylation system so as to maintain said preselected amount of acid soluble oils in said system hf catalyst. Alkylation product separation, july 2008, page 2 figure 2 is a trend of inference against lab values and it indicates what can be accomplished by the way of first principles modeling. The catalyst is also saturated with the hydrocarbons involved in the process e. New technology for analyzing hf alkylation processes. Alkylation is the transfer of an alkyl group from one molecule to another. For hf alkylation, the reaction temperature is less significant and is between 21 and 38 c 70 and 100 f. The main scope of the course is to create strong basis and fundamentals regarding the processes in the petroleum refining.
The refinery, operating a phillips petroleum hf alkylation process, was looking for a significant improvement from gate and plug valves commonly used in the unit. This course is designed for process engineers and operations personnel who work with the uop hf alkylation process or supervise those who do. For alkylation at carbon, the electrophilicity of alkyl halides is enhanced by the presence of a lewis acid such as aluminium trichloride. The most widely used process for octane production is hf alkylation. The flowsheet simulation program is used for process material and energy balances. Process analyzer install nir analyzer for hf alkylation process measures hf, water and aso content.
Hydrofluoric acid hf alkylation units, often referred to as hf alky units, are process units used in petroleum refining to convert isobutane and alkenes primarily propylene or butylene into alkylate, which is used to make gasoline before being transferred to the alkylation unit, the alkenes are generated in a fluidized catalytic cracking unit fccu. The alkylation process itself generates a significant amount of heat. Ppt alkylation continues to be a very important process. This article outlines the relationship between key operating parameters and corrosion that has been used to develop a set of guidelines to define an operating envelope. Jun 14, 2014 alkylation definition alkylation is the transfer of an alkyl group from one molecule to another. Olefin and isobutane feed streams are dried to remove water before they are mixed with the isobutane recycle stream. There are two primary licensors of the hf alkylation process. The data obtained were essential and subsequently formed the basis for a successful patent registration under which abb offers the hf process ftir 3. Lastly, benzene is alkylated with monoolefins to lab using hydrofluoric hf acid as the catalyst in alkylation process.
Discover the alkylation process used by refiners to convert light hydrocarbons to alkylate, an excellent blending component for gasoline make this video samp. Hf alkylation process incorporating exxonmobil concepts. Continued growth in alkylation capacity has occurred through the last decade as u. A novel liquid acid catalyzed alkylation process utilizing a liquid acid catalyst comprising a surfactant and a liquid acid is disclosed which incorporates a fixed bed of contact material to improve the alkylation reaction zone efficiency. In both processes, the volume of acid used is approximately equal to the volume of liquid hydrocarbon feed. The fresh olefin feed is combined with isobutane ic4 before entering the reactor where the olefins react with ic4 in the presence of hydrofluoric acid catalyst. On average, these 50 refineries each store 212,000 pounds of hf. Mei can provide the complete range of services, including frontend engineering design, detail engineering, procurement, construction management, startup and operator training, to insure a successful brownfield or maintenance project. The process modeling was performed using a commercial software taking. Alkylation process is one of the most important refinery processes for producing conventional. Phillips latest major process improvement is its socalled splitolefin feed technology soft. Process collaboration hydrofluoric acid alkylation. To illustrate the point in a one page editorial we discuss only one of the important isostripper variables.
Block flow diagrams of the direct alkylation hf and h2so4 catalysed alkylation configurations evaluated 3. It is designed to maximize the benefits from the hf alkylation process in an environment with difficult and particularly slow, multivariable interactions. Alkylation units were installed in petroleum refineries in the 1930s, but the process became especially important during world war ii, when there was a great demand for aviation gasoline. Process analyzer nir analyzer for hf alkylation process measures hf, water and aso content. In this study a commercial sulfuric acid catalyzed alkylation process is.
These must be separated from the product in order to reach the product quality specifications and purged from the system to avoid their accumulation. Successful operation of the first alkyclean solid acid alkylation unit. 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. The major riskrelated differences of sulfuric acid and hf as a catalyst in the alkylation unit lies in each compounds volatility. Hf alkylation equipment is a global business bringing to market the most advanced proven technology for equipment and services to those refineries using the uop and phillips technology for hf alkylation. An improved process for removing polymeric byproduct aso from the hf alkylation acid in an hf alkylation unit used for the production of gasoline boiling range alkylate product by olefinisoparaffin alkylation, comprises fractionating a portion of the circulating hf alkylation acid inventory of the unit with a portion of hot alkylate product in a fractionation zone. Measuring hf acid purity using online analyzer technology.
Process engineers and operations personnel who work with the uop hf alkylation process or have played a supervisory role. Likewise, in any crude distillation process, an excess of light end products such as butane tend to be formed that are of limited use. In hf alkylation units, hydroflouric acid is used as the catalyst. Alkylation and dealkylation in industrial processes reactor engineering class 148. The publication recommends that access to an hf alkylation unit be restricted due to the potential hazards of hf. 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. An alkylation unit alky is one of the conversion processes used in petroleum refineries.
A computer implemented method for online determination of concentrations in an hf alkylation process catalyst stream containing hf acid, aso, water and optionally an additive which suppresses the vapor pressure of hf acid. Environmental assessment of hf alkylation process using. Figure 1 is a typical process flow diagram of a hydrofluoric hf acid alkylation unit. Olefin and isobutane feed streams are dried to remove water before they are mixed with. The fixed bed of contact material also allows the process to be efficiently operated at lower acid to olefin molemole feed ratios than normally. 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.
A process for maintaining hf acid soluble oils aso in an hf alkylation reaction zone in an amount sufficient to ensure formation of an alkylate containing a high octane number is provided by returning to the reaction zone a portion of acid soluble oil recovered from an hf catalyst rerun system. Alkylation definition alkylation is the transfer of an alkyl group from one molecule to another. Superior refinery hf alkylation unit animation youtube. Mar 11, 2015 alkylation and dealkylation in industrial processes reactor engineering class 148. Performance of alkylation process a schematic diagram of the alkylation process is shown in figure below. The process occurs in the presence of an acid such as sulfuric acid h 2 so 4 or hydrofluoric acid hf as catalyst. In 1982, a major european refiner contacted descote to find a durable and reliable solution to their hf valve problems and high maintenance costs. Refining alkylation process solutions guide improvingefficiency recommendedproductsolution application interstageandspentacid strength. C alkylation can also be effected by alkenes in the presence of acids. Safety issues environmental issues operational issues. Hf alkylation process with internal acid regeneration. Honeywells training courses on uop are designed to empower participants teams and drive effective, efficient and safe operations in petroleum refining, gas processing, petrochemical production and other major manufacturing industries. Lewis acids are particularly suited for c alkylation. Effective separation is a critical component of an efficient, reliable and safe h2so4 alkylation process.
In the hf alkylation process, it is important to monitor and control the purity of the catalyst. Superior refinery hf alkylation unit animation duration. It is now used in combination with fractional distillation, catalytic cracking, and isomerization to increase a refinerys yield of automotive gasoline. The network grid diagram that makes use of the external utilities. Nov 08, 2018 likewise, in any crude distillation process, an excess of light end products such as butane tend to be formed that are of limited use. Since then the relative importance of processes using hf has increased. The effect of operating conditions on corrosion in hf.