INSPECTION TRAINING MANUAL MEROX UNIT709001 XXI-1 PROK General The UOP Merox Process is an efficient and economical catalytic Process developed for the chemical treatment of petroleum distillates for removal of sulfur present as mercaptans (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. Merox treatment can, in general, be utilized in the following ways. 1, Improve lead susceptibility of light gasolines. (Extraction) 2. Improve susceptibility of gasoline stocks to oxidation inhibitors added to prevent gum formation during storage. (Sweetening and Extraction) 3. Odur improvement on a1 stocks. (Extraction and sweetening or both when Extraction cannot remove all of the mercaptans.) 4. Meet product specifications requiring a negative Doctor Test. (Sweetening) 5. Reduce sulfur content of LPG products to meet specifications. (Extraction)709001 XXI-2 6. Reduce sulfur content of FCC, coker or visbreaker C3/Cy olefins resulting in decreased acid consumption in alkylation operations using these materials as feedstocks and meeting the requirement of low sulfur for sensitive catalyst used in variouc chemical synthesis processes. (Extraction) Dependent on the application and the results desired, the Merox Process is applicable to the treatment of stocks boiling to 650°F end point or higher. ‘B._Hrocess vescription ‘The UOP Herox Process accomplishes either mercapts eatractiun or mercaptan sweetening. Depending on the application, extraction and sweetening can he 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 iquid phase operation; for neavier stocks, operating Pressure is normally set to keep air dissolved in the reaction section. Downstream pressure requirements are easily taken care of by use of appropriate size product pumps. d either ceparately ar in combination. Tho 1, Merox Extraction Low molecular weight mercaptans are soluble in caustic soda solu- tion. Therefore, when treating LPG and light gasoline fractions, Nerox process can be used to extract mercaptans, thus reducing the sulfur content of the treated product. In the extraction unit, sulfur reduction is directly related to the extractable mercaptan content of the fresh charge.709001 XXI-3 In mercaptan extraction units, fresh feed is charged to an extrac- ‘ion column, tn which mercaptans are counter-currently extracted by a caustic stream containing Merox catalyst. The treated material passes overhead to a settler in which any entrained caustic solution 4s separated and returned to the circulation system. The mercaptan-rich caustic solution from the bottom of the extrac- tion column flows to the regeneration section, through a steam heater which functions principally to maintain temperature during cold weather. Air is injected into this stream and the mixture flows upward through the oxidizer where the mercaptans are converted to disulfides. The oxidizer effluent flows into the disulfide separator where spent air, disulfide of1 and the caustic solution are separated. Spent air is vented to a safe place while disulfide of1 is docanted and sont to disposal; it can be, for example, injected into the charge to a hydrotreating unit or FCC unit. The regenerated caustic stream is returned to the extraction column, Merox catalyst is added periodically to maintain required activity. 2, Herox Sweetening For sweetening units, the mercaptans are converted directly to Ulsulfides which remain in the product; there is no reduction in total sulfur content. Merox Sweetening entails the application of four different types of units. In addition to the regular liquid-liquid and fixed bed sweetening with continuous or intermittent circulation of caustic solution, a recent development is the fixed bed using minimum alkali or Minalk for short. These versions are described below:709001 XXI-4 Hydrocarbon, air, and aqueous caustic soda containing dispersed Moray catalyct are simuTtanoously contacted in a mixer, where mercaptans are converted to disulfides. Mixer effluent is directed to a settler from which the treated hydrocarbon stream is routed to a coalescer for removal of any entrained caustic solution. Caustic solution from the separator and also that. which is recovered from the coalescer, is circulated to the mixer system, Periodically, a small amount of Merox catalyst is added to maintain the catalystic activity of the caustic system. In general, liquid-liquid sweetening is appl able to virgin gasolines and components having endpoints of 275-300°F (135- 150°C). Since experiance has chown the mercaptan typos associated with cracked naphthas are easier to sweeten than those contained in naphthas from other sources, liquid sweetening has been successfully applied to cracked gasolines having endpoints as high as 450°F (230°C). This version of the process has essentially been replaced by the T1xed Ded minalk type because the Iiquid-Iiquid type is catalytically less active, needs more major equipment, and yields a much greater amount of caustic to dispose of. The Viquid-liquid unit is no longer being designed, except in cases where the client specifically requests one, perhaps due to familiarity and satisfaction. Fixed Bed Sweetening (Conventional) Fixed bed sweetening is normally employed with charge stocks having end points above 275-300°F (135-150°C). With these SUOcKS, the heavier mercaptan types associated with the nigher end points are only partially soluble in caustic solution and are more difficult to sweeten. Contact and residence time requirements become uneconomical for liquid-liquid designs.709001 XXI-5 Mercaptans are converted to disulfides in a fixed bed reactor system. This consists of a reactor which contains a bed of specially selected activated charcoal impregnated with Merox catalyst and wetted with caustic solution. Air is injected into the feed hydrocarbon stream ahead of the reactor and, in passing through the catalyst-impregnated bed, the mercaptans in the feed are oxidized to disulfides. The reactor is followed by a settler which also serves as a caustic reservoir. A caustic Circulation pump is provided for intermittent circulation of caustic from the settler to wet the catalyst bed. The frequency of caustic circulation over the bed can vary from a day to a month or more depending on the difficulty of the stock being treated and the activity of the catalyst. ‘A very important application of the Merox fixed bed sweetening relates to the production of jet fuels and Kerosines. AS a result of the development of the Merox fixed bed system, jet fuels and kerosines (also stove or heating oils) can now be treated at costs which are incomparably lover than the simplest hydrotreater. The same general basic process flow described above is used. However, because of the particular jet fuel quality requirements and the raw jet fuel characteristics, somewhat more extensive pretreatment and post treatment are needed. tent 19 This most recent version of the Morex process {2 the same as conventional sweetening except that a much more active catalyst system is employed includina the continuous addition of a catalyst promoter. This is necessary for treating difficult to sweeten kerosine and distillate streams derived from various crude sources,709001 XXI-6. d. Merox Minalk This version of the process began in the early 1970’s and has become well accepted in the industry. As the name suggests, this variation refers to the minimum use of alkali (minalk). It is presently applied to stocks that are relatively easy to sweeten, like light to heavy catalytically cracked naphthas in addition to light virgin naphthas with endooints of up to 350- 370°F (175-190°C). The Merox Minalk process relies on a small, controlled, continuous injection of an appropriate strength alkali solution rather than gross intermittent alkali saturation of the catalyst bed as instituted in conventional Merox fixed bed sweetening. Thie continuous, small injection of alkali, such as atlute sodium hydroxide solution (2-5 wppm) is held to @ minimum but enough to provide the needed alkalinity such that mercaptans arc oxidized to disulfides and do not enter into a peroxidation reaction in case of insufficient alkalinity. The basic flow scheme is similar to that of the conventional fixed bed unit, but involves a minimum of equipment. As previously mentioned, this version of the process has virtually replaced the 11quid-11quid process in all its applications. Protreatment and Post Treatment For Merox extraction and for sweetening systems, pretreatment and Post treatment are frequently required depending on feed characteristics, treated product specifications, and end-use.709001 XXI-7 Pretreatment For light stocks such as LPG or possibly light gasoline where more than low ppm levels of hydrogen sulfide ere ur may be Present, the charge stock is passed through a guard caustic scrubber to ensure essentially complete removal of HpS which, if Present in the charge, will cause excessive consumption of caustic solution containing Merox catalyst. Hydrogen sulfide does not poison the catalyst but rather competes with mercaptans for the available catalytic sites and available oxygen. Virgin petroleum fractions boiling higher than about 300°F (180°C) may contain naphthenic acids which have several objectionable properties when present in a product and which interfere with treating operations, regardless of the type uf process used. In general, therefore, naphthenic acids must be reduced to tolerable level prior to treatment. This is usually achieved using an alkaline prewash. With conventional Merox fixed bed sweetening, the catalyst bed is maintained wet with caustic. If naphthenic acids are not removed, sodium naphthenates are formed, which being Surfactants, coat the catalyst and block the pores of the charcoal catalyst support. Ins requires more trequent hot water washing of catalyst in order to maintain the catalytic activity needed to obtain a Doctor negative product or the specified mercaptan content of the product. UoP recommends that effective pretreatment be used in conjunction with Merox sweetening of virgin stocks having an Acid Number greater than about 0.01 mg. KOH/gm. It should be recognized that this is an arbitrary value and that it could be greater or Tess depending on the specific stock and circumstances. The usual procedure is to wash the feed with aqueous caustic soda.709001 XXI-8. b. Post Treatment Post treatment varies with the product specifications and end- use but normally consists only of a sand filter to coalesce any caustic haze that might be present. An example of extensive post treating ic that needed far jet fualce Pact treatment could include a water wash to remove entrained caustic solution and water-soluble surfactants which may have been present in the Jet fuel feed to the unit. 4. Merox Adv: Relative to other treating processes, the Merox Process nas the following advantages: a. Low operating cost and investment requirement. The non- corrosive environment in which the pracess operates requires no alloys or other special materials, thus minimizing investment; investment in many applications is essentially nil based on the conversion of existing equipment to Merox treating. Utility and chemical requirements are minimal. Ease of operation - Merox process units are simple to operate; ‘the arr injection rate 1s tne only direct adjustment necessary to accommodate wide variations in feed rate or mercaptan content. Operating labor requirements are minimal. ©. Draven reliability - The Meraox process has been widely accepted by the petroleum industry; many units of various kinds (extraction, liquid, and fixed bed sweetening) have been placed in operation. Minimal chemical disposal requirements.709001 XXI-9 Proven ability to produce specification products - The is no damage of product deterioration due to side reactions or addition of undesirable materials to the treated product. This ie cepecially important for jet fuel treating in that in the Merox process, sweetening is carried out in the presence of only air. caustic soda solution, and a catalyct which 4 both hydrocarbon and caustic solution and cannot, therefore, have a detrimental effect on other properties which are important to fuel specifications. The importance of this is best illustrated by listing the materials not present in the Merox process. insoluble in (2) Copper The proconce of minute quantities of copper in the product causes failure in the thermal stability (coker) test and in the case of cracked gasolines promotes gum formation in storage. The copper sweetening process is very prone to this failure. (2) Lead Lead mercaptide is oi] soluble, and if present in the Product, 18 supsequentiy oxidized in storage to lead oxide and disulfide, leaving finely divided lead oxide in suspension. This will result in failure on the water separometer and clarity specifications, and cause filter clogging. The Doctor sweetening process and its other variations must have very close control of lead mercaptide in the product.709001 XXI-10 (3) Elemental Sul fur Some processes require the addition of elemental sulfur. Ite quantity must be regulated with changes in mereaptan content in the feed, otherwise excessive mercaptan or elemental sulfur could easily cause sour product or failure of the copper and/or the silver strip corrosion tests. This occurrence is common with the Doctor sweetening process. -c¢ To fully understand the Merox process and how it can be applied to such a broad range of treating problems, it is necessary to review the basic chemical reaction of the process and how it is applied in a variety of ways. UOP may have been remiss in using the name "Merox" to designate a variety of applications of a single catalyzed chemical reaction. The use of a single name to designate what may appear to be a multiplicity of processes has unfortunately been the cause of some confusion in understanding the various applications ot the process. ‘The Herox process in all of its applications is based on the ability of an organo-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 will proceed only in an alkaline environment. The overall reaction can be written: RSH + 1/4 02 =: mm> 1/2 RSSR + 1/2 Hy0 a)709001 XXI-11 R is a hydrocarbon chain which may be straight, branched, or cyclic. These chains may pe saturated or unsaturated. In its various aspects, under the proper circumstances, and depending upon the results desired, it 12 applicable to the treatment of stucks bull ing up to 650°F (345°C) endpoint. There are two principal divisions in the application of this reaction: Extraction, in which the mercaptans are more or less completely removed from the hydrocarbon using caustic soda solution as the extraction solvent. The caustic is then regenerated by bringing it into contact with air and catalyst to bring about oxidation of mercaptans to disulfdies. Finally, the disulfides, which are insoluble in the caustic, are separated from the regenerated (lean) caustic. Sweetening, in which a hydrocarbon containing mercaptans is brought into contact with caustic soda solution, air, and catalyst to convert the mercaptans to oil-soluble disulfides without changing the sulfur content of the hydrocarbon. 1. Extraction Extraction is applied to both gaseous and liquid hydrocarbon streams. The degree of completeness of mercaptan extraction depends upon the solubility of a mercaptan in the alkaline solution. That, in turn, depends primarily upan the Following: molecular weight of mercaptan degree of branching of mercaptan molecule caustic soda concentration temperature of the system709001 XXI-12 As the molecular weight of the mercaptan increases, solubility in the alkaline solution decreases, and as chain branching increases, solubility decreases. The following equation illustrates the mechanism of mercaptan extractian: RSH + Hed @ on Aqueous Aqueous Phase —Phase Phase The ability of the Merox process to completely regenerate caustic for reuse depends on the following equation: MaSR + 1/4 Oz + 1/2 HzO =====7 NOH + 1/2 RSSR @) Aqueous ‘Aqueous Aqueous Phase Phase Incolublo Using the extraction route, the sulfur content of the treated Product will have a reduced sulfur content by the amount of. mercaptan extracted 2 ning Sweetening is applied to distillates containing mercaptans which cannot be more or less completely removed by caustic extraction. Sweetening converts the mercaptans to disulfides which remain in the distillate. Sweetening takes place by contacting the mercaptan containing distillate with caustic soda solution, air and catalyst. The overall sweetening reaction is given by the following equat ior 2 R°SH + 2 RSH + 0p =meme> 2 RYSSR + H70 (9)709001 XXI-13 R and R’ represent hydrocarbon chains. In most petroleum fractions, there will be a mixture of mercaptans to the extent that the R chain might have 1,2,3.... 10 or more carbon atoms in the chain. When this reaction occurs, two difforant morcaptane might enter the reaction. This is indicated by showing R and R’ in the reaction. This reaction occurs spontaneously, but at a very slow rate, whenever any sour mercaptan bearing distillate is exposed to atmospheric oxygen. It is the purpose of a sweetening process to speed up this reaction. Most sweetening processes do this indirectly by using supplemental chemical reagents. In about 1958, UOP introduced the Merox process which directly speeds up this reaction at or near anbient Lemperature by using a unique catalyst. dispersed in an alkaline environment. It is believed on the basis of UOP studies, that the mercaptan, or at least the thiol (-SH) functional group, first transfers to the aqueous alkaline phase (Figure 4) and then combines with the catalyst. The simultaneous presence of oxygen causes this mercaptan-catalyst complex to oxidize, yielding a disulfide molecule and water. D.__Commercial Experience and Feedstock Applications As of December, 1985, more than 1,600 Merox units have been licensed; more than 1300 of these units representing in excess of 10,000,000 barrels per stream day capacity have been commissioned. The total design capacity of all units exceeds 12,000,000 barrels per stream day.709001 XXI-14 ‘The various applications of the operating units are distributed percentage-wise approximately as follows: Extraction 30% Extraction + Sweetening 13% Liquid-Liquid Sweetening 27% Conventional Fixed Bed Swectening 22% Minalk Fixed Bed Sweetening &% ure 1 MERCAPTIDE AT INTERFACE033 (ousnva gaczt woLowae swmaua ‘Xow ‘usnvs aNd Lae/ANISOWA> HO4 LNAWLVSYL LSOd/dud VIN4 H.LIM G38 GAXI4 TWNOLLNSANOD SSHOOUd KOWGH don ST-IXX Too60Lwvals ‘a aaas uly LNadS ALIOVUHLNY HS3WW 8+) HOLVHVd3S ore ‘agi1Nsia valid (sont DIMOSVH ONY ousnvs NORHYD ..%t) St-Obl WaZIGIXO Hvala ‘USNS woLovuLXa WwTDwIKa ssao0dd KON Jon 9T-IXX Too6OL — 8 - . [email protected]...