ett Uop ZEOLITIC ISOMERIZATION PROCESS GENERAL OPERATING MANUAL - Limited Distribution - ‘This material is UOP's technical information of a confidential nature for use ‘only by personnel wihin your orpahization requ the Information, “The material shel sot Be in or isttbuted for any purpose whatsoever ence by wriRen permision of UCP and a3 authorized under agreemens with LF February, 1963:Vi. vu. TABLE OF CONTENTS INTRODUCTION GLOSSARY OF TERMS. PROCESS DESCRIPTION PROCESS CHEMISTRY moom> Isomerization Catalyst Feedstock Components Isomerization Isomerization Chemistry Monitoring Catalyst Peformance: Product Ratios PROCESS VARIABLES moom> Reactor Temperatures Reactor Pressure Space Velocity Feed Composition Hydrogen fo Hydrocarbon Ratio PROCESS CONTAMINANTS. PRECOMNMISSIONING ACTIVITIES. CAL "Lommoom> Check Unit Inspect Tower and Vessel Intemals Hydrostatic Testing Clean and Service Utility Systems Line Flushing Initial Run-in of Pumps and Drivers Instrument Checkout Dryout of Fired Heaters Initial Run-in of Compressor Fin-fan Exchangers Run-in Reactor Circuit Dry-out Catalyst LoadingVIL XL XIL START-UP PROCEDURES A. Preparation for Start-up Plant Purge B. C. Stabilizer Start-up BD. Reactor Section Start-up SHUTDOWN PROCEDURE EMERGENCY PROCEDURES LABORATORY TEST SCHEDULE. CATALYST REGENERATION PROCEDURE147060 - I. INTRODUCTION The component of many refinery gasoline pools which frequently offers the best opportunity for quality improvement is the pentane-hexane fraction. Light straight run naphtha, which is the source of the bulk of this material, is characterized by a low octane number, typically 65-70 research clear. Generally, this light straight run fraction which constitutes approximately 10% of a typical gasoline pool has been blended directly into gasoline without additional processing, except perhaps treating for mercaptan removal. Its low octane was compensated for by its excellent lead susceptibility (i.e., the octane number increase affected by the addition of lead) of approximately 16 to 18 numbers, This placed the Cs/Cg straight run in the position of being that segment of the gasoline pool helped most by the addition of lead and least in need of upgrading by processing. When the petroleum industry moved toward marketing fuels with lower lead levels, it became increasingly difficult to use light straight run in the gasoline pool, Conversion of the low octane Cs/Cg normal paraffins to their corresponding branched isomers in order to increase their clear octane number is recognized as a logical and necessary step in a lead reduction program. UOP has a number of catalytic processes that allow the refiner to achieve this goal. The Zeolitic Isomerization process is one such scheme. The Zeolitic Isomerization Process utilizes a zeolitic hydro-isomerization catalyst system that is specifically designed for the continuous catalytic isomerization of pentanes, hexanes, and mixtures thereof. The reactions take place in the vapor phase in a hydrogen atmosphere, over a fixed catalyst bed at conditions, which promote isomerization while minimizing undesirable side reactions, such as hydrocracking. Ideally, the isomerization catalyst would convert the feed paraffins to the highest octane-number branched structures, ie.. Cs to isopentane and Cg to dimethylbutanes. However, the isomerization reaction is equilibrium limited. The C5147060 12 paraffin mixture will consist of low octane normal pentane and high octane isopentane, in a concentration determined by the equilibrium at the reactor outlet. The Cg isomer equilibrium distribution is approximately evenly split between high octane dimethyl butanes and lower octane methyl pentanes, and some low octane normal hexane. Since the lower octane methyl pentanes are present, this fraction offers a lower product octane potential than the Cs fraction. Feedstock to the Zeolitic Isomerization unit does not generally require costly or elaborate feed pre-treatment. Sulfur has a depressing effect on the isomerization catalyst activity, and should be removed from the feed either by conventional hydrotreating or with UOP's proprietary SafeCat technology, which, when integrated with the Zeolitic Isomerization unit, achieves substantially complete desulfurization at a considerable cost and utility savings over hydrotreating. Small amounts of benzene, Ce naphthenes, and C7 hydrocarbons may be tolerated in the feed to the Zeolitic Isomerization unit. However, sending the cyclohexane and C7's to the catalytic reforming unit offers the best octane upgrade potential. In the Zeolitic Isomerization reactor, high octane benzene quickly saturates to lower octane cyclohexane. This reaction is very exothermic. In addition, C7 material in the feed is also associated with large exotherm on the catalyst, excessive cracking, yield loss, and accelerated catalyst deactivation. For this reason, the sum of benzene and C7 plus material in the feed to the Zeolitic Isomerization unit should be maintained at less than 5 wt%. This is achieved by adjusting the operation of the feed prefractionation facilities. Water, in concentrations typically found in the naphtha splitter overhead (200-400 ppm) has ttle effect on the Zeolitic Isomerization Process. At higher concentrations, water does have a detrimental effect on catalyst activity. Charging free water to the unit should be avoided at all costs, since permanent damage to the isomerization catalyst will result. Olefins are not normally present in light straight run. If present in the feed, the olefins are quickly saturated to paraffins in the isomerization reactor. Like the147060 Rev.1 is benzene saturation reaction, olefin saturation is exothermic, and the amount of olefins in the reactor feed should be minimized. With time the hydro-isomerization catalyst will slowly become deactivated, primarily due to the slow build up of coke on the catalyst, which restricts the number of active sites available for isomerization. As the catalyst activity drops, it is manifested as a decline in the conversion of the paraffins to their isomers, and a decline in the product octane. The catalyst activity may be wholly or partly recovered by regenerating the catalyst. The regeneration procedure is simple, and, where coke is the primary agent of deactivation, highly effective.ISOM. RX. { \& HEAT EXCH. Ss P reep | L FROM | J NET | op RECYCLE @ T E GAS R PLATFORMER, 147060 Rev. 1 ia ISOMERIZATION UNIT STABILIZER Q COND. & SEP. L ISOMERATE TO STORAGE147060 Rev. 1 is SIDE-CAR ISOMERIZATION UNIT a Ss P FEED L FROM I NHT T PROD. eT STABILIZER 8 E R (7 [PLATFORMER147060 Rev. 1 Tet Il. GLOSSARY OF TERMS USED Product Ratio - The degree of isomerization taking place in the reactor. It is the weight or mol% of isoparaffins in the total paraffins found in the reactor effluent separator liquid, Equilibrium Product Ratio — Since the isomerization reaction is an equilibrium reaction, a mixture approaching an equilibrium mixture of iso and normal paraffins will be reached at the reactor effluent. The equilibrium product ratio is the highest product ratio attainable at a given temperature. Achieving it would require an infinitely long reactor residence time. In practice, therefore, the product ratio will be less than the equilibrium product ratio. Catalyst Activity - The activity of the Hydro-isomerization catalyst is a measure of its ability to convert normal paraffins to isoparaffins. As the catalyst ages, its activity drops due to coke build up or due to catalyst poisons in the feed stock. Delta Temperature - The Delta "T" is a short cut symbol used when referring to the temperature rise across the catalyst bed. It is related to the exothermicity of the reactions taking place in the bed, Since benzene saturation and hydrocracking are highly exothermic reactions, the Delta "T" increases with increasing amounts of these constituents in the feed. Liquid Hourly Space Velocity (LHSV) - The liquid hourly space velocity is a term which relates feed rate over the catalyst with catalyst volume. The units are volumes of Cg plus hydrocarbon over the catalyst per hour per volume of catalyst. In general, the higher the LHSV, the shorter the feed residence time in the reactor. Hydrogen:Hydrocarbon Ratio (H2/HC) — This is the ratio of the moles of hydrogen to the moles of Cs plus hydrocarbon to the reactor.147060 Rev. 1 we Partial Pressure — The partial pressure of a component in a vapor phase system may be approximated as the product of the mole fraction of that component in the system and the total pressure of the system. For example, if the reactor outlet pressure is 36 kglem2A (512 psia), and the hydrogen content of the reactor effluent is 50 mol % hydrogen, then the hydrogen partial pressure at the reactor outlet is 18 kg/cm2A (256 psia). Temporary Poisons — A temporary poison has the effect of lowering the catalyst activity while it is in the presence of the catalyst. The catalyst may recover activity by either regeneration or by the removal of the temporary poison from the feed. Coke on the catalyst is an example of a poison that may be removed by regeneration; moisture in the feed (at below saturation levels) is an example of a temporary poison which, when removed from the feed, results in a recovery of the temporarily lost activity. Permanent Poisons — Permanent poisons are compounds which permanently affect catalyst activity. Examples of permanent catalyst poisons are metals such as sodium and arsenic. Catalyst regeneration will not recover activity lost due to permanent poisons.147060 Rev 1 Met lll. PROCESS DESCRIPTION The UOP Zeolitic Isomerization Process is a catalytic isomerization process employing HS-10 catalyst to convert low octane hydrocarbons into higher octane hydrocarbons in the presence of hydrogen. The reactor section is equipped with one or more reactors, a product separator, a compressor for recycling hydrogen and a charge heater to heat the combined reactor feed material. In a single reactor scheme, multiple beds are used. The Zeolitic Isomerization Process consumes hydrogen; therefore a continuous hydrogen makeup is necessary. The fresh feedstock, which is rich in low octane normal paraffins, joins the hydrogen recirculation stream and, after heat exchange with the reactor effluent, passes through the heater and into the lead reactor. In the lead reactor or single reactor top bed, a portion of the normal paraffins is isomerized to isoparaffins. A higher octane distribution of iso-hexane is also achieved by increasing the relative concentration of dimethyl butanes. Some ring opening of naphthenes, hydrogenation of aromatics, and feed cracking to butanes and lighter materials also occurs. Since the aromatics saturation and cracking reactions are highly exothermic, the lead reactor effluent is cooled by either cold hydrogen quenching or heat exchanging with a cold stream to take advantage of the improved isomer distribution at lower temperatures, as well as to minimize cracking (yield loss) in the lag reactors. The final isomerization occurs in the lag reactor or single reactor bottom bed, along with some hydrocracking side reactions. The reactor performance parameters (i.¢., the product ratios and yield) are dependent on space velocity, feed composition, operating temperature, and the condition of the catalyst.147080 Rev. 1 M2 Adjusting the inlet temperatures to the lead and second reactors regulates the extent of conversion and cracking. The reactor temperatures are set to achieve an adequate product ratio without excessive yield loss.147060 Rev. 1 ti-3 The lag reactor effluent material is heat exchanged with the combined feed, condensed, and collected in a separator. The hydrogen from the separator is circulated back to the reactor with the recycle compressor. The hydrogen circulation rate is such that the mol ratio of hydrogen te hydrocarbon is 1.0. The separator liquid is pressured to the stabilizer column where the C4 minus material is taken overhead. The Cs+ isomerization product leaves the bottom of the tower and is sent to gasoline blending. An net LPG stream is taken from the stabilizer overhead.Typical Isom. Unit Flow Scheme Isomerate M/U Gas 147060 Rev. 1 ik147060 eV. 5 Typical Two Reactor Isom. Unit Recycle po Gas : Reactor Reactor 1 2 m1 To StabilizerTypical Stabilizer Flow Scheme Unstabilized Isomerate from Separator Stabilizer Tsomerate147060 Rev. Wet IV. PROCESS CHEMISTRY The isomerization process is a fixed bed, vapor phase system for the catalytic isomerization of low octane normal pentane and normal hexane to higher octane isoparaffins. The isomerization reaction is typically carried out at approximately 15 kg/cm2G to 35 kg/cm2G (215-500 psig) in the presence of hydrogen. The catalyst is a noble metal loaded zeolitic catalyst that does not require a halide activator. The catalyst has good stability, and is regenerable when coke is the deactivation agent. Most refiners have experience with zeolitic catalysts in catalytic cracking and hydrocracking service. A. ISOMERIZATION CATALYST The catalyst is a platinum loaded zeolitic catalyst with the following physical properties: Designation HS-10 Catalyst Particle Size 4.6mm Shape Extrudate Bulk Density 680 kg/m? 42 Ib/ft (approximately) Color Cream Platinum Loading 0.31-0.35 Weight percent The catalyst does not contain a halide activator. Due to changes in the catalyst manufacturing process, activation of the catalyst is no longer necessary. B. FEEDSTOCK COMPONENTS Feedstock to the isomerization reactors should be predominantly paraffinic and consist of a mixed Cs/Cg cut. The feedstocks will normally contain some other147060 We hydrocarbon types, the effect of which has been carefully evaluated in both pilot plant and commercial operations. Butane-and-lighter paraffins pass through the catalyst reactor unaffected, and can be treated for all practical purposes as inert with respect to the catalytic reaction, Heptane and heavier paraffins are hydrocracked by the isomerization catalyst, and in addition can promote cracking of the Cs and Cg paraffins. The major by- products (approx. 90%) are i-butane, n-butane, and propane. For optimum results, the C7+ content of the feed should be kept below 2 volume percent. Benzene is rapidly hydrogenated to cyclohexane without any harmful effect on catalyst performance. However, for benzene feed concentrations higher than several percent, the temperature rise at the inlet end of the catalyst bed can become significant enough to have a detrimental effect on isomerization conversion and yield, due to high bed temperatures. In this situation, an intermediate quench will control the overall temperature rise in the reactor section Naphthenes undergo substantial ring opening. The extent of ring opening increases with increasing temperature. Since any benzene in the feed is rapidly hydrogenated to cyclohexane by the catalyst, benzene can be effectively treated as. Cg naphthene when analyzing the effect of naphthenes in the feed or product composition. Figure IV-1 demonstrates the effect of cyclics on the conversion to |-pentane and 22 dimethylbutane. The term X-factor is the sum of the C, cyclies and the C," compounds. It is theorized that the C, cyclics adsorb on the active sights of the catalyst thereby inhibiting the normal paraffins, This effect raises the liquid hourly space velocity and requires a higher temperature to compensate for the lost active sights. The C, cyclics will desorb readily when the feedstock is changed to lower cyclics.147060 Rev. 7 W3 One way of compensating for the C, cyclics is by using the knowledge that more C, cyclic rings open into paraffins at higher temperatures. in a dual reactor system, the lead reactor temperature can be increased to lower the cyclics going to the lag reactor. The lag reactor would then be more active at the lower temperature. Higher isomerization conversion would results, but more cracking to light ends resulting in a yield oss would be observed. Methyicyclopentane (MCP) and cyclohexane exist at equilibrium at the reactor outlet conditions, As the temperature is increased, more of the higher octane MCP is produced. Olefins are rapidly hydrogenated without catalyst coking, and then behave as their paraffin counterparts, A temperature rise is associated with the hydrogenation which, if significant, could have a detrimental effect on the conversion and yield in the reactor. A small amount of hydrogen, typically of the order of 0.5 wt.% of the feed, is required to replace that consumed in the slight hydrogenation and hydrocracking side reactions. The source of this make-up hydrogen is usually reformer make gas which is sometimes further processed by a POLYBED PSA Unit. C. ISOMERIZATION The term isomer refers to compounds which have the same molecular formula but different structural formula or different arrangement of molecules. In general, compounds that are linear or straight chain are termed normals; if they are in a different arrangement, (i.e., branched) they are termed isomers.Examples n-pentane CsHy2 CH,-CH,-CH,-CH,-CH, pentane C.Hyp CH, I CH,-CH-CH,-CH, 147069 W-4 Pentane has five carbon atoms. When in ‘straight chain as shown this is called normal pentane or n-pentane. The octane number (RON) of n-pentane is about 62. This is isopentane, an isomer of n-pentane, it has the same molecular formula but a different arrangement or structure. Isopentane has a research octane number (RON) of 93. Isomerization is simply the conversion of compounds to their isomer, i.e., to a higher octane arrangement. ‘Similarly with hexane n-hexane C,H, (CH,-CH,-CH,-CH,-CH,-CH, i-hexane CH, | CH,-C-CH,-CH,, I CH, Hexane has six carbon atoms. When in a straight chain as shown this is called normal hexane or n-hexane. The research octane number (RON) of n-hexane is about 25. This is i-hexane, one of the isomers of the n-hexane. Again, it has the same molecular formula but a different arrangement. This is called 2,2, - Dimethyibutane (2,2DMB) and has a research octane number (RON) of above 92.147060 Rev. 1 V5 D. ISOMERIZATION CHEMISTRY No attempt is made here to present the mechanisms of the process chemistry to a degree of sophistication acceptable to a chemist specializing in the area. The intention is simply to provide practicing engineers with a basic introduction to the subject. The first step in the isomerization process is the formation of an olefin intermediate by the platinum. (1) CHy-CH,-CH,-CH,-CH, —™> CHy-CH,-CH,-CH=CH, +H, This reaction is reversible and, since the catalyst is under substantial hydrogen pressure, the equilibrium is far to the left. However, the acid function of the catalyst consumes the olefin by the formation of a carbonium ion and thus permits more olefins to form despite the unfavorable equilibrium. e (2) CHy-CH,-CH;-CH=CH, + H+A > CH,-CH,-CH,-CH-CH, + Ar The usual arrangement ensues: CH; i (3) CHs-CH,-CH,-CH-CH, -> CH-CH,-C-CH, e e The iso-olefin is then formed by the reverse analog of (2): CH, CH, | l (4) CHy-CH,-C-CH, +A" > CHy-CH,-C=CH, + H*A7 ®147060 Ve The iso-paraffin is finally created by hydrogenation across the platinum site: CH; fis | (8) CHyCH,-C=CH,+H, —B> CHy-CH,-CH-CH, As the isomerization reaction progresses, hydrocracking takes place. The rate of hydrocracking increases as the temperature is raised. The isomerization reaction is slightly exothermic at a rate of 2,200 K-cal/kg-mole. In the presence of the catalyst, and at appropriate conditions, @ portion of the normal pentane and normal hexane will convert to their isomer. This conversion is determined by equilibrium; i.e., a certain percentage or equilibrium amount will exist at given operating conditions. This, then, is the measure of the performance of the isomerization reactors; i.e,, the percentage of the isomer in the reactor effluent. The conversion of n-pentane to i-pentane, and n-hexane to 2,2DMB, are only two of the many isomerization reactions which occur in the isomerization process. Figure II-2 shows equilibrium compositions of i-pentanes and the i-nexanes versus temperature. Note that these equilibria are imposed by thermodynamics, and can only be achieved after an infinite length of time, (i.e., with an infinitely long reactor). In practice, therefore, the reactor effluent will contain less than these equilibrium ratios of isoparaffins. As the reactor feed rate is decreased, (higher residence times), or the temperature is increased, the equilibrium composition will be more closely approached. At excessively high temperatures, the concentration of isoparaffins in the reactor effluent will actually slightly decrease because of the downward shift in the equilibrium curve, even though the high temperatures will result in higher reaction rates, The use of temperatures higher than necessary to achieve a reasonably close approach to equilibrium will accomplish nothing other than to increase the amount of hydrocracking, thereby reducing the product yield. High temperatures447060 Rev. 1 NT will also lead to premature deactivation of the catalyst, due to the increased rate of coke laydown on the catalyst. As the catalyst ages, its activity will slowly decline due to the effect of gradual coke laydown and of any catalyst poisons which may be present in the feed stream; this, will result in increased amounts of unconverted normal paraffins in the reactor effiuent, and feed to the adsorber section. To maintain product octane, it will be necessary to increase the reactor temperature. However, if increasing the peak catalyst bed temperature to 295°C (560°F) does not produce the desired reduction in the normals content of the reactor effluent stream, catalyst regeneration should be considered. Some reactions other then isomerization take place, which may have a negative effect on the product octane and yield: (a) Benzene Hydrogenation This reaction takes place readily in the first 10% of the catalyst bed. It is accompanied by a large exotherm of approximately 50,000 K-cal/kg-mole, consumption of hydrogen and a negative octane effect, i.e., benzene converting to its lower octane arrangements, cyclohexane or C, paraffins. (b) Ring Opening (Naphthenes) This reaction also takes place readily producing an exotherm of approximately 14,100 K-callkg-mole. () Paraffin Hydrocracking This reaction is catalyzed by the acidity of the catalyst. It increases with increasing temperature, and produces an exotherm of approximately 11,100 K-cal/kg-mole, This reaction should be minimized by controlling reactor temperatures to preserve yield. Heavier hydrocarbons crack much more readily than lighter species. At147060 Rev. 1 V8 normal operating conditions, only a small a small amount of the C, and C, paraffins crack. However, a significant portion of the C,'s, (on the order of 40 to 80%, depending on the reactor temperature and catalyst activity) charged to the unit will crack to C, and lighter material. £, MONITORING CATALYST PERFORMANCE: PRODUCT RATIOS Catalyst performance should be monitored by calculating the product ratios. The product ratio is defined as the weight percentage of the key isomer component to the total aliphatic paraffins of the same carbon number. For example, the isopentane product ratio is equal to the wt% i-Cs in the reactor effluent, divided by the total wt percent of i-Cs and n-Cs in the reactor effluent. For consistency, the Product ratios are expressed on a percentage basis. Ideally, the reactor effluent product ratios would be similar to the equilibrium product ratios. However, close approach to the equilibrium product ratios can only be achieved with extremely long reactor residence times. In practice, then, the product ratios are lower than the equilibrium product ratios; the closeness with which these approach the equilibrium product ratios depends on the liquid hourly space velocity, the reactor temperature, and the catalyst condition. The flow rate of recycle hydrogen also plays a minor part, by affecting the residence time in the reactor. ‘As reactor temperatures are increased, a point is reached beyond which the product ratio shows only a marginal or even no improvement, while the liquid yield decreases due to excess hydrocracking. At constant reactor temperature, decreasing the reactor feed rate (liquid hourly space velocity) has the same effect of increasing the severity of the reactor operation. Thus, in planning for a reduction in the feed rate to the reactors, it is important to anticipate the direction in which the reactor temperatures should be tuned. If the feed rate is to be decreased, first decrease the reactor temperature, then the feed rate. Once the new feed rate has been established, the temperature may be optimized, by monitoring the product ratios.If the feed rate is to be increased, the reactor temperature should be adjusted based on the product ratios) only after the feed rate change has been made.147080 -40 FIGURE IV-1 EFFECT OF X-FACTOR ON ICS PROD. RATIO} All data at 96 wt% C5+C6 yield 3 a WHsve1.6 z+ y WHSV=2.5 3 2 z 15 & 20 i 25 o 6 10 5 20 25 30 36 FEEDSTOCK X-FACTOR, WT% EFFECT OF X-FACTOR ON 22DMB PROD. RATIO All data at 96 wt% C5+C6 yield ° WHSV=1.6 g 4 a. 3 WHSV=25 2s é Ea Q + 4 o 6 10 16 20 25 0 36 FEEDSTOCK X-FACTOR, WT%Figure IV-2 147080 Rev. 1 watt Mole Fraction 09 08 a7 06 05 04 Vapor Phase Equilibrium Curves 420 216 440 460 480 «500 520 840 227-238 249260271282 560 580 203 304 600 316147060 Rev 1 Vel V. PROCESS VARIABLES The purpose of this section is to discuss the principle process variables, and to ‘examine the effect that these have on unit performance. The process variables which may be used for controlling the unit performance are: Reactor Temperature Reactor Pressure Space Velocity Feedstock Composition Hydrogen/Hydrocarbon Ratio. moom> The catalyst activity also affects the operation, but this variable is not normally within the control of the operator. A. REACTOR TEMPERATURE The catalyst bed temperature is the prime and most sensitive variable available to control product yield and quality. Temperatures higher than necessary will generally enhance conversion but will increase cracking and coke laydown, resulting in a lowered product yield and accelerated catalyst deactivation. Therefore, an optimum temperature is determined by balancing conversion and yield. Increasing the temperature above the optimum will cause a rapid decrease in yield with only marginal improvement in conversion or octane number, and lowering the temperature below the optimum will lower conversion with little gain in yield. Optimum reactor inlet and outlet conditions can change with feedstock variations. The temperature operating window for catalyst activity is typically from 240 to 295°C (460-560°F), Temperature control can be split into two areas:147060 Rev. 1 v2 Lead reactor catalyst bed inlet temperature - This is controlled by monitoring the temperature of the combined hydrogen-hydrocarbon feed entering the reactor. The reactor inlet temperature should be adjusted based on the delta T across the lead reactor. This delta T will change with the concentration of benzene and heptanes in the reactor feed; the greater their concentration, the larger the delta T. The reactor inlet temperature should be adjusted upward or downward to hold a relatively constant reactor outlet temperature. High catalyst bed temperatures due to exothermic hydrogenation and cracking reactions should be avoided. For most feedstocks, the lead reactor inlet temperature range should be in the range of 240 to 260°C (460-500°F). The bed outlet temperature should be in the 260 to 295°C (500-560°F) range. The lead Reactor outlet temperature is only limited by the metallurgical limitations of the reactors. Therefore, the reactor temperatures should only be raised enough to obtain product quality. Occasionally, an upset in the naphtha splitter operation may result in a sudden increase in the benzene and/or heptane content of the feed; in this event, the lead reactor inlet may be lowered below 240°C (460°F). However, the feed temperature should never be allowed to fall below about 210°C (410°F), due to concerns about condensing hydrocarbon on the catalyst. Condensed hydrocarbon on the catalyst will form coke and potentially alter the structure of the catalyst resulting in permanent catalyst deactivation. Note that due to a phenomenon known as capillary condensation, hydrocarbon may condense on the catalyst at temperatures well above the dew-point of the feed. It is typical to maintain at least a 30°C (50°F) margin over the dew-point. Lag reactor catalyst bed inlet temperature - This controls the extent of the isomerization reaction; i.¢., the final conversion occurring in the last two reactors. For a feedstock containing benzene, olefins, or heptanes, the lag reactor will normally show a much smaller delta T then the lead reactor. This is because most of the highly exothermic hydrogenation and cracking reactions take place in the lead reactor. The lag reactor inlet temperature is controlled by injecting a cold hydrogen quench stream at the inlet to the second reactor bed. The inlet temperature should be adjusted based on the reactor effluent separator liquid147080 Rev.1 v3 SS product ratios. A typical lag reactor inlet temperature range is 250 to 277°C (480- 530°F). B. REACTOR PRESSURE Pressure has little or no effect on product yield and quality over the range of typical operating pressures. Operation at higher pressures tends to suppress the rate of coke formation. Conversely, operating at too low a pressure will slightly accelerate the rate of coke laydown on the catalyst. If the pressure (or the recycle hydrogen rate) is allowed to drop such that the hydrogen partial pressure at the reactors is less than 9.8 kg/cm?A (125psia), the rate of coke laydown on the catalyst increases dramatically. . SPACE VELOCITY Space velocity is a measure of the amount of naphtha which is processed over a given amount of catalyst over a set period of time. The liquid hourly space velocity (LHSV) is the ratio of the volume of Cs+ hydrocarbon processed per hour over the catalyst to the volume of the catalyst. When weights are used, the term is WHSV, weight hourly space velocity. Space velocity affects product quality. Lower space velocity, i.e, 2 lower reactor charge rate, increases the number of active catalyst sites per molecule of hydrocarbon. This causes higher conversion and increased cracking. Decreasing reactor temperatures will offset this effect. Conversely, operation at higher space velocities will require higher reactor temperatures to offset the shorter residence time of the feed in the reactor.147080 Rev.1 V4 D. FEED COMPOSITION Feed composition is an indirect variable, a variable the operator reacts to rather than controls. Changes in the feedstock composition will have an effect on the octane of the isomerate product. This occurs due to differences in the blending octanes of the Cs and Cg isomers. In general, the higher the feedstock pentane content, the higher the isomerate octane. The operator must try to minimize the effect that changes in the feedstock may have on catalyst performance and product yield. Directionally, the following adjustments should be made: Variable Adjustment Higher benzene content Operate at a lower lead reactor inlet temperature because of the higher delta T. Higher C7’ content Reduce lead and lag reactor inlet temperatures because of higher delta T. Lower Cs/Ce ratio Operate at a higher average bed temperature because the conversion is more difficult with a heavier feedstock —. HYDROGEN/HYDROCARBON RATIO The hydrogen-to-hydrocarbon ratio is the molar ratio of hydrogen to Cs plus material in the charge. The hydrogen must be circulated over the catalyst at all times, to keep the catalyst free from coke buildup. In general, the hydrogen-to- hydrocarbon ratio should be maintained at about 1.0. Operation at a significantly lower ratio can result in premature coking of the catalyst, while a high ratio results in aneediess waste of utilities.147080 Rev. 1 via Vi. PROCESS CONTAMINANTS The purpose of this section is to discuss and highlight the effect of various catalyst poisons, both permanent and temporary. ‘Sulfur — Sulfur depresses catalyst activity even when present at fairly low levels in the feed (less than 5 wt ppm). The isomerization catalyst converts all of the sulfur in the feed to HzS; the platinum on the catalyst becomes sulfided, resulting in a deactivation of the platinum activity. Over a long period of time, the platinum activity is completely lost. Since the platinum is responsible for the hydrogenation function, platinum poisoning (by sulfur) is usually seen as loss of benzene saturation to cyclohexane. Most of the sulfur may be removed by performing a hot hydrogen strip on the catalyst. Metals — Arsenic, lead, copper, mercury, and sodium are permanent catalyst poisons which will suppress the platinum activity as well as neutralize the acid sites of the isomerization catalyst. Any possible source of contamination with these materials should be carefully investigated Nitrogen — Nitrogen compounds will be absorbed on the zeolitic isomerization catalyst, reducing the active sites available for paraffin isomerization. This will show up as a decline in the reactor effluent product ratios. Most of the nitrogen can be stripped off the catalyst by sweeping it with high temperature hydrogen, resulting in a partial recovery of activity. However, the activity will not fully recover. Basic nitrogen compounds should be treated as permanent catalyst poisons. Water — The catalyst is unaffected by water in the concentrations typically found in the naphtha splitter overhead or the LSR stabilizer bottoms, (up to 20 ppm). At higher concentrations, water will temporarily suppress the catalyst activity. Correction of the problem (drying the feed or make-up gas) should see the activity retum. However, charging free water to the unit will permanently damage the147080 Rev.1 Vi2. catalyst. For this reason, extra care must be taken when charging the unit from tankage, to ensure that the tank has been drained of water. Oxygen and oxygenates — Oxygen and oxygenates in the feed or make-up gas streams have a similar effect as water on the catalyst activity. Benzene and C;'s - The benzene saturation reaction (to cyclohexane), and the hydrocracking of C7's to C4 minus material are both highly exothermic reactions, leading to large delta T's in the reactor. Excessive cracking, low yields, and accelerated coke laydown on the catalyst are associated with these feed constituents, The total amount of benzene and C7's in the feed should, therefore, be closely monitored, and should never exceed a total of 5 wt% of the feed.147060 Rev. 1 Viet Vil. PRECOMMISSIONING ACTIVITIES During the final stages of construction and on completion of construction, there is a large amount of detailed preparatory work which should be done by operating personnel in cooperation with others at the job site. The primary purpose of this work is to acquaint the operators with the equipment, to inspect the equipment to make certain the construction was done exactly as shown on the piping and instrument diagrams, to ensure the equipment is free of debris and construction trash, to "run in" pumps, drivers, and compressors, and to commission all utilities and supporting facilities so these will be ready for the startup of the process equipment. This section covers the work required in preparing the unit for operation. This work (such as testing and cleaning) is generally carried out during final stages of construction and, on the whole, is generally carried out only once; however, it may be necessary to repeat some procedures after major turnarounds. Careful and thorough preparation is a requisite for satisfactory performance and will eliminate much trouble and delays during the startup. An outline is presented for a general method of cleaning and flushing lines and equipment. The outline for checking pumps, after installation and prior to operation, is applicable on all startups. Much of the work noted in this section is performed by construction personnel. No attempt is made herein to designate the personnel performing this preparatory work. There are some phases of the preparation, such as run-in of pumps during water circulation for line cleaning, which are best completed by the refiner's operating personnel. Much valuable experience can be obtained in this manner. A breakdown of the various precommissioning activities are listed below: A. Check Unit against Piping and Instrument Diagrams. B. _ Inspect Tower and Vessel Internals. C. Hydrostatic Testing. D. Clean and Service Utility Systems. E. Line Flushing147060 ev. vile Initial Run-in of Pumps and Drivers. Instrument Checkout Dryout of Fired Heaters. Initial Run-in of Compressors. Fin-Fan Heat Exchanger Run-in Reactor Circuit Dryout. Catalyst Loading rPrRerroen A. CHECK UNIT AGAINST PIPING AND INSTRUMENT DIAGRAMS. Following construction, it is necessary that a careful inspection be made of the equipment, making certain that the construction was done exactly as shown on the flow chart. This can best be done by covering every line and every notation with print marking pencils as the check is made. Particular attention should be paid to the details where errors in construction are most likely to occur. Any deviations from the design should be brought to the attention of those concemed for special consideration. B. INSPECT TOWER AND VESSEL INTERNALS All vessels and towers should be carefully inspected before they are headed up. Here again it is necessary that particular attention is paid to details. Carefully check such things as tray installations, reflux and feed nozzles, internal gaskets, extended ‘suction lines, vortex breakers, weep holes, location of nozzles, slotted inlet pipes, etc. Finally, each vessel should be cleaned before it is headed up. C. HYDROSTATIC TESTING Following the completion of construction the unit must be pressure tested to make certain that no leaks exist in any joints or welds. A hydrostatic test must also be made to make certain the plant can safely withstand normal operating pressures.147060, Rev.1 Vik3 These tests should be carried out in the presence of a UOP representative. The recommended procedure is to divide the unit into groups of similar test pressures and isolate them by installing blinds. The individual groups are then filled with a fluid, usually water, to a pressure 1.5 times the design operating pressure. If pressure vessels or towers are included when the piping is tested, precautions must be taken not to exceed the manufacturer's recommended test pressure at the bottom elevation. The test gauge should always be mounted at the lowest elevation in consideration of the hydrostatic head. After the test, reduce the pressure developed during the test very slowly. Some further suggestions which should be followed prior to and during the hydrostatic test period are as follows: 1. _ Relief valves or rupture discs must be removed, blinded or gagged. 2. Remove all orifice plates in lines to be tested. 3. All items under test must be liquid filled and all air vented. 4, Internals, such as level ball floats, which are not designed for the test pressure, must be removed 5. Items, such as piping connected to a vessel under test, which are capable of withstanding the test, may be subjected to the test. 6. Items, such as vessels connected to piping under test, which are not capable of withstanding the test, must be isolated by blinding. 7. A water filled system must be vented while draining to avoid collapsing equipment not designed for vacuum. 8. The minimum temperature at which hydrotesting can be conducted is 15°C (60°F).147060 Vii 9. All relief vaives (PSV's) must be bench tested and set before final installation. This testing and setting may be done while hydrostatic testing is in progress. D. CLEAN AND SERVICE UTILITY SYSTEM Following construction, all the utilities - such as cooling water, steam, air, etc, — should be put in service and checked out. First, the equipment should be pressure tested. Then the lines should be washed free of any construction trash by circulation or by blowing with air. All steam lines should be warmed up slowly to prevent damage by water hammer and, as the lines get hot, checked for freedom of expansion. All steam traps and control valves should then be put in service and tested. Likewise, control systems in the air, water, and fuel gas should be tested for operability. E. LINE FLUSHING 1. All piping should be thoroughly cleaned of debris and scale. Generally, fluid handling lines are flushed with water and thoroughly drained. Where practical, clean water should be supplied to the vessels and the contiguous lines be flushed away from the vessel. Do not flush debris into equipment. 2. Water flushed lines which do not drain freely should be blown clear with air. 3. Gas-handling piping may be either water flushed or air blown. Water should be thoroughly blown from the gas lines on completion of flushing. 4. Instrument air lines should be thoroughly blown with clean dry air, 5. During all cleaning by flushing, whether with water, steam or air, maximum volume and velocity should be used for thorough cleaning.147080 Rev. 1 Vis: Care must be taken to avoid a vacuum condition when draining any pieces of equipment. When flushing from a vessel or other equipment, adequate venting must be provided. The following is a guide for flushing @. Orifice plates should not be installed prior to flushing. b. Control valves should be removed or rolled out. Flexitallic gaskets cannot be reused so they should not be put in until final installation. Temporary gaskets can be used for initial installation. c. _ Instrument lines should be closed off or disconnected. d. Flush pump intake and discharge piping while disconnected. 2. Supply and exhaust steam lines to turbines may be cleaned by blowing while disconnected. {Flush through open end lines. Do not restrict flow. g. Regulate rate of flushing medium from the source. For example, water from a tower should be regulated at the tower; and steam should be regulated at the valve in the supply header to the line being blown. h. Flush through all drains and vents. Where possible, flush downward or horizontally. j. Always flush through bypass to an open end before flushing through equipment. k. For steam systems flush well through dirt leg drains and steam trap bypasses before placing the trap in service.147080 Rev. 1 Vii |. Disconnect lines at exchangers and flush to open end lines. Upon completion of fine flushing of any system, carefully check that all temporary breaks are reconnected, control valves replaced, and pump alignments are normal. INITIAL RUN-IN OF PUMPS AND DRIVERS Proper installation and operation of pumps and drivers is essential for trouble- free performance. The pumps and drivers should receive careful handling during initial run-in. The initial run-in of pumps is generally done by circulating water through the new equipment. Temporary strainers are installed in the intake of the pumps. During run-in of pumps, flow to the pump will decrease as debris collects in the strainers. In this event, the strainer should be removed and cleaned. The pump should not be permitted to cavitate, ie, “lose suction," which may cause damage to the pump. In starting a centrifugal pump, the rotation should be brought up to speed as rapidly as possible. An operating speed is attained rapidly and automatically with motor drive pumps and the usual motor starting control, The development of discharge pressure is essential to flush and lubricate the wearing rings. it is advisable, where practical, to close the pump discharge immediately prior to shutting down a centrifugal pump. ‘The discharge valve on an operating positive displacement type pump should not be closed as this will cause over-pressuring,147060 Rev. 7 Viie7 The following is a check list for prior to run-in: a. The manufacturer's operating instructions should be reviewed for any specific precautions that should be observed. b. Check that overalll installation is complete. ©. Verify that the pump and driver have been aligned for cold operation There must be no undue strain on the pump or driver by the piping. d. Check the water piping. Verify that water piping is connected, where required, to bearing jackets, pedestals, stuffing boxes, etc. Also, check that the direction of water flow is correct. @. Check the steam piping. Verify that steam piping where required, is complete. f Check the seal or gland oil piping. Conventionally packed pumps in hot service are generally furnished with gland oil; verify that this installation is correct and complete. When a pump is furnished with mechanical seals, verify that all of the components of the flushing system - such as strainers, separator, restriction orifices and coolers, when required — have been correctly installed and are clean. It is very important that the flush system be clean because the loss of flush or dirty flush can cause seal failure. g. Verify that the packing or seals are installed. hh. Check that the temporary strainers in suction piping, when required, have been installed. i Verify that the bearings and shafts have been cleaned prior to final lubrication.447060 0. Vile j Check that the pump and driver are lubricated according to lubrication instructions. Check the rotation of electric motor drivers uncoupled from the pump. Run-in uncoupled, verifying operability. Run-in, uncoupled from pump, drivers other than electric. During run-in of driver, overspeed trip bearings, controls, vibration, etc., should be satisfactorily checked to confirm operability. Abnormal conditions must be corrected before coupling to the pump. 5. The pumps are normally delivering a material of lighter weight than the water circulated during initial run-in. The pump driver is sized for the normal Pumping fluid, consequently while pumping water, the electric motors are easily overloaded. To avoid overloading the motor driving a centrifugal pump, the flow must be limited by throttling the pump discharge valve. If possible, check the amp usage against design. 6. The following list is for operating the pumps during run-in: Rotate pump and driver by hand, verifying that they roll freely. Check that run-in water supply and delivery circuits are lined up. Open suction valves fully, venting air from piping and pump, completely filling with liquid. Establish cooling water flow, where required. ‘Check that lubrication is satisfactory. Make sure electric power is available from the switch gear to the starter of the electric motor drivers. For steam turbine drivers, the turbine is warmed by slowly opening the exhaust valve and backing in steam while147060 Rey. Vio draining water from the casing. The exhaust valve is always fully opened before starting. Where the exhaust system is under vacuum, the case must be warmed by gradually introducing the driving steam, after opening the exhaust valve. In vacuum exhaust systems, sealing steam to the turbine shaft labyrinths should be admitted to avoid loss of vacuum. Barely open the discharge valve of a centrifugal pump and fully open the discharge valve of a positive displacement pump before starting. Start the pump and bring up to speed immediately, observing the discharge pressure. If the pressure does not build immediately, stop the pump and find the cause. Refill the pump and restart when the previous difficulty is corrected, When the discharge pressure of @ centrifugal pump has increased satisfactorily after starting, gradually open the discharge valve to obtain the desired flow rate. In the event of unusual noise, vibration, overheating or other abnormal conditions, shut the pump down immediately. Correct the cause before resuming operation. Continue checking for abnormal conditions as these may occur after prolonged operation. Check shaft sealing. Conventionally packed stuffing boxes must always be permitted to leak slightly, to provide some lubrication and prevent overheating. Stuffing box gland nuts are generally only finger tight. However, a mechanical seal may show some leakage on startup. After the pump has been started and stopped a few times, the leakage should stop. If the seal leakage persists, then steps should be taken to correct the problem.147060 Rev. 1 ViEwo | Operate the pump, directing flows through all suction and discharge piping circuits. m. Inspect and clean screens as required. n. Recheck and realign, if required, after any disturbance of piping, such as suction screen inspection, ©. In shutting down a centrifugal pump, close the discharge valve first, thereby maintaining discharge pressure while the pump rolls to a stop. This also prevents rolling backward after shutdown if the discharge check valve leaks. Positive displacement pump discharge valves must not be closed until the pump is shut down and rolling stops. P. After all lines available to the pump have been suitably fiushed, the temporary suction strainer may be removed only after showing free of debris on two successive examinations. The permanent strainers may then be installed where required. 9. Packing, in conventionally packed pumps normally not in water service, must be replaced upon completion of run-in and screen removal. G. INSTRUMENT CHECKOUT Prior to initial startup, instrumentation must be completed and checked out. The following is the required check list: 1. Testing and setting of all safety valves prior to operation. 2. Checking out all transmission systems of each instrument after installation. 3. Testing of air system to all control valves. Control valves are removed while flushing lines; when replaced, this section of air system should be retested.147060 Rev. 7 Vila 4. Checking of control valve operability; i.e., stem travel, action on air failure, etc. 5. Calibration of all pressure and temperature gauges. 6. Testing all instrument lead lines for leaks. 7. Checking sealing fluid, where required. 8, Calibrate all instruments and synchronize the transmitter and receiver readings for each instrument. 9. _ Installation of meter factor cards. 10. After line flushing, calibrate and install all orifice plates. Check the orifice plates for plate direction, weep hole and tag. 41. Check all instrumentation for correct metallurgy. H. DRY OUT FIRED HEATERS Before startup circulation is established, the heating systems should be put into operation to ensure that they are in proper condition. If the unit has fired heaters, it is necessary to slowly expel the excess moisture from the refractory by gradually raising its temperature. During this initial period it is preferable that no material be flowing through the tubes. For UOP type heaters, the following dryout procedure and precautions apply, (Other types of heaters may require changes in the procedure which should be made according to the manufacturer's recommendations.) 1. Make a temporary installation of thermocouples for temperature measurement in the hip sections of the heater. The tips of these thermocouples should extend 15 to 20 cm beyond the inside face of the insulating concrete.147080 Rev. 1 vil, ee 2. Before lighting any burners, all individual burner block valves should be closed, and the fire box steamed out to remove any gas accumulation. Open all dampers. 3. Light one or more burners, as required, in each section of the heater and fire slowly so that the temperatures in the fire box, as indicated by the thermocouples in the hips, are increased at a rate of about 10°C (20°F) per hour until a level of 110-120°C (230-250°F) is reached. 4. Maintain this temperature for at least 48 hours. During this period the burner operation should be rotated frequently in order to distribute the heat as evenly as possible throughout the length of the setting, and to check out each bumer. 5. Light additional burners as required after the 48 hour period to increase the temperature at a rate of about 40°C (75°F) per hour to a level of 480°C (900°F). Hold this temperature for ten hours. 6. All of the bumers should be shut off and the heater allowed to cool slowly by keeping the air inlet doors and stack dampers closed. 7. After the heater has been dried out, the temperatures can be subsequently raised or lowered at any desired rate unless the heater has been shut down for a prolonged period of time. 8. When the unit is shut down, the gas supply line should be blinded off (and pilot gas line, if a separate system) to prevent gas from leaking through the block valves at the heaters into the fumace, thereby creating an explosion hazard.147060 Rev. 1 views 1. INITIAL RUN-IN OF COMPRESSORS Before the plant is started up, it will be necessary to check the operation of the compressors. Preliminary compressor operations will be carried out in accordance with the manufacturer's recommendations. Prior to the first compressor startup, screens must be placed in the suction line to each cylinder to trap welding slag and other debris. These traps should be conical in shape and made of 100 mesh screen. For strength, this fine screen must be backed up with a suitable heavy gauge mesh. The manufacturer's representative will probably prepare and operate the compressors before releasing them for operation. This discussion will cover the procedure for preparing and placing the machines in service with hydrogen in the system. Refer to the startup procedure for air freeing the gas loop before putting hydrogen into the system. 4. Prestartup Checks There are several points that should be checked before the compressor is ready to run. a. _Alltrips and alarms — high discharge temperature, low lube oil pressure, etc. — must be checked and be operational b. The cooling water to the lube oil cooler and cylinder cooling jacket must be commissioned. Check that the flow is in the proper direction. c. The Sundyne compressor may be provided with a permissive start system, which will check the lube oil temperature and pressure before permitting the compressor to be started. Follow the vendor recommendations for compressor startup. 2. Startup Procedure for the Compressor147060 Rev. 1 view a. Purge the compressor with nitrogen through the suction purge valve to the atmospheric vent line. b. After nitrogen purging of the machine, introduce hydrogen to the compressor via the hydrogen pressuring line or by cracking open the suction block valve. c. Gradually open the compressor suction valve to pressure up the machine to line pressure. d. Make sure that there are no restrictions to the gas flow from the compressor. Open any upstream flow control valves or spillback control valve prior to starting the machine. J. FIN-FAN HEAT EXCHANGERS: An air fin exchanger consists of a fan with one or more heat transfer sections mounted horizontally on a frame. The heat transfer sections consist of finned tubes fixed between header boxes. Allowance for thermal expansion of the tubes is accomplished by anchoring only one header box and permitting the other end to move. A fan that is mounted above the tubes is called an induced draft fan because air must be drawn (induced) past the tubes. A fan mounted below the tubes is known as a forced draft fan because air must be blown (forced) past the tubes. The Fin-Fan heat exchangers should be installed and commissioned with manufacturer's recommendations. Special attention should be given to: 1. Check on condition of fins and remove any debris that might be left such as wool, insulating scraps, etc.“hove Views 2. Alignment and coupling of motor. 3. Check free rotation by hand. 4, Belt tension on Fin-Fan drive pulleys. 5. Check guards — must be safe. 6. _ Check bearings ~ clean and lubricate only if necessary — check for oil leaks. 7. Proper motor-fan rotation. 8 Check earthing (ground connections) 9. Check amperage to ensure proper pitch setting. 40. Check on metallurgy and pressure/temperature ratings. 11. Vibration switches — check for vibration during startup and load runs. 42. Louvers above fin-fans - grease sufficiently to prevent rusting. 413. Vents and drains where applicable. K. REACTOR CIRCUIT DRYOUT It is not necessary for the reactor circuit to be bone dry, but any free water should be removed. Drain all low points in the system and air blow the lines as dry as possible. Individual charge heater passes should be blown clear separately to ensure that no liquid pockets are present. Small amounts of moisture are not harmful to the catalyst, but care must be taken so it does not become wet.147080 fev. 1 vine eS L. LOADING CATALYST The reactor is a fixed bed catalytic reactor. The catalyst used, HS-10 catalyst, is a select material, prepared to promote specific reactions, The active ingredients are carefully compounded and should be protected in order to ensure long life. Like all other catalysts, HS-10 catalyst will suffer activity decline if subjected to improper operation or to improper feed. Prior to and during loading of the catalyst certain precautions should be taken to ensure that the catalyst will perform at its best. The catalyst is shipped in 55-gallon drums and should not be opened and exposed to the atmosphere for any longer period than necessary when loading. The loading of catalyst is normally the last item attended to before startup. Since it is necessary to work in the reactor, it must be made safe for entry. NO PERSON SHOULD ENTER THE REACTOR UNTIL THE REFINERY SAFETY DEPARTMENT HAS ISSUED AN ENTRY PERMIT. Care should be exercised to avoid excessive handling that might produce fines. To protect the catalyst against mechanical breakage while the reactors are being loaded, care must be taken that the catalyst is not dropped from the top head into the bottom of the reactor. To overcome this difficulty it is recommended that a hopper be installed over the top head of the reactor that is capable of holding a few drums of catalyst. A canvas sock is clamped on the hopper outlet and inserted inside the reactor. The other end of the sock should have a reducer attached to it 0 the sock remains full while loading. A rope is also attached to the bottom of the sock so catalyst flow can be stopped whenever the hopper goes empty. The end of the sock should be no more than five feet above the catalyst bed. As the bed level rises, the sock length will have to be shortened to keep catalyst flowing. The catalyst support material, thermowells, etc. should be added as outlined in the detailed loading diagram made for each unit. Before loading the catalyst support material make sure the reactor is clean and the CSM is the proper type and size. Lower the CSM into the reactor with a rope and buckets to minimize breakage.147080 Rev. 1 Vila? ee As spent HS-10 catalyst is returnable for a credit, the normal practice is to store the ‘empty catalyst drums in a safe place for eventual returm to UOP of the spent catalyst. It must also be remembered that HS-10 catalyst contains platinum, a relatively expensive material. Thus care should be taken during any handling to avoid spillage. Once loading is complete, all rings and flanges should be thoroughly cleaned before assembly, since they must hold high pressure hydrogen once the startup begins. M. UNLOADING OF UNREGENERATED CATALYST CONTAINING IRON PYRITES The following precautions are recommended for use during unloading of unregenerated HS-10 catalyst. The main concer is that no oxygen be allowed to contact the catalyst inside the reactors, since this will result in spontaneous combustion of the iron pyrites. The temperature generated by this combustion can be quite high, and left unchecked can result in severe damage to the catalyst and reactor internals. Of secondary, but no less importance, is protection of personnel and proper handling of catalyst during unloading. All personnel involved with the unloading must be properly informed of the dangers involved and the proper safety measures. 4. Follow the shutdown procedure as outlined in the procedures section. Be very careful to drain all residual hydrocarbons from the system low points, the separator and the feed line down stream of the feed flow control valve. 2. After all residual hydrocarbons have been drained from the system, cut out the heater fires and cool the reactor beds to less than 65°C (150°F)- preferably to 55°C (130°F). At temperatures above this level, combustion of iron pyrites is greatly accelerated and more difficult to control. If the catalyst is to be screened during unloading, the catalyst beds should be cooled to less than 55°C (130°F).147060 Rey. 1 viEwB. —— _ 3. After cooling the beds to 65°C (150°F), the unit should be evacuated and purged with Nz at least twice. The unit should then be properly isolated and a ‘small N2 purge established at the compressor discharge or preferable at the inlet to each reactor. Do not open the reactors at the top until all reactors have been unloaded. 4. Connect the unloading nozzle and be sure that a full opening but positive shutoff valve is installed. This is best accomplished by using a ball type or slide valve. 5. Remove all combustible materials from the area. 6. Be sure that several CO2 extinguishers are available. 7. Use only metal drums for unloading, and dump directly into drums if possible. It is best to screen the catalyst after it has had time to cool to ambient temperature, Each drum should be either purged with Nz during unloading or @ piece of dry ice placed at the bottom of each drum. Should the catalyst be screened at the same time as it is being dumped from the reactors, nitrogen should be purged through the dumping nozzle to the top of the first screen to provide additional protection from pyrite ignition. Do not seal the drum air tight since this could result in sudden rupture of the drum should combustion occur. Burning of catalyst in the drums is not serious and can be quickly extinguished with nitrogen or CO 8. tis expected that some “sparking” of the pyrites will take place in any event Therefore, all workmen in the area must be supplied with face and eye Protection. In addition, they should wear long sleeve shirts with the collars and cuffs tightly buttoned. 9. Maintain a positive flow of Np out of the unloading nozzle throughout the unloading. If the catalyst becomes bridged in the unloading zone or is not free147060 Rev. 1 vito flowing, break the plug with a blast of N2 or steam. Do not allow air to be drawn into the reactor. 10. If ignition of pyrites takes place inside a reactor, stop unloading in that reactor and increase the Nz purge to maximum until buming has been stopped.147060 Rev. 1 vill Vill. STARTUP PROCEDURE NOTE: This procedure is general in nature and is not intended to cover every possible mechanical and process combination. Particular care should be taken not to exceed equipment limitations. Variations of the procedure will be made by the supervisor according to the type and extent of the previous shutdown. The initial startup procedure for the unit consists of five steps. These are: (A) Preparation for startup (B) Plant purge (C) Stabilizer startup (D) Reactor startup. A. PREPARATION FOR STARTUP Prepare the unit for startup: 1. Check that all safety valves, instruments, utilities, blinds, and valve positions are ready for startup. 2. Drain water from alll low points. 3. Close all drain lines and bleeders. 4. _ Isolate the recycle compressor. Notify operating supervisor and other operating units concemed as to the exact time when startup activity will begin. Pumpers, tank farm, and others who may be involved should also be notified.147060 Rev. 1 vili2 B. PLANT PURGE The plant is evacuated using the steam ejector, then purged with nitrogen until the oxygen concentration is less than 0.5% by volume. (Alternative methods can be used to oxygen free the system.) The following steps should be followed: 1 Complete the plug and bleed list. Check that flare valves, relief bypass valves, and all drain valves on unit lines and equipment are closed. Make sure the entire system is open, i.e., all pathways between pieces of ‘equipment are clear. Isolate all instruments not suitable for vacuum service. Pull a vacuum to 150 mm Hg (abs) using the steam ejector. Place at least one vacuum gauge as far as possible from the ejector, Pull and break the vacuum from opposite ends of the unit. Flow across the reactor should always be downflow, to avoid lifting the catalyst bed. Hold vacuum for 1 hour. Watch for pressure rise on system indicating leaks. Pressure should not rise more than 0.07 bar, 50 mm Hg (abs). Pressurize the system with nitrogen and perform a thorough leak test on the unit. Depressurize the system to atmospheric pressure and repair any leaks that are found. When the system is tight and ready, pull vacuum again to 150 mm Hg (abs) and check for leaks. Pressurize the system again to 1 kg/cm2G (15 psig) with nitrogen.147060 Rev. 1 Vui-3 10. Repeat steps 8 and 9 two more times and pressurize the system. If this is the initial startup on fresh catalyst, leave the system under about 7 kg/cm2G (100 psig) nitrogen pressure, (or nitrogen header pressure, if less than this). If this is a subsequent startup, evacuate and pressurize with hydrogen. 14. Sample gas for oxygen at one of the sample connections. If oxygen content is not less than 0.5% by volume, repeat Steps 7-11 12. Recommission all instruments originally isolated. C. STABILIZER STARTUP Prior to commissioning the stabilizer, the column and associated piping must be air- freed. The column must be positively isolated from the reactor section and the fuel gas stream. A steam-out connection has been provided to enable air-freeing of the column and associated piping. Steam-out should be performed per refinery practice. Once the stabilizer section has been air-freed, the column, overhead receiver, and associated piping can be left under fuel gas system pressure, by backing fuel gas into the overhead receiver and column via the stabilizer net gas line. With the column air-freed and under fuel gas pressure, LSR naphtha may be brought into the stabilizer section. Prior to doing this, ensure that all low points in the system have been drained of condensate, Proceed to stabilizer startup as follows: 1. Establish a liquid level in the stabilizer column by pumping some fresh LSR feed to the column via the startup line from the discharge of the naphtha charge pumps to the stabilizer feed line. 2. When liquid starts accumulating in the stabilizer bottoms, start steam to the stabilizer reboiler and begin heating the column bottoms liquid. Heat up slowly,147060 Rev. 1 Vii-g to avoid tray damage due to the rapid vaporization of water that may be in the column. 3. Ensure that the stabilizer overhead condenser is in service. Commission the column pressure controller. Note: It may be difficult to line out the column at this point, due to the lack of light ends in the feed. 4. When a liquid level is established in the overhead receiver, commission the overhead pumps and put the stabilizer on total reflux. Line out the column at conditions near to its normal operating temperature and pressure. It may be difficult to line out the column at this point, due to the lack of light ends in the feed. The pressure may have to be lower than normal to get enough vapor up the column and into the overhead system. NOTE: As required, introduce more fresh feed to the stabilizer to maintain a reasonable liquid level in the stabilizer during the warm-up operation. If desired, a continuous flow of LSR naphtha may be sent to the column via the startup bypass and the column bottoms routed to storage. —. REACTOR SECTION STARTUP If this is the initial startup of the unit on a fresh catalyst charge, the reactor section will be under hydrogen following the completion of the plant purge. Pressure the reactor section to about normal compressor suction pressure with hydrogen. The pressurization rate should be about 10 kg/cm? per hour (150 psig per hour. If this is a re-start following a shutdown, the unit will already be under hydrogen pressure. NOTE: HYDROGEN SHOULD BE AT LEAST 70 MOL% PURE. CHECK THAT SULFUR, NITROGEN, AND OTHER POSSIBLE IMPURITIES ARE WITHIN SPECIFICATION.147060 Rev. 1 Vili-S, — NOTE: CHECK THAT THE REACTOR SECTION IS COMPLETELY ISOLATED FROM THE FRACTIONATION SECTION SO THAT THE FRACTIONATION SECTION ISN'T ACCIDENTALLY OVERPRESSURED. NOTE: WHENEVER RAISING OR LOWERING PRESSURE, DO SO IN A STEADY, LINEAR MANNER RATHER THAN STEPWISE. DO NOT ALLOW PRESSURE SURGES. - a. Establish recycle gas flow at the maximum possible rate. The compressor may be started at any time during the pressuring up period once the minimum compressor suction pressure is reached. However, the rate of pressurization may need to be decreased if it exceed the safe rate for the compressor seals. b. Purge the reactor charge heater firebox and light fires following normal refinery practice. Increase the reactor inlet temperature to 225-230°C (435- 445°F) at approximately 55°C/hr (100°F/nr). This may be begun any time after the recycle gas flow is established. Continue heating until all bed and outlet temperatures are over 220°C (430°F) c. The next step will be to cut feed into the reactor. 1. Verify that feed composition, sulfur, nitrogen, and any expected impurities are within specification. 2. Check that the heater outlet temperature is sufficient to ensure that the feed is 100% vaporized throughout the reactor (bed and outlet TI's). Allow for slight slumping of reactor temperature profile once feed is introduced. Have operator standing by at the charge heater, so that additional burners may be lit off, as required. The feed temperature should never be allowed to fall below about 220°C (430°F), due to concems about condensing hydrocarbon on the catalyst. Condensed hydrocarbon on the catalyst will form coke and potentially alter the structure of the catalyst resulting in permanent catalyst147060 Rev. 1 Vili-s deactivation. Note that due to a phenomenon known as capillary condensation, hydrocarbon may condsnse on the catalyst at tempera- tures well above the dew-point of the feed. Check that H2/HC ratio will be at least 1.0 when feed is cut into the reactor, Recycle gas should be at least 70% hydrogen. Stroke reactor charge and reactor products separator level controllers and verify valve response.147060 Rev. 1 VII? 6. Check reactor products separator boot for water and drain if present. d. Slowly close the startup bypass to the stabilizer column, and begin charging feed to the reactor at about 50% of the design rate. NOTE: IF NECESSARY, TEMPORARILY DECREASE HEAT TO STABILIZER COLUMN TO MINIMIZE ANY UPSET CAUSED BY STOPPING FLOW TO THE COLUMN. e. Within 15 to 20 minutes a level should appear in the reactor products separator. When the level reaches 30%, slowly begin charging to the stabilizer column. NOTE: IT IS A GOOD PRECAUTION TO INITIALLY POST AN OPERATOR AT ‘THE REACTOR PRODUCTS SEPARATOR LEVEL GLASS TO VERIFY LEVEL CONTROLLER READINGS. . Establish normal plant operation (the following may be done simultaneously): 1. Line out product separator level to about 50%. Avoid making sudden flow fate changes which might upset stabilizer column operation. 2. Slowly raise stabilizer column pressure to normal operating pressure and line out the column. Close the hydrogen line from the separator to the stabilizer reflux drum vent gas line, if this has been opened. 3. Adjust reactor charge to the desired rate. 4. Line out the reactor inlet temperature to about 240°C (460°F). Closely monitor the reactor outlet temperatures and introduce quench if the outlet temperature shows signs of increasing rapidly. Commission the hydrogen quench or other means for control of the lag reactor inlet temperature.147060 VIS 5. Increase the reactor products separator pressure to design at a rate of 3 kg/em2thr (50 psig/hr). 6. Adjust the hydrogen-to-hydrocarbon ratio to specification, if this was not already done. Recycle gas should be at least 70% hydrogen NOTE: FOR THOSE UNITS WITH A MULTIPLE-PASS REACTOR CHARGE HEATER, THE INDIVIDUAL CHARGE HEATER PASS OUTLET TEMPERATURES SHOULD BE CHECKED AT LEAST EVERY 5 MINUTES AS THE HEATER OUTLET TEMPERATURE IS INCREASED. IF ONE OR MORE PASS OUTLET TEMPERATURES LAG BEHIND, THIS COULD INDICATE A LIQUID SEAL OR POCKET OBSTRUCTING FLOW. THIS MAY CAUSE LOCALIZED OVERHEATING OF THE TUBE(S). IF THIS OCCURS, SHOCK THE SYSTEM MOMENTARILY BY CHANGING THE CHARGE FLOW ABRUPTLY. IF THE SEAL PERSISTS, LOWER TEMPERATURES AND SHOCK THE SYSTEM AGAIN BY ABRUPTLY CHANGING THE CHARGE RATE. IF THE SEAL PERSISTS, STOP HEATER FIRING, STOP THE REACTOR CHARGE AND MAKE CERTAIN THE PASS IS CLEARED BEFORE RESTARTING CHARGE TO THE UNIT. ENSURE THAT THE HEATER IS NOT OVERFIRED DURING ANY OF THESE ACTIVITIES. A liquid seal can be broken or prevented by adjusting the flow so that the charge heater delta P is greater than the head developed by a liquid pocket in any pass. Once the unit is lined out at these conditions, the reactor temperatures may slowly be increased to achieve the desired product ratios and octane.147080 Rev. 1 oA IX. SHUTDOWN PROCEDURE The following shutdown procedure covers a normal planned complete shutdown of the isomerization unit such as would be required for a complete catalyst change and/or the periodic cleaning and inspection of vessels. Variations of this procedure may be required from time to time because of special operating conditions that may arise. 1. _ Notify the operating supervisor and other operating units concerned as to the exact time when shutdown activity will begin. Pumpers, tank farm, and others who may be involved should also be notified. 2. Simultaneously reduce the reactor inlet temperature to 230°C (440°F) at approximately 50°C/hr (90°F) and the reactor charge to about 50% of design. 3. Cut charge out of the unit and block in the reactor charge line. 4. Continue to sweep the reactors with recycle gas to remove hydrocarbons for two hours at normal operating pressure. Maintain the reactor temperature at approximately 230°C (440°F) during this period. 5. When liquid stops accumulating in the product separator, drain the separator and all reactor section low points to remove all hydrocarbons. NOTE: The separator must be drained while the pressure in the separator is above the pressure downstream of the control valve. Draining should be carefully monitored to avoid blowing hydrogen downstream and overpressuring the stabilizer column. Block in the product separator level control valve when finished draining. 6. The stabilizer should be cooled down by stopping reboiler heat input, and should be left under positive pressure. If entry into the column is required, at a147080 1X2 minimum, it should be drained, steamed out, blinded off from other equipment, and air purged for safe entry. After sweeping the reactor with recycle gas for two hours at 230°C (440°F) and normal operating pressure, the reactor charge heater may be shut down following normal refinery procedure. If the catalyst will be dumped, cool the reactor down to 40°C (100°F). If the catalyst will not be dumped, cool the reactor down to 90°C (200°F). Shut down and isolate the recycle compressor following normal refinery procedure. Block in hydrogen makeup line if this was not already done. If it is not necessary to open the reactor section or regenerate catalyst, it may be left under positive hydrogen pressure. If the reactor section will be opened, or if the catalyst will be regenerated: a. Depressure the product separator to a safe location at approximately 15 kg/cm2/per hour (200 psi/hr). NOTE: Whenever the unit is depressured, depressure downflow through the reactor in a steady, linear manner. Do not allow surges. b. Evacuate the reactor section to 500-600 mm of mercury vacuum, Break with nitrogen to 0.5 kg/emG (5 psig). Repeat four more times to purge hydrocarbon from the reactor section. c. The reactor section should now be ready for insertion of necessary blinds and opening of equipment. Verify with safety department. d. If the catalyst will be dumped unregenerated, keep the drums under a small nitrogen purge while unloading catalyst into them. This is to protect against possible pyrite ignition,147060 Rev. 1 XI X. EMERGENCY PROCEDURES Emergencies must be recognized and acted upon immediately. The operators should carefully study, in advance, the steps to be taken in such situations. While some of the emergencies listed in this section may not result in a unit shutdown, they could cause serious trouble on the unit if not handled properly. In addition, damage to the catalyst might occur. Hard and fast rules cannot be made to cover all situations which might arise. The following outline lists those situations which might arise and suggested means of handling the situation. A. LOSS OF RECYCLE COMPRESSOR 4 Stop reactor charge heater fires immediately and cut steam through the furnace boxes for its cooling effect. Check to be sure the pilots were not blown out. ee Ensure that the reactor charge pump is shut down and blocked in. 3. Begin steadily depressuring the reactor section via the separator PSV bypass at approximately 15 kg/cm? per hour (200 psi/hour) to help purge hydrocarbons from the reactor and keep flow through the charge heater tubes. Do not depressure below the minimum pressure needed to restart the ‘compressor. NOTE: THE ABOVE THREE STEPS MUST BE PERFORMED AS QUICKLY AS POSSIBLE. NOTE: IF THE REACTOR SECTION TEMPERATURE APPROACHES DESIGN LIMITATIONS AND CANNOT BE CONTROLLED, COMPLETELY DEPRESSURE THE UNIT AS QUICKLY AS POSSIBLE. INTRODUCE MAKEUP HYDROGEN TO. THE REACTOR INLET VIA THE REACTOR SWEEP LINE. THIS WILL INVOLVE147060 Rey. 1 X2 BLOCKING IN THE MAKEUP GAS TO THE SEPARATOR, AND OPENING THE BLOCK VALVE IN MAKEUP GAS TO THE LEAD REACTOR EMERGENCY QUENCH LINE. OPEN THE EMERGENCY QUENCH TO THE LEAD REACTOR. 4. Restart the compressor as quickly as possible. 5. Put the stabilizer column on total reflux and adjust heat input to keep overhead and bottoms levels stabie. 6. As soon as liquid stops accumulating in the product separator, drain level to about 20% and block in control valve. NOTE: IF THE CONTROL VALVE IS NOT BLOCKED IN AND THE REACTOR SECTION PRESSURE DROPS BELOW THE STABILIZER SECTION PRESSURE, HYDROCARBONS FROM THE STABILIZER COLUMN MAY BACK UP INTO THE REACTOR PRODUCT SEPARATOR. IF THE PRODUCT SEPARATOR LOSES ITS LIQUID LEVEL, HYDROGEN MAY BLOW OVER TO THE STABILIZER AND OVERPRESSURE THE COLUMN. 7. When the compressor is again in service, come back on stream in the normal manner. B. REPAIRS WHICH REQUIRE STOPPING COMPRESSOR WITHOUT DEPRESSURING OR COOLING REACTORS 1. Drop reactor temperature to 220°C (430°F) by cutting back on heater outlet temperatures while reducing reactor charge rate to about 50% of design. Cut out reactor charge, Block in separator and stabilizer column as in normal shutdown. 2. _ Ifunit has been operating at a low pressure, it would be proper to increase the unit pressure before the shutdown, so that leakage during the down period will not be so great as to require extra outside hydrogen to be purchased and147060 Rev. 1 x3 used in the subsequent startup. However, DO NOT EXCEED DESIGN PRESSURE FOR THE UNIT. Continue firing heater and circulate recycle gas for two hours. Cut fires from heater and stop compressor. EXPLOSION, FIRE, LINE RUPTURE, OR SERIOUS LEAK — DO IF POSSIBLE Cut fire from all heaters. If heaters or control valve are beyond reach, main gas valve can be used. Block in fuel gas. Stop reactor charge pump. Stop other pumps, if possible Leave compressor running if possible while other items are attended to since it will contribute little extra pressure to the system. Shut down compressor. Depressure plant. Use of separator safety relief valve will depressure the separator and the reactor system. This relief valve may be activated from grade, via cable control. Shut down balance of plant as circumstances permit or require. If leak or line rupture is in a heater, add snuffing steam to cool down firebox AFTER THE SOURCE OF COMBUSTIBLES HAS BEEN ELIMINATED. DO NOT CLOSE THE HEATER DAMPER as it may force the fire out of the heater, Purge unit of hydrocarbon as soon as possible. DO NOT EVACUATE.147060 Ka D. CHARGE PUMP FAILURE 1. Cool reactor temperature to 220°C (430°F), with recycle gas and (if necessary) emergency quench. 2. Follow normal startup procedure. —. COMPLETE OR PARTIAL LOSS OF MAKEUP HYDROGEN 1. If the loss is temporary, it may not be necessary to shut down the unit if the reactor section pressure can be reasonably maintained and the H2/HC ratio can be held at or above 0.7. 2. If the unit must be shut down, follow the normal procedure as much as possible. F. TEMPERATURE RUNAWAY A reactor temperature runaway may occur if: (1) The feed becomes contaminated by high levels of aromatics and/or C7+ material. This may occur whenever there is an upset on an upstream fractionation unit. There is a sudden increase in the feed residence time in the reactor, as might occur if the feed rate is decreased without decreasing reactor temperatures; or, by a decrease in the recycle gas rate, such as might occur during a compressor shutdown. 2 (3) The reactor inlet temperature suddenly increases. As the reactor temperature rises for any of the above reasons, there is a resultant increase in the rate of hydrocracking reactions.147080 Rev. 1 XS Since the hydrocracking reaction is exothermic, this causes a further increase in temperature. As a result, very high reactor temperatures may be reached in a short time. Associated with these high temperatures is increased coke laydown o the catalyst, and in extreme cases, the possibility of exceeding the maximum allowable temperature for the equipment. To guard against the possibility of a temperature runaway, high temperature shutdowns have been provided at the reactor outlets. When activated, these result in shutting down the naphtha charge pump and the charge heater. In addition, ‘emergency quench to the lead reactor has been provided. This permits additional cooling in the event of a temperature excursion. The exact handling of a temperature runaway will depend on the extent and speed of the temperature use. Generally, stopping the cherge and shutting down the charge heater will be sufficient to control the situation. In addition, quench hydrogen can be introduced to the lead and second reactor. 1. Verify that the charge heater is shut down. NOTE: ENSURE THAT PILOTS ARE NOT BLOWN OUT. 2. Maximize recycle gas flow and makeup gas. NOTE: IF RECYCLE GAS GRAVITY BECOMES TOO HEAVY AS A RESULT OF HYDROCARBON CRACKING, THE RECYCLE COMPRESSOR MAY OVERAMP. IF THIS HAPPENS, GO TO RECYCLE COMPRESSOR FAILURE EMERGENCY INSTRUCTIONS. 3. Restart the unit following the standard startup procedure.147060 Rev. 1 XS G. FUEL GAS FAILURE A fuel gas failure will affect both the reactor charge heater and, perhaps the stabilizer column reboiler, if steam generation is stopped 1. It is not necessary to cut feed out of the reactor as long as the reactor feed can be maintained as 100% vapor. Condensed hydrocarbon on the catalyst will form coke and potentially alter the structure of the catalyst resulting in permanent catalyst deactivation, Note that due to a phenomenon known as capillary condensation, hydrocarbon may condense on the catalyst at temperatures well above the dew point of the feed. If this is not possible, follow the normal shutdown procedure as much as possible. 2. The stabilizer column will siump. Send bottoms to the inlet of the crude unit debutanizer (note that RVP will be high). Shut down the stabilizer column reflux pump before the overhead drum level drops below 50%. However, do not allow the overhead drum to overfill H. INSTRUMENT AIR FAILURE 1, Locate reason for failure. 2. If the problem is in the air drier system, bypass that section. This can then be repaired when possible. 3. Hair cannot be obtained, the altematives are a plant shutdown, or operation of the various controls on hand control. Action will depend upon the desires of the supervisor. 4. Due to the possibility of instrument air being used for breathing equipment and/or pneumatic instruments venting in the control room, be wary of adding nitrogen to the instrument air system.147060 XT 5. Be familiar with action of all control vaives — memorize all actions on air failure. 1. POWER FAILURE Emergency procedures during a power failure will vary greatly, depending on: 1) the extent of the failure, 2) which utilities may be affected by a failure, and 3) the length of the failure. In general, the first consideration in case of a power failure is to bring the plant to a safe standby condition. Of almost equal importance, however, is the protection of the catalyst. 1. Be sure the charge heater fires trip out and that the individual bumer fuel valves are blocked in. Cut steam through fumace boxes for its cooling effect. 2. Block in reactor charge. 3. If the compressor is turbine driven, it should be run long enough to sweep hydrocarbons from the system and cool down the reactor and charge heater before it is shut down. If the compressor is motor driven, begin depressuring the unit at approximately 15 kg/cm? per hour (200 psi/hr). Do not depressure below the minimum pressure needed to restart the compressor. Block in makeup hydrogen to the separator, and open the reactor sweep line to the lead reactor inlet. This can be used to purge the reactor section, NOTE: IF REACTOR SECTION TEMPERATURE OR PRESSURE APPROACH DESIGN LIMITATIONS AND CANNOT BE CONTROLLED, DEPRESSURE THE UNIT AS QUICKLY AS POSSIBLE. Do not allow the reactor to cool with hydrocarbon in it. The hydrocarbon must be removed by purging or depressuring. Condensed hydrocarbon on the447060 Rev. 1 Xe catalyst will form coke and potentially alter the structure of the catalyst resulting in permanent catalyst deactivation. Note that due to a phenomenon known as capillary condensation, hydrocarbon may condense on the catalyst at temperatures well above the dew point of the feed. 4. As soon as liquid stops accumulating in the product separator, drain level to about 20% and block in control valve. 5. When power is restored, follow the normal startup procedure. J. LOSS OF COOLING WATER The reactor product separator, stabilizer column bottoms product, and recycle compressor lube oil temperatures will be affected. A shutdown may be necessary if temperatures rise too much. Do not jeopardize the recycle gas compressor by allowing lube oil temperatures to increase above the compressor vendor's specifications. This can happen in less than fifteen minutes. It may be possible to control temperatures for a short time by directing fire monitors on the coolers.147060 Rev t Xia XI. LABORATORY TEST SCHEDULE STREAM AND TEST TEST METHOD FREQUENCY Fresh Stock Charge ee Compostion we UOP 551 Daily Relative den: Calculate from above Daily Total Sulfur, wt-ppm UOP 727 or ASTM D-4045 Daily Total Nitrogen, wi-ppm UOP 384 or ASTM D-4628 Occas. Arsenic, wpe UOP 296 Occas.* Lead, wt-ppl UOP 350 Occas. Copper, wt-ppb OP 144 Occas. Fluoride, wt-ppm UOP 619 Occas. Moisture Mitsubishi moisture analyzer, Occas. Model CA-05 or UOP 481 Bromine No. UOP 304 Occas. Total Oxygenates method base on suspected compound Hydrogen Makeup Gas oe Coniposttion, mor % oP 539 Daily Relative Density Calculate from above Daily H2S, mol-ppm Draeger Tube or UOP 212 Daily Total nitrogen, mole-ppm — UOP 430 Occas. CO, mole-ppm UOP 630 Occas. €0'+ CO,, mole-ppm UOP 603 Occas. HCI, mole-ppm UOP 405 Occas. H,0, mole-ppm UoP 213 Occas. Recycle Gas nee Smpostt ion, mol-% UOP 539 Daily Relative density Calculate from above Daily H2S Draeger tube Daily Stabilizer Column Off-gas ae Compostion, mole UOP 539 Daily Relative Density Calculate from above Daily H2S Draeger tube Occas. Stabilizer Reflux ‘OMposition, wt-% UOP 539 Occas. Relative Density Calculate from above Occas.Separator Off Gas ‘omposition, mol-% Relative Density He UOP 539 Calculate from above Draeger tube Daily Daily Daily 147060 Xi147000 ‘Ki STREAM AND TEST TEST METHOD FREQUENCY Stabilizer Column Bottoms ~“Composition, we% oP 551 Daily Relative density Calculate from above Daily RON - Clear (**) ASTM D-2699 Daily MON - Clear (**) ASTM D-2700 Daily Notes: * Items marked “occasionally” should be scheduled at least twice or week or when requested in order to thoroughly evaluate unit performance. Samples for octane must be taken in stainless steel cylinders and kept cool to avoid flashing cor light ends. The C5+ octane can alternately be calculated from UOP 51 and the UOP blending octane for the individual components.147060 Rev. 1 xt Xi. HYSOMER PROCESS HS-10 CATALYST REGENERATION PROCEDURE A. GENERAL COMMENTS The need for regeneration of HS-10 Isomerization catalyst is normally determined when the economic yield decline or product octane limit has been reached. The catalyst deactivation is primarily a result of carbon deposition on the catalyst. ‘The carbon deposition rate is a function of the feedstock quality and operating conditions of the unit. A properly controlled regeneration will restore the catalyst performance. The need for regeneration can also result from plant upsets such as high end point feed, compressor failure, sulfur ingress to the unit, and excessive catalyst temperatures. Regeneration of HS-10 Isomerization catalyst is accomplished by combining the basic steps of a hot hydrogen strip, a carbon burn, and reduction. The following discussion will review the important aspects of HS-10 Isomerization catalyst regeneration. It is not intended for the regeneration procedure to apply to all refinery situations. The purpose is to provide guidelines for the refiner to use when preparing the procedures that will be used on an individual unit. B. INTRODUCTION The HS-10 Isomerization catalyst regeneration incorporates the following steps. ‘Shutdown Hot Ho Strip Evacuation and Purge Hydrocarbon and Carbon Bum Nitrogen Purge APRONS147060 Rev. 1 xli-2 LL The HS-10 Isomerization Catalyst is deactivated over time by coke. The catalyst may be regenerated by doing a short carbon bum. The time that the catalyst is exposed to high temperatures should be minimized. The atmosphere that the catalyst is exposed to during the carbon bum and reduction should be kept dry. This is accomplished by conducting the regeneration at the highest allowable pressure possible for the design of the unit. C. PROCEDURE 1. Unit Shutdown This period can be used beneficially not only to free the unit of liquid hydrocarbons but to properly prepare the unit and additional equipment for the regeneration. All Necessary supplies should be on hand such as nitrogen, air, analyzers, etc. All Meters, pressure gauges, and thermocouples should be checked and placed in good working order, calibrating this equipment as necessary. In order to shorten the carbon burn as much as possible, it is important to strip and drain the maximum amount of liquid hydrocarbons from all low points in the recycle gas circuit. a. Notify the operating supervisor and other operating units concerned as to the exact time when shutdown activity will begin. Pumpers, tank farm, and others who may be involved should also be notified. b. Simultaneously reduce the reactor inlet temperature to 230°C (440°F) at approximately 50°C/hr (90°F) and the reactor charge to about 50% of design. ©. Cut charge out of the unit and block in the reactor charge line. d. Maintain maximum recycle gas circulation.147060 IES e. Adjust the heater firing to maintain the catalyst beds at about 230°C (400°F). Drain the products separator and check all low point drains until liquid hydrocarbon free. Hold for 2 hours. f. Now raise the reactor inlet temperature to 285°C (545°F), and hold until all 3 catalyst beds have reached 260°C (500°F) minimum. Hold for one hour. 2, HotHe Strip Excessive sulfur contamination will interfere with successful regeneration. The amount of interference depends upon the amount of sulfur as sulfate, which forms on the catalyst during the regeneration. Sulfate on the catalyst promotes platinum crystallite growth and retards the metal activity of the catalyst. Sulfur in general can be effectively stripped from the catalyst by circulating relatively high purity hydrogen at elevated temperatures. The conditions required are 400- 485°C (750-900°F) catalyst bed temperatures, 7 kg/cm2A (100 psia) minimum hydrogen partial pressure, and the absence of H2S in the circulating hydrogen. A high makeup gas rate and separator purge are maintained to purge H2S from the reactor section. For effective sulfur stripping, the catalyst bed temperature must be at least 400°C (750°F). Higher temperatures (to 485°C, 900°F) result in faster and more complete sulfur stripping. However, for most Zeolitic Isomerization units, metallurgical or other equipment limitations may limit the maximum temperature attainable during the hot H, strip, and can govern the catalyst bed temperatures achieved during the strip, Maximum gas circulation should be used. This step should be continued until all reactor outlets show less than 5 mole ppm H2S, as measured by a Draeger-type tube. If a plot of the H2S concentration in the purge gas indicates little reduction, the hot He strip may be discontinued after 24 hours or when less than 5 mole ppm147060 Rev. 1 xia -— H2S concentration in the recycle gas has been reached. The heater fires should be cut and gas circulation continued to cool the catalyst. During the hot H2 strip, the catalyst will tend to crack any hydrocarbon present in the reactor. Consequently, it is possible to have a temperature excursion in the catalyst bed, especially if the makeup gas from the reformer is of a low purity (<70 mol% H,). Catalyst bed temperatures should be closely monitored throughout the hot hydrogen strip. If the catalyst bed temperatures start to increase, introduce quench or, in an extreme case, shut down the charge heater and cool down the catalyst beds with recycle and makeup hydrogen. 3. Evacuation and Purge After the hot Hp strip, hydrogen must be removed from the system by either nitrogen purging or repeated evacuations, breaking each time with nitrogen. Prior to this, the reactor must be cooled to below the design temperature for vacuum conditions. The unit should then be pressured with nitrogen and maximum recycle gas circulation should be started. Heater fires can then be lit, and carbon bum conditions should be established. Water injection (BFW or cold condensate) is typically used upstream of reactor effluent air condensers that are not designed for the high regeneration temperatures. The water heat of vaporization will adsorb heat and reduce temperature. @. Begin reducing the reactor inlet temperatures to 200°C (400°F) at approximately 30°C (50°F) per hour. b. Maintain maximum recycle gas circulation. ©. At 200°C (40°F) reactor inlet temperatures, shutdown the heater firing. Continue recycle gas circulation to cool the reactor to 100°C (200°F) or to the maximum allowable temperature for the equipment under vacuum conditions, then shutdown, isolate, and purge the recycle gas compressor. Follow the manufacturer's recommended procedure for shutdown and purging of the recycle compressor.147060 XLS Depressure the unit to fuel gas then evacuate the unit three times to about 50 to 75 mm Hg, breaking each vacuum with nitrogen to 0.2 to 0.5 kg/em2G (3-5 psia). Isolate and blind the reactor section as required to prevent contamination of and from other equipment and units (feed, net separator gas, separator liquid, fuel gas, etc.). While maintaining a nitrogen blanket on the reactor section, make all connections for controlled addition of air, the oxygen analyzer, and water injection to the inlet of the effluent air cooler. Remove the blind in the regeneration waste gas line, which provides a means for controlling the plant pressure, venting the excess regeneration gases to atmosphere from the separator. Check the calibration of the air flow meter and the recycle gas meter. For nitrogen circulation, the recycle gas meter factor must be changed. Hydrocarbon and Carbon Burn Throughout the regeneration, maintain a record of all operating conditions and analytical results. Pressure the unit to about 7 kg/cm?G (100 psig) with nitrogen, consistent with the nitrogen supply pressure, air supply pressure, plant pressure limitations and compressor horsepower and discharge temperature limitations. Establish maximum nitrogen circulation and fire the heater to adjust each reactor inlet temperature to about 200°C (400°F). The higher the pressure and the nitrogen circulation rate, the faster the carbon burn will proceed as long as sufficient air is available. Drain all liquid hydrocarbons from the regeneration gas circuit low points prior to the next step.