Hydrocracking Processes Homsrefinery Sy-Books Pdf

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67 75 Btu scf of hydrogen consumed but the amount of nitrogen in the. feed is generally very small on the order of a few parts per million and. hence its contribution to overall heat of reaction is negligible. Amine Paraffin Ammonia,OLEFIN HYDROGENATION, The hydrogenation of olefins is one of the most rapid reaction taking. place and therefore almost all olefins are saturated The heat of reaction. is about 140 Btu scf of hydrogen consumed Olefin content is generally. small for straight run products but for stocks derived from secondary. thermal processes such as coking visbreaking or resid hydrocracking. H OIL etc it can contribute a considerable amount of heat liberated in. the hydrocracker reactor,RCH2CH CH2 H2 RCH2CH2CH3,Olefin Paraffin. SATURATION OF AROMATICS, Some of the aromatics in the feed are saturated forming naphthenes. Saturation of aromatics accounts for a significant proportion of both the. hydrogen consumption and the total heat of reaction The heat of reaction. varies from 40 to 80 Btu scf of hydrogen consumed depending on the. type of aromatics being saturated In general higher reactor pressure and. lower temperature result in a greater degree of aromatic saturation. AROMATIC NAPHTHENE, H 0IL is a commercial processed for resid hydrocracking resid desulfurisation licensed by. Hydrocarbon Research Inc USA,HYDROCRACKING OF LARGE MOLECULES.
Hydrocracking of large hydrocarbon molecules into smaller molecules. occurs in nearly all processes carried out in the presence of excess. hydrogen These reactions liberate about 50Btu scf of hydrogen con. sumed The heat released from the hydrocracking reactions contributes. appreciably to the total heat liberated in the reactor Cracking reactions. involving heavy molecules contribute to lowering the specific gravity and. forming light products such as gas and light naphtha in the hydrocracker. An example of a hydrocracking reaction is,RCH2CH2CH2CH3 H 2 RCH3 CH3CH2CH3. The yield of light hydrocarbons is temperature dependent Therefore. the amount of light end products produced increases significantly as the. reactor temperature is increased to compensate for a decrease in catalyst. activity toward the end of run conditions,FEED SPECIFICATIONS. Hydrocracker feed is typically heavy diesel boiling above the saleable. diesel range or vacuum gas oil stream originating from the crude and. vacuum distillation unit atmospheric resid desulfurizers coker units. solvent deasphalting units and the like The hydrocracking catalyst is. very sensitive to certain impurities such as nitrogen and metals and the. feed must conform to the specifications laid down by the catalyst man. ufacturers to obtain a reasonable catalyst life,FEED NITROGEN. Nitrogen in the feed neutralizes catalyst acidity Higher nitrogen in the. feed requires slightly more severe operating conditions particularly the. temperature and causes more rapid catalyst deactivation. FEED BOILING RANGE, A higher than designed feed distillation end point accelerates catalyst. deactivation and requires higher reactor temperatures thus decreasing. catalyst life, The feed properties have little direct effect on light product yield but.
they affect the catalyst temperature required to achieve the desired con. version The yield of light gases C4 and naphtha boiling range material. is increased when the catalyst temperature is increased. ASPHALTENES, In high cut point vacuum distillation there is always a possibility that. excessive high molecular weight multiring aromatics asphaltenes can. be found in vacuum gas oil distillates In addition to causing excessive. catalyst poisoning asphaltenes may be chemically combined with the. catalyst to deactivate the catalyst permanently, Metals particularly arsenic and alkalies and alkaline earth deposit in. the catalyst pores reduce catalyst activity Common substances that can. carry metallic catalyst contaminants include compounded lubricating oils. or greases welding fluxes and gasketing, Iron carried in with the feed is likely to be the most troublesome. metallic catalyst contaminant It may be chemically combined with heavy. hydrocarbon molecule or it may exist as suspended particulate matter In. either case it not only deactivates the catalyst but also plugs the catalyst. interstices such that excessive pressure drop develops Normally this. plugging appears as a crust at the top of the first catalyst bed. The feed may contain trace amounts of organic and inorganic chlor. ides which combine with ammonia produced as a result of denitrification. reactions to form very corrosive deposits in the reactor effluent exchanger. Oxygenated compounds if present in the feed can increase deactiva. tion of the catalyst Also oxygen can increase the fouling rate of the feed. effluent heat exchangers, Hydrocracking reactions can be divided into two groups 1 desulfur. ization and denitrification hydrogenation of polyaromatics and mono. aromatics are favored by the hydrogenating function of the catalyst. metals and 2 hydrodealkylation hydrodecyclization hydrocracking. and hydroisomerization reactions are promoted by the acidic function of. the catalyst support The support function is affected by the nitrogen. content of the feed, The catalyst employed in hydrocracking is generally of the type Ni.
Co Fe Mo W U on a silica alumina support The ratio of alumina to. silica is used to control the degree of hydrocracking hydrodealkylation. hydroisomerization and hydrodecyclization Cracking reactions increase. with increasing silica content of the catalyst Metals in the form of. sulfide control the desulfurization denitrification and hydrogenation of. olefins aromatics and the like, The choice of catalyst system depends on the feedstock to be treated. and the products required Most of the time the suitable system is. obtained by the use of two or more catalysts with different acidic and. hydrogenation functions The reactor may also contain a small amount up. to 10 of desulfurization and denitrification catalyst in the last bed of. the reactor,PROCESS CONFIGURATION, Hydrocracker units can be operated in the following possible modes. single stage once through mode operation single stage operation with. partial or total recycling and two stage operation These operation modes. are shown in Figures 3 1 and 3 2, The choice of the process configuration is tied to the catalyst system. The main parameters to be considered are feedstock quality the product. slate and qualities required and the investment and operating costs of. SINGLE STAGE OPERATION, This operating mode has large effect on the product yield and quality. Single stage operation produces about 0 3 bbl naphtha for every barrel of. middle distillate The single stage scheme is adapted for conversion of. FRESH FEED REACTOR,SECTION DISTILLATION,FRACTIONATOR BTMS.
ONCE THROUGH MODE,FRESH FEED REACTOR DISTILLATION,SECTION KEROSENE. DESULFURISED,FRACTIONATOR BOTTOMS GAS OIL,PARTIAL RECYCLE MODE. Figure 3 1 Hydrocracker operation once through and partial recycle modes. FRESH FEED NAPHTHA,REACTOR DISTILLATION,SECTION SECTION. FRACTIONATOR BOTTOMS,FIRST STAGE,REACTOR DISTILLATION. SECTION SECTJON,2ND STAGE 2ND STAGE,RECYCLE STREAM FRACTIONATOR BOTTOMS.
OPTIONAL J,Figure 3 2 Two stage hydrocracking process. vacuum gas oils into middle distillate and allows for high selectivity The. conversion is typically around 50 60 The unconverted material is low. in sulfur nitrogen and other impurities and is used as either feed for fluid. catalytic cracking units FCCU or a fuel oil blending component. The single stage process may be operated with partial or total recyc. ling of the unconverted material In total recycling the yield of naphtha is. approximately 0 45 bbl per barrel of middle distillate products In these. cases the fresh feed capacity of the unit is reduced Thus increased. conversion is achieved basically at the cost of unit s fresh feed capacity. and a marginally increased utility cost The partial recycling mode is. preferable to total recycling to extinction as the latter results in the. buildup of highly refractory material in the feed to the unit resulting in. higher catalyst fouling rates,TWO STAGE OPERATION, In the two stage scheme the unconverted material from the first stage. becomes feed to a second hydrocracker unit In this case the feed is already. purified by the removal of sulfur nitrogen and other impurities and the. second stage can convert a larger percentage of feed with better product. A heavy gas oil feed contains some very high boiling aromatic mol. ecules These are difficult to crack and in feed recycling operation tend. to concentrate in the recycle itself High concentration of these molecules. increase the catalyst fouling rate In a two stage operation the first stage is. a once through operation hence the aromatic molecules get no chance to. concentrate since there is no recycle The first stage also reduces the. concentration of these molecules in the feed to the second stage there. fore the second stage also sees lower concentration of these high boiling. aromatic molecules, The two stage operation produces less light gases and consumes less. hydrogen per barrel of feed Generally the best product qualities lowest. mercaptans highest smoke point and lowest pour point are produced. from the second stage of the two stage process The poorest qualities are. from the first stage The combined product from the two stages is similar. to that from a single stage with recycling for the same feed quality. The two stage scheme allows more flexible adjustment of operating con. ditions and the distribution between the naphtha and middle distillate is more. flexible Compared to partial and total recycling schemes the two stage. scheme requires a higher investment but is overall more economical. PROCESS FLOW SCHEME, The oil feed to the reactor section consists of two or more streams see. Figure 3 3 One stream is a vacuum gas oil VGO feed from the storage. tank and the other stream may be the VGO direct from the vacuum. distillation unit Also there may be an optional recycling stream consist. ing of unconverted material from fractionator bottom The combined feed. is filtered in filters F Ol to remove most of the particulate matter that. could plug the catalyst beds and cause pressure drop problems in the. reactor After the oil has passed through surge drum V 02 it is pumped to. the reactor system pressure by feed pump P Ol, Hydrogen rich recycled gas from the recycling compressor is combined with.
oil feed upstream of effluent feed exchangers E 01 02 The oil gas stream than. flows through the tube side of exchanger 02A and 02B where it is heated by. exchange with hot reactor effluent Downstream of the feed effluent exchan. gers the mixture is further heated in parallel passes through reactor feed heater. H Ol The reactor inlet temperature is controlled by the Temperature Recorder. and Controller TRC by controlling the burner fuel flow to the furnace. A portion of the oil feed is by passed around the feed effluent exchan. ger This bypass reduces the exchanger duty while maintaining the duty. of reactor feed heater H Ol at a level high enough for good control of. reactor inlet temperature For good control a minimum of 50 75 0 F. temperature rise across the heater is required, Makeup hydrogen is heated on the tube side of exchanger E Ol by the. reactor effluent This makeup hydrogen then flows to the reactor. Hydrocracker reactor V Ol is generally a bottle type reactor The. makeup hydrogen after preheating in exchangers E Ol flows up through. the reactor in the annular space between the reactor outside shell and an. inside bottle The hydrogen acts as a purge to prevent H2S from accumu. lating in the annular space between the bottle and outside shell It also. insulates the reactor shell, After the makeup hydrogen has passed upward through the reactor it. combines with the recycled gas and the heated oil feed from the feed. heater in the top head of the reactor The hot vaporized reaction mixture. then passes down the reactor Cold quenching gas from the recycling. compressor is injected to the reactor between the catalyst beds to limit the. temperature rise produced by exothermic reactions, The reactor is divided among a number of unequal catalyst beds This. is done to give approximately the same temperature rise in each catalyst. STEAM STEAM,2715 PSIG C 01 01 BLEED,185 F RECYCLE,COPPRESSOR. i LEAN DEA FROM,REGENERATOR,TO DEA FLASH H S ABSORBER.
V 01 03 RICH DEA TO,K O DRUM REGENERATOR,HIGH PRESSURE. SEPARATOR OFF GASTOHP,V 01 01 2d50 PS G AMINE CONTACTOR. MAKEUP 800 PSIG LOW PRESSURE,HYDROGEN 2200F SEPERATOR. 550 PS G TO H2S STRIPPER,F 01 01 H 01 01 PREFLASH,FEED FEED HEATER DISTILLATION SECTION. 2515 PSIG E 01 04 SOURWATER,800 F REACTOR EFFLUENT TO TREATMENT.
58 VAPOR1 AIR COOLER,H2S STRIPPER FEED,INERT GAS FROM V OMO. BLANKET E 01 03 DISTILLATION SECTION,E 01 02 REACTOR EFFLUENT. V 01 07 FEED EFFLUENT H2S STRIPPED FEED,FEED SURGE DRUM EXCHANGER EXCHANGER. 15 MINUTES,TO H2S STRIPPER,N2 POLYSULFIDE,P 01 01 V 01 08. FEED PUMP E 01 01,MAKEUP HYDROGEN,WATER B F W,REACTOR EFFLUENT.
FEED FROM STORAGE,POLYSULFIDE,FEED FROM UNITS DRUM. BOTTOM RECYCLE,FROM FRACTIONATOR, Figure 3 3 Distillate hydrocracker reactor section K O knockout. bed and limit the temperature rise to 500F Thus the first and second beds. may contain 10 and 15 of the total catalyst while the third and fourth. beds contain 30 and 45 of the total catalyst, Reactor internals are provided between the catalyst beds to ensure. thorough mixing of the reactants with quench and ensure good. distribution of vapor and liquid flowing to each bed Good distribu. tion of reactants is of utmost importance to prevent hot spots and. maximize catalyst life, Directly under the reactor inlet nozzle is a feed distributor cone inside. a screened inlet basket These internal elements initiate feed stream. distribution and catch debris entering the reactor Below the inlet basket. the feed stream passes through a perforated plate and distributor tray for. further distribution before entering the first catalyst bed. Interbed internal equipment consists of the following. A catalyst support grid which supports the catalyst in the first bed. covered with a wire screen, A quench ring which disperses quenching gas into hot reactants.
from the bed above, A perforated plate for gross distribution of quenched reaction mix. A distribution tray for final distribution of quenched reaction mix. ture before it enters the next catalyst bed, A catalyst drain pipe which passes through interbed elements and. connects each catalyst bed with the one below it, To unload the catalyst charge the catalyst from the bottom bed is. drained through a catalyst drain nozzle provided in the bottom head of. the reactor Each bed then drains into the next lower bed through the bed. drain pipe so that nearly all the catalyst charge can be removed with. a minimum of effort, Differential pressure indicators are provided to continuously measure. pressure drop across top reactor beds and the entire reactor. The reactor is provided with thermocouples located to allow obser. vation of catalyst temperature both axially and circumferentially Thermo. couples are located at the top and bottom of each bed The temperature. measured at the same elevation but different circumferential positions. in the bed indicate the location and extent of channeling through. EFFLUENT COOLING, The reactor effluent is at 800 8500F start of run SOR to end of run.
EOR at reactor outlet The reactor effluent is cooled in makeup hydro. gen reactor effluent exchanger E Ol and reactor effluent H2S stripper. feed exchanger E 03 The reactor effluent is further cooled in reactor. effluent air cooler E 04 to about 1400F,WATER AND POLYSULFIDE INJECTION. Condensate is injected into the reactor effluent just upstream of efflu. ent air cooler The function of the injection water is to remove ammonia. and some H2S from the effluent The effluent temperature at the injection. point is controlled to prevent total vaporization of the injected water and. preclude deposition of solid ammonium bisulfide, Trace amounts of cyanide ion in the reactor effluent contribute to. corrosion in the effluent air cooler A corrosion inhibitor such as sodium. polysulfide is also injected to prevent cyanide corrosion. HIGH PRESSURE SEPARATOR, The high pressure separator V 02 temperature is controlled at. approximately 1400F by a temperature controller which adjusts the. pitch of half the fans of the air cooler The temperature of the separator. is closely controlled to keep the downstream H2S absorber temperature. from fluctuating The hydrogen purity is lower at higher temperatures. However at lower temperature poor oil water separation occur in the. separator drum,LOW TEMPERATURE SEPARATOR, The high temperature separator liquid is depressurized through a HP. separator level control valve to 550 psig and flashed again to low pressure. separator V 06 The low pressure separator overhead vapors flow to high. pressure amine contractor V 04 The hydrocarbon stream leaving the. separator is fed to H2S stripper V Il via a stripper preflash drum The. sour water drawn from the low pressure separator is sent to sour water. treating facilities,RECYCLE GAS ABSORBER, DEA diethanolamine absorption is used to remove H2S from the.
recycled gas in recycle gas absorber V 04 H2S gas is absorbed by the. DEA solution because of the chemical reaction of DEA with H2S Typical. properties of DEA are shown in Table 8 19, The amount of H2S that can react depends on the operating conditions. The low temperature high pressure and high H2S concentration in the. H2S absorber favor the reaction In the DEA regeneration facilities high. temperature and low pressure are used to reverse the reaction and strip. H2S from the DEA solution, About 90 of the H2S formed by the desulfurization reactions is. removed from the recycled gas in a high pressure absorber by scrubbing. the gas with aqueous diethanolamine solution The absorber is a vertical. vessel packed with stainless steel ballast rings Recycled gas flows. through a support plate and upward through the packing A lean DEA. solution from the DEA regenerator enters the top of the absorber through. an inlet distributor and flows downward through the packing Rich DEA. from the bottom of the absorber is sent to the H2S recovery unit. RECYCLE GAS COMPRESSOR, Recycled gas is circulated by recycle gas compressor C Ol driven by. a steam turbine The largest portion of the recycled gas stream joins the. oil feed stream upstream of feed effluent exchangers A portion of the gas. stream from the recycling compressor flows on temperature control to. interbed quenching,DISTILLATION SECTION, The purpose of distillation section see Figure 3 4 is to remove H2S. and light ends from the first stage reactor effluent and fractionate the. remaining effluent into naphtha kerosene and diesel cuts The bottom. stream is either fed to the second stage of the hydrocracker recycled to. extinction with the fresh feed or withdrawn as product. Hydrocarbon liquid flows to H2S stripper V Il from stripper preflash. drum V IO The preflash drum removes some of the light ends and H2S. from the low pressure separator oil before it is stripped and fractionated. The stripper column contains packed sections below the feed plate and. two sieve trays above the feed inlet Stripping is achieved with steam. CONTRACTOR,VENTTORELIEF,110 F E 01 08,10 PSIG V 01 14.
155 F REFLUX DRUM,REFLUX DRUM,CONDENSATE,STRIPPER 215 F TOOILYWATER DRAIN. SEPERATOR LIQUID PREFLASH 105 PSIG,198 F P 01 06,150 PSIG CONDENSATE. FRACTIONATOR,WATERTO 32 TRAYS P 01 05,OILY WATER 440 F. V 01 17 V 01 15,WATER DRAWOFF P 01 04 SIDE CUT,REACTOR SIDE CUT. 6 TRAYS FRACTIONATOR,P 01 07 STEAM E 01 12,REACTOR SECTION 99 VAPOR.
H2S STRIPPER,150 PSIG STEAM 20 PSIG,E 01 15 390 F,110 PSIG FROM H2S. P 01 10 TO,FRACTIONATOR,10 PSIG E 01 12,STM SIDE STRIPPER. FROM FRACTIONATOR,HEAVY DIESEL,E 01 15 TO RECYCLING 2ND. E 01 16 DIESEL PRODUCT STAGE, Figure 3 4 Distillate hydrocracker distillation section. which removes H2S and light ends The stripper overhead vapor is. partially condensed in air cooler E 07 and a trim water cooler then flashed. in reflux drum V 12 The sour gas from the reflux drum is sent to a low. pressure amine contactor The condensed hydrocarbon liquid is refluxed. back to the stripper H2S stripper bottoms are sent to product fractionator. V 13 after heat exchange with diesel in E 16 circulating reflux in E 18. and fractionator bottoms in E 18 The fractionator feed is then brought to. column temperature by heating in the feed heater H 02 After heating the. partially vaporized fractionator feed is introduced into the flash zone of. product fractionator V 12 In the flash zone the vapor and liquid separate. The vapor passes up through the rectifying section containing approxi. mately 27 trays, Heat is removed from the fractionator column in the overhead con.
denser and in a circulating reflux heat removal system Vapor leaving the. top tray of the column is condensed in overhead condensers The con. densed overhead vapor is separated into hydrocarbon and water phases. Part of the hydrocarbon is recovered as overhead product and the rest is. sent back to the column as reflux to ensure good separation. The portion of the column below the flash zone contains five trays. Superheated steam is injected below the bottom tray As the steam passes. up through the stripping section it strips light components from the. residual liquid from the flash zone,OPERATING CONDITIONS. The operating conditions for single stage hydrocracking are shown in. Table 3 1 The yields and qualities for once through operation two stage. hydrocracking and one stage operation with partial recycling of uncon. verted material are shown in Tables 3 2 to 3 5 It must be stressed that the. yields depend on the catalyst composition and process configuration. employed and these can vary significantly,TEMPERATURE. The typical hydrocracker reactor operates between 775 825 F and. 2600 psig reactor inlet pressure The high temperatures are necessary. for the catalyst to hydrocrack the feed The high reactor pressure is. Single Stage Hydrocracker Operating Conditions,OPERATING PARAMETERS UNITS. CATALYST AVERAGE TEMPERATURE F 775,SPACE VELOCITY LHSV hr l 1 72. REACTOR INLET PRESSURE psig 2600,REACTOR PRESSURE DROP psi 50.
HYDROGEN PARTIAL PRESSURE INLET psi 2000,HYDROGEN CHEMICAL CONSUMPTION scf bbl 1150. MAKEUP RECYCLE AT REACTOR INLET SOR scf bbl 5000,MAKEUP H2 PURITY VOL 95. HP SEPARATOR TEMPERATURE F 140,HP SEPARATOR PRESSURE SOR psig 2415. BLEED RATE SOR 100 H2 scf bbl 200,RECYCLE COMPRESSOR SUCTION PRESSURE psig 2390. RECYCLE COMPRESSOR DISCHARGE PRESSURE psig 2715, necessary for catalyst life Higher hydrogen partial pressure increases.
catalyst life To keep the hydrogen partial pressure at a high level high. reactor pressure and high hydrogen content of the reactor feed are neces. sary To accomplish this an excess of hydrogen gas is recycled through. the reactor A makeup hydrogen stream provides hydrogen to replace the. hydrogen consumed chemically in hydrocracking olefin aromatics. saturation and the hydrogen lost to atmosphere through purge or dis. solved in oil A cold hydrogen rich gas is injected between the catalyst. beds in the reactor to limit the temperature rise caused by exothermic. hydrocracking reactions, In the hydrocracking process the feed rate operating pressure and. recycle gas rate are normally held constant The reactor temperature is. the only remaining variable requiring close control to achieve the. required liquid feed conversion, As the catalyst activity declines with time on stream due to catalyst. fouling it becomes necessary to increase the reactor temperature to. maintain the original liquid feed conversion rate This rate of increase. of reaction temperature with time is called the fouling rate Additional. temperature variation may be required to compensate for changes in. reactor feed rate or feed properties gas oil ratio hydrogen partial pres.


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