GASOLINE MEROX UNIT PROCESS PRINCIPLES

GENERAL Gasoline sweetening is a process of converting mercaptans in the product (gasoline) directly to disulfides. Because the vapor pressures of disulfide are so low relative to those of mercaptans, their presence is much less objectionable and these disulfides remain in the product and there is no reduction in total sulfur content. The conventional Merox fixed bed sweetening make use of the gross intermittent alkali saturation of catalyst bed but the Merox Minalk unit relies on a small, continuous injection of an appropriate strength alkali solution. This continuous, small injection of alkali such as dilute sodium hydroxide solution (2-5 wppm), is held to a minimum but enough to provide the needed alkalinity. In this way mercaptans are oxidized to disulfides and they do not enter into a peroxidtion reaction in case of insufficient alkalinity. For a complete removal of H2S from the charge stock (light gasoline) where more than low ppm (parts per million) levels of H2S are present, the charge stock is passed through a guard caustic scrubber. H2S does not poison the catalyst but it competes with mercaptans for the available catalytic sites and available oxygen. Post treatment is not required on Minalk sweetened streams. MEROX PROCESS OVERVIEW The UOP (universal oil product) Merox Process is an efficient and economical catalytic process developed for the chemical treatment of petroleum distillates for removal of sulfur present as mercaptan (Merox Extraction) or conversion of mercaptan sulfur to another much less objectionable form (Merox Sweetening). The name Merox is an acronym derived from MERcaptan OXidation. The process relies on a special catalyst to accelerate the oxidation of mercaptans to disulfides at or near economical product rundown temperature. The MINALK unit is a sweetening process. Depending on the application, extraction and sweetening are used either separately or in combination. The Merox process is based on the ability of a catalyst or catalysts composed of iron group metal chelates in an alkaline environment to promote the oxidation of mercaptans to disulfides using air as the source of oxygen. The reaction proceeds at an economically practical rate at normal temperatures for refinery rundown streams. For light stocks, operating pressure is controlled slightly above the bubble point to assure liquid phase operation; for heavier stocks, operating pressure is normally set to keep air dissolved in the reaction section.

Applications of the Merox Process Typical Hydrocarbon Streams Treatment Gas, Natural Gas, Fuel Gas LPG (C2, C3, C4) Pentanes Light, Straight-Run Naphtha Light, Thermally Cracked Naphtha FBR, Straight-Run Naphtha FBR, FCC Cracked Naphtha Heavy, FCC Cracked Naphtha Heavy, Straight Run Naphtha Aviation Turbine Fuel Gasoline Distillate Fuel (to 350C EP) Applicable A A A, B, C, E A, B, C, E A, D C, D, E B, C, E C, E D D, F D, F D Merox

Key to Treatment Methods A Mercaptan Removal (Extraction) B Liquid-Liquid Mercaptan Conversion (Sweetening) C Minimum Alkali (Minalk) Fixed-Bed Mercaptan Conversion (Sweetening) D Fixed-Bed Mercaptan Conversion (Sweetening) E Caustic-Free Fixed Bed Mercaptan Conversion for Gasoline (Sweetening) F Caustic-Free Fixed Bed Mercaptan Conversion for Kerosene (Sweetening) NOTE: FBR = Full Boiling Range 2.3 REACTION CHEMISTRY Merox Reactions The Merox process in all of its applications is based on the ability of an organic metallic catalyst to accelerate the oxidation of mercaptans to disulfides at or near ambient temperatures and pressures. Oxygen is supplied from the atmosphere. The reaction only proceeds in an alkaline environment. The overall reaction is as follows: RSH + 1 1 1 O2 RSSR + HO2 4 2 2

The R is a saturated or unsaturated hydrocarbon chain which may be straight, branched, or cyclic. In most petroleum fractions the R might have 1, 2, 3 or more carbon atoms in the chain. Sometimes when this reaction occurs, two different mercaptans may enter the reaction. This is illustrated as R and R in the reaction equation as: 2 RSH + 2 RSH + O2 2 RSSR + 2HO2

This reaction occurs spontaneously, but at a very slow rate.

Detailed Sweetening Chemistry On the basis of Licensor (UOP) studies, the thiol portion of the mercaptan (-SH) functional group, first transfers to the aqueous alkaline phase and then combines with the catalyst. The presence of oxygen causes this mercaptan catalyst complex to oxidize, yielding a disulfide molecule and water. The system works efficiently for all lower molecular weight mercatpans which are partially soluble in caustic soda solution.

It is the function of the catalyst not only to accelerate the oxidation without allowing side reactions to occur. Most of the other mercaptan oxidation processes utilize oxidation reactions which occur in the oil phase. An oil phase reaction is much less desirable because there are many competing oxidation reactions which can occur in the oil phase to leave contaminants in the product. Mercaptide at Interface The purpose of the caustic soda is in two folds: 1) 2) To transfer the thiol portion of the mercaptan to the aqueous phase and To supply the alkaline environment needed for the reaction to proceed in the direction desired.

2.4 MEROX CATALYSTS The fixed bed Merox process has the Merox catalyst deposited upon the extended hydrophilic surface of specially selected activated charcoal. The function of the activated charcoal is to provide a vast surface area where mercaptans, catalyst, caustic, and oxygen may come into contact for completion of the sweetening reaction. To provide the alkaline medium, the charcoal is kept saturated with caustic solution. The fixed bed process utilizes a type of Merox catalyst that is not dispersible in caustic so as to prevent caustic from removing the catalyst from the charcoal surface. The Minalk version of the fixed bed Merox process utilizes the same catalyst/charcoal reactor bed as other fixed bed Merox processes. A brief description of Merox catalysts and reagents for the Minalk process is given below. MEROX FB (fixed bed) is the catalyst reagent used to impregnate the specially selected activated carbons to form fixed bed Merox catalysts. Merox FB is supplied as a dark blue water slurry which is packaged in 9.5 liter (2.5 gallon) sealed polyethylene bottle. Each bottle contains 2.5 kg (5.5 lb) of active ingredient. MEROX FB requires no additional handling or mixing prior to use. It is recommended that the bottle of reagent be well shaken before dispensing to avoid settling and ensure proper addition to the process.

PROCESS VARIABLES

The following represent the five primary process variables.

C atalyst O xygen A akalinity C ontact H eat 3.1 CATALYST CONCENTRATION 3.2 OXYGEN INJECTION Oxygen is supplied to all versions of the Merox process in the form of compressed atmospheric air. The amount of excess air injection necessary is highly dependent upon the individual feedstock, but normally ranges between 1.2 to 2.0 times the theoretical requirements. For Minalk and other fixed bed units the air injected must be completely dissolved in the hydrocarbon; otherwise a separate air phase will exist within the fixed bed and eventually lead to channeling. The most important factor for solubility is pressure on the system. Thus sufficient pressure to dissolve the required air must be maintained at all times. Pressure is in fact secondary variable, since pressure is directly proportional to the

solubility of air in hydrocarbon.

ALKALINITY 3.3 Alkalinity is needed to selectively drive the mercaptan oxidation reaction. Alkalinity is provided by aqueous sodium hydroxide or caustic solution. A sufficient quantity of caustic injection should be maintained to yield a peroxide number of 0.3 or less. Any acids present in the feed lead to caustic neutralization. As caustic is neutralized, it must be replaced in order to maintain acceptable operation. 3.4 CONTACT Contact can be characterized by duration of mixing time, by volumetric ratio of reactants, or by differential pressure, which implies degree of dispersion. With a fixed bed flow restriction, the differential pressure is directly related to the linear velocity so that velocity is often taken to be the process variable. The primary source of contact is a fixed bed unit is the charcoal bed itself. The porous structure of the charcoal provides vast interfacial surface area necessary for contact between gasoline, caustic, and catalyst. The variable used to characterize contact is residence time in the charcoal bed. Residence time is often expressed in terms of volume of feed per hour, per volume of catalyst bed. As residence time increases mercaptan increase.

Sweetening

As the catalyst bed accumulates residence time, the charcoal pores tend to plug and become blinded by extremely heavy hydrocarbon molecules. This reduces contact and is largely the cause of fixed bed deactivation. Fixed bed deactivation result in higher mercaptan content in the product. 3.5 HEAT (TEMPERATURE) Minalk fixed bed sweetening is favored by higher temperature. Increasing the Gasoline feed temperature increases the rate of mercaptan conversion. However, increasing the temperature will also enhance other oxidation reactions, which may be undesirable because of color deterioration, gum precursor formation, and premature catalyst deactivation. Therefore, the feed temperature should be kept as low as possible while still maintaining the desired degree of mercaptan conversion; normally this is in the range of 38o to 50o. 3.6 FEED QUALITY Successful MINALK unit operations requires the removal or neutralization of any compounds or impurities that could cause catalyst deactivation, interference, or degradation of the treating chemicals and solvents. 3.6.1 Elemental Sulfur Elemental sulfur, once formed, is very difficult to remove. None of the equipment in a Merox unit is capable of removing elemental sulfur. 3.6.2 Hydrogen Sulfide

Low concentrations of H2S may be removed by caustic prewashing, that is, by washing the hydrocarbon stream with dilute solution of caustic soda. Dilute caustic solutions are necessary to prevent the precipitation of sodium sulfide (Na2S) crystals. 3.6.3 Carbon Dioxide

Carbon dioxide (CO2) is commonly present in light hydrocarbon fractions, mainly as a result of contamination, which occurs in catalytic cracking. However, CO2 is an acidic contaminant and thus may be simultaneously removed with H2S caustic washing or ethanolamine extractive absorption.

PROCESS FLOW AND CONTROL

Air and caustic are injected into the hydrocarbon feed stream, which then enters the Minalk reactor down flow. Sweetened product, essentially free of entrained caustic, is withdrawn directly from the side of the fixed bed near the bottom of the Reactor (15-R-501) The coalesced aqueous phase collects at the bottom of the vessel and is discharged via a small drain pot to sewer or to the spent caustic disposal system. The charcoal bed is an excellent coalesces. A flow diagram of the Minalk unit is shown below;

Fixed Bed Minimum Alkali Merox Sweetening Unit

The hydrocarbon feed and process air to the Minalk unit enters on flow control and sweetened product leaves on pressure control. This spent caustic leaves the drain pot on level control. Air is injected into the hydrocarbon stream via an Air Mixer (15-MX-501). This ensures a uniform dissolution of air in the hydrocarbon just before entering the Reactor (15-R-501). The air injection line is provided with a cutoff valve which stops the air flow on low hydrocarbon flow rate. An excessive amount of air injection for a given feed rate can cause the formation of separate air phase at the top of Reactor(15-R-501) which will promote channeling in the catalyst bed. A continuous injection of dilute caustic is required to maintain a minimum level of alkalinity in the Reactor(15-R-501). Caustic is injected through an atomizing nozzle to ensure uniform distribution in the feed.