i" PROCESS DEVELOPMENTS Mitigate fouling in ebullated-bed hydrocrackers New monitoring tools help track and control asphaltene levels and solubility issues in resid products 4. KUNNAS, Neste Oil, Porvoo, Finland; ©. OVASKAINEN, Baker Hughes, Finland; and M. RESPINI, Baker Hughes, Italy the same time, the requirement for clean sulfur-free prod- ucts is increasing. During the last decade, ebullated-bed residue hydrocracking has gained increasing interest due to its capability to produce high-quality, light and middle distillate in an economically effective way from heavy residuum oils! Major economical drivers for ebullated-bed hydeocracker processes are run lengch, maintenance costs and most important, the achieved T: lobal supply of high-quality crude is decreasing and, at mn. Veay often, a compromise is made between unie opera tions and conversion due to fouling? ‘The limiting facto is fouling ofthe ebullated-bed unit fraction: ation section, especially che bottom stream ares, atmospheric- and vacuum-column bottoms, and vacuum-column furnace? The bortom steam heat exchanger run lengths and maintenance require ‘mes typically limit rota unie conversion and dictate unit economics efficiency. Fouling can also acc the high- and mid-pressin sep ‘ators downstream of the ebullated reactors. The ebullaved-bed ait distillation columns and related farnaces can alo foul significa. The deposic generation mechanism from distillation residuals ceansed by thermal cra ition and condensation of asphaltenes. This mechanism is slowed and partly controlled by catalytic hydrogenation.’ This allows much higher Yields compared to thermal processing, such as visbreaking and delayed coking, Conversion vs. fouling. Conversion reaction rate (ther ‘mal cracking), leading to fouling by asphaltenes decomposition, increase more rapidly with rising temperatures compared to the hydrogen-saturation reactions that inhibit sediments formation © Accordingly, increasing temperature and conversion above certain limits and beyond the optimal operational window will lead wo uncontrolled sediments and coke generation. These generated foulanes will deposit in critical plant sections ot will cause problems regarding sediments specification for heavy fuel oil Fig. 1). However, operating below the optimal operational windows cre- ates no major advancages, and decreasing severity will ot impact fouling rats significanty. Such actions will only result in lost ome version with no major advantages in terms of sediments deposition control and eun lengehs Most exposed to fouling, The sections most exposed to fouling are the atmospheric and vacuum columns and bottoms ‘heat exchangers, as shown in Fig. 2. At very high conversion, the reactor and separator may also suffer from high coke generation. Duc to extensive fouling, the separators and columns ean lead to ‘unplanned shutdowns, downtime and lost production, “The sume increasing trends can be seen for sediments generation in fue oil products, depending on the ebullated-bed hydrocracker severity, Below certain conversion limits, fuel oil will be stable. While above the optimum operating window, the tendency to enerate sediments overtime is very high dusing fuel oil scoring equirements. Consequently, is clear that seting the appropriate operating conditions are importanc. Ic allows the best tradeoff between maximizing conversion and producing stable fue! oil in relation to acceptable fouling control Parameters that define severity, The optimal severity depends on the feed processed, unit operating conditions and cats 'yst properties. The cbullated-bed hyeeocracker fed will change whenever the refinery feed quay, residual feed makeup or the pane feed rates changed. * Therefore, optimal pant managernent ious control of the fee aon with esd products stability. Several feed composiion-eelated factors do influence ebullaced-bed uni severity and conversion, such as * Stability reserve of asphaltenes in the vacuum resid (also known as che p-value) * Asphaltene content * Solubilcy ofthe asphaltenes Conesin oss, vOROCARBOM FROCESSING OCTOBER 2010PROCESS DEVELOPMENTS “Typically, alow-stability reserve, high-asphaltene content and Tnsolubiliy will result in higher fouling tendencies in the cbullated-bed unit and increased coke formation, thus yielding an unstable resid product. ‘Additionally, the amount of metallic contaminants can affect process performance by impacting catalyst performance, and, in rome cases, by increasing coke Formation. Sodium and iron, in particular, have a high impact on coking tendency. "To avoid deposit generation in the ebullated-bed unit, the extrudate catalyse plays a major role.> Catalyst type itself can have ‘a geat impact on unit performance. In ebullated-bed reactors, che catalyst is changed continuously to maintain catalyst activity and INTRODUCING THE VEGAMAG Combination MLY/Bridle for Liquid Level Measurement “The VEGAMAG a magnetic level indicator pared withthe components of Bypass bridle system The bri syste ules aVEGAFLEX guided micronave rar for tlecronclevelindcation. TheVEGAMAG'S separate chambers, roving redundancy through separate visual nd electronic measurements. GAMAG options include a agatostrcive sensor for rue electronic redundancy sand pont evel monitoring for dlsretealeming The VEGAMAG seal for any appiation that requires visual and electron monitoring. key Specifications + gto 752° (40°10 400°) ‘operating temperature + Upto 8009 (400 ba) operating + Visual indeation rom upto 200 ft + sila Qualifies (EC 6508/6511 Standards) + Compliant with ASME 83113 Select 168 at wove HycrcarbonProcessng comlRS metals removal efficiency. In addition, catalyse and unit operations alfec the reactor-fluent quality and cbullated-bed unit fouling The quality ofthe catalyst and che effect ofthe extrudate catalyst management ro downstream unit’ bottoms oil quality and fouling tendencies are direcly observed with monitoring techniques. Traditional fouling control. Traditionally, the ebullated bed reactor units are concrolled by measuring asphaltenes stabil- ity by adding asphaltenes precipitants (paraffins) o the cracked resid or fuel, and then measuring the precipitant quantity needed to cause flocculation. These detection methods may be based on simplified paper chromatography (spot test) or microscopy- based methods, known generally as p-value ‘Apart from detecting the “stability reserve” by probing with paraffinic-solvent addi jon, the sediments can also be measured by filtration methods. These are known as hot filtation tests (HFTs)—eg., IP375 and ASTM D4870—when performed on heavy fe ol ‘When fuel oil is submitted co aging procedures to reproduce long-term fuel oil behavior with respect to sediments deposi- tion, icis usually reported as otal sediment potential and total sediments by accelerated aging, These are included in the IP 390 A&B and ASTM D4870 A and B proce- dures. In addicion, the toluene insoluble testis ofien used to detect the amount of coke formed by the process However, these methods have some limitations due to inherent errors and low accuracy of the analytical techniques. In practice, chis cam toring results and to a reduced capability to operate at optimal severity. When these methods are applied, there sequences, such as ad to incorrect moni are possible com + Ineffective fouling control feading, to reduced run lengehs, high maintenance ‘costs and increased safety risks ‘+ Difficulties in reaching fuel oil quality or sediments specifications ‘The pressure drop, AP, and loss of heat transfer in the fractionation-bottom-steam® hheat exchangers are monitored continuously eer because they typically foul. Ala ity of the maintenance costs are directed in this area, as AP sets processing limits for the hydrocracking unit, However, if dhe refiner wants co operate just below where major exponential fouling increases, the processing limits must be found by other monitoring methods rather than just observing AP. Ebullated-bed unit vacuum-columa swash grids can also be affected by fouling Unstable resi flashing can increase coking sates at the column-veash grid. The sme problem can occur in che vacuum-columt Furnace. The column-furnace passfouling rate, as determined by the increasing tube-skin tempera- tute, can become too high, thus decreasing run length, Therefore Famace parameters must be monitored continuous, expecially skin temperatures, Techniques for unit conversion optimization. To overcome these difficulties from traditional methods, several Propritary technologies for analyzing impacts on refinery con- version unit operations by fouling and fuel oil stability have been developed. These developments have been used succesfully for ‘over 10 years in visbreakers and cokers.”8 More important, the advanced monitoring programs are proving to be vital soluxions for optimizing hydrocracker operations, controlling fouling and fine-tuning antifoulant chemical reatment. The processing objec {ive is to obtain maximum conversion, with the best balance berween conversion and run length, while avoiding uncontrollable depositions of foulants. The end result will determine the mose ‘cconomical operating scope for an ebullated-bed reactor unit, Neste Oil was interested in developing more advanced moni- toring methods for an ebullated-bed hydrocracker, The methods described here have been adopted by this refiner as part of theie Process monitoring routine and are used to maintain the process 2 the optimal operacing window. These methods also help in ‘dentfying sudden process changes chat may affect fouling con. trol, Continuous reporting and information exchanges take place With the refinery operations, as well as with the refinery technol. oy and process development. Ebullated-bed hydrocracker optimization, The meth- ods discussed here are based on monitoring two aspects related {© controlling the impacts of severity/conversion on fouling and sediments: Stability measurement for asphaltene-containing resids. This measurement is based on adding paraffin precpitants, Compazed {0 the traditional methods, asphaltene flocculation is detected by a very accurate eurbidimetric measurement in the near-infrared spectrum, This technique offers very good accuracy and low ane Iycial error. Tis fast, easy to operate and provides test results in lag than 30 minutes. A wide database from tefincry conversion 1 3s conscructed, and specific correlations for fouling and sedi- ‘ments afer accelerated aging procedures (IP 390 A&B and ASTM 'D4870 parts A and B) were further developed. Therefore, this 1 be used effectively co optimize unic conversion, Sepertor section (eer srs) Proc ‘Atm. isin iu (O ess atetos by fouling rary ae reer Ssierstnaen PROCESS DEVELOPMENTS Particle measurement of coke and precursors. High sever ties in thermal cracking reactions cause exponential coke genera. tion due to thermal stress at high conversion. For ebullated bed Process, coke generation must be controlled. Otherwise twill ‘ause catalyst problems and generate excesive coke levels that will dlsposit downstream of the reactors, Ths impact ean also be sen 4 fouling and as sediment issues in the fue, Generation of unstable asphaltenes wil easily create fouling ‘These asphaltenes are measured as sediments (HFT) in the fuel. A.new method based on sizing and counting coke particles and highly insoluble asphaltenes, using a patented technique with 2 light obscuration-based instrument, is available. This technique is very accurate measuring trace levels of coke; accordingly, sel. ‘ment- generation control significandy improves unit management When compared to traditional methods Technology application areas, Key areas prone to fouling in ebullated-bed hydrocracking units include: Ebullated-bed reactor bottom-stream exchangers fouling control. The stability of cracked resid will impace fouling in the bborrom-stream exchangers and ths is atypical location for exten. sive fouling, However, fouling inthis section can be controlled by adapring severity until the stability limit is reached where excessive fouling potential can occur. Fouling control for atmospheric- and vacuum-column sec- dons. Fouling in atmospheric and vacuum columns is related to reaction severity and lash-zone temperature in the columns, Rais ing severity will increase conversion whileafash-zone temperature increase wll enable recovery of more distillates. Boch aspects have ‘Say aoe re Soni: rer , Typical processing [seers sy cory HyOROCARBON FROCESSNG OCTOBER 20¥0 | 61PROCESS DEVELOPMENTS an exponential impact on column fouling, thus causing column- bottom coking and fouling above the flash zone. All will contrib- te to gasoil blackening and, sometimes, excessive pressure drop across the column. A new monitoring approach prevents fouling in this section and optimizes column management. Fluzing of ebullated-reactor streams. [cis a common pr tice in ebullated-bed hydrocrackers to flux with aromaticrich streams such as fluid catalytic eracking heavy oyele ol to increase fsphaltenes stabilization, and decrease coke and foulanes genera- tion, Fhurants can be added at various locations within the ebu fared reactor processes, chus allowing increased conversion. The impact of this operation depends, apart from flux quantity, on the tesid-feed quality and fhxant quality. In some situations, the fluxane isnot able to stabilize the resid feed. Using the analytical techniques described here, the refiner can determine the capability of selected fluxants to stabilize designated streams and the sta- blization asa function of percent fluxant. Ths allows an opcimal choice for type and amount of fluxanss applied. Sobity bling Haden Rabid bed Ato baton Vacium botom FIG. 5 Solubility blending index changes in ebullated-bed Peas Coking inde ctor topo ae + I ‘Coke formaten neesses ‘OCTOBER 2010 ySROCARAON PROCESSING Blending fuel oil with fluxants. Resid fuel ol soften fluxed with lighter distillate eefinery steams o contol viscosity and specific gravity specifications. The Hluxant will impact asphaltene stability and alzer sedimene generation for fuel-oil aging. The previously mentioned techniques can be used to quantitatively Bnd accurately measue the impacts from fluxants on seability and fon sediments generation. Monitoring experience at Neste Oil. Typically, ebullate: bed units are operaced very close to the limits of total insolubility of asphaltenes (Fig, 3). To produce a more stable, high-qual- ity bottom product for heavy fuel-oil blending, unit severity is, decreased so that conversion and total unit economies do not suffer. However, the asphaltene stability measurement provides a {good indication of the medium- and long-term fouling trends and, related unit operating condicions. I provides a good measurement to detect whether the reactor conditions influence che insolubil ity of asphaltenes or the solubility blending capability of the oil matrix. In addition, the asphaltene stability measurement shows how distillation will impact the stability of the column-botcom products. As the distillation process extracts more paraffinic com: pounds, i will also increase asphaltenes dispersion. Additional stability-related indices. Asphaltenes insol biliey index is a quantitative measurement of precipitation of the asphaltenes. I is highly increased by thermal cracking, as shown in Fig, 4. This index is of particular interest asthe ebullated- bed hydrocracker and thermai cracking causes dealiylation of asphaltenes to yield polynuclear aromatics-type structures. These asphaltene structures have increasingly higher aromatic-carbon concent and will impact che solubilicy ofthe resid matrix. Solvating power/solubility blending index dercrmines the capability ofthe resid to keep asphaltenes dissolved. Ie can also be applied co measure the impact of distillate flaxants on asphaltene Stability. As catalytic hydrogenation in the ebullated-bed hydrocracker decreases, the resid capability to solvate asphaltenes ecteases; he resulting ebullated-bed resid produce has a lower solubility blending index compared co the parent feed resi atmospheric resid is distilled in the vacuum column. Paraffin components are removed a light-and heavy-vacuum gasoil, while aromatics ate not extracted (o the same level. Therefore, more aromaties remain in che vacuum eesid, which increases the caps 1 asphaltenes, This stability index is not impacted greatly by temperature as the catalytic hydrogenation rate has 2 bility to disp Parte amount nx 567 8 8 01 2 8 eS Parti sze index Corre re nnylower activation energy compared to thermal cracking. Therefore, ‘po lear correlation can be observed against temperature. ‘As shown in Fig. 5, there is a definitive decrease in the solu- bility blending index due to the catalytic hydrogenation when ‘comparing the residue feed to the ebullated-bed hydrocracker «atmospheric bortom. Also, a partial recovery is seen when atmo. spheric resid is distilled in the vacuum column, ‘The coking stability index is a measurement of che most insoluble asphaltenes, otherwise called coke precursors, The lower the index, the higher the level of coke precursors, as shown in Fig 6. These precursors are quickly converted to coke at temperatites above 400°C; Fig, 6 can be used to evaluate and to support the coke-partile measurement method. — The coking stability index defines the asphaltene class that polymerizes at erack- ing temperatures co produce coke. There fore, this index can be used to measure coke-formation tendencies ofa feed when reactor temperatures inctease, The lower the coking stability index, the higher the consequence increase in coke generation, Particle analysis. The coke particle index measures the concent and size distri bution of solids/coke precursors and coke particles within a certain range of particles The advantages, compared to traditional soluble meehods, Quantitative accuracy of the method * Particle size range and its changes ean be devected * Very sensitive to process changes + Very quick cest method The amount and size of these particles can be related to fouling and unie run length. ‘Typically, the coke particle forma: th tion follows an exponential curve increasing reactor cemperatute and se iy: therefore. a threshold can he found. Fig. 7 illustrates che coke particle index increase asa function of the ebullaed-bed hydrocracker conversion, The particle distribution is measured in micron-sized range and shows the distri bution of solids, coke precursors and coke particles. The changes in coke-partile size and number can be detected, as shown in Fig. 8. Comparing samples ar different unit severities or feed qualities in Fig. 8 show particle growth and increase in quantity thae will lead co more severe fouling condi- tions, Larger particles accumulate easily in various places in the fractionation section, such as in separators and calumn bottoms. Particles size will also affece the fouling in heat exchangers as larger sized particles «an be easly deposited even when velociies, by design, are clevated to minimize foulant deposition. Coke and solid particles cre- surfaces thar require mechanical cleaning. hhard deposic on heat-ex ~~ MODERNIZI PROCESS DEVELOPMENTS ‘The very small toluene insoluble filtered in the HET procedures bur, by growth mechanism, they will ead to increases in fuel-il sediments, The particle analysis is also an excellent method to detect fractionstion-column operation errors and problems. By analyzing the particles in he gasoll streams above che lash zone, the refines ‘can detect fouling in upper parts of the columns. Coke particles in gasoil can also be sign of foaming issues in the colurnn, particles (< 1.6 microns) are not Antifoulant program. Nesce Oil decided to test an anti- foulant program to improve unit fouling control and run length Before the trial a baseline for process and monitoring values was Level Measurement. elena Sa ei] Selec 169 at wor HydrocarbonProcesting.com/RSPROCESS DEVELOPMENTS created. The program was adopted and modified forthe ebullated- bed hydrocracker from high-severity and high-temperature appli- cations.” The program improved operations through controling diffrent related mechanisms: + Thermal degradation of oils + Asphaltene destabilizati + Foulant creating catalytic effects of metals in feedstocks and ‘on equipment surfaces + Precipitation of organic and inorganic solids ‘Therun lengch ofthe bottom-stream heat exchangers depended ‘on the eullated-bed hydrocracker severity, catalyst management and feedscock. Therefor, its important to consider the process and catalyst conditions when comparing different operating cases. (On average, the antifoulanes have shown a clear increase in the bottom-stream heat exchanger run lengths (Fig 9). ‘mi Treated wih antiooants ‘Time n serio 1-23-45 6 7 8 9.1011 1213 1615 1017 18 19.20 Period of heat exchangor boing nserce between ceaings ldrojet... & BB Rearedteres dl) fase re Pe ree seeps a Aenea nade eee SCPE ana Bey a area ere eee Fein Sym Machine fol heres fr bral oe ae eect eee, «= ee oman ire aicractrnet ‘Select 170 at wor HydeocabonProcessing comvRS Results. The economics of ebullated-bed hydrocracking units are greatly affected by fouling and control methods. Stability methods detect asphaltene destabilization and precipitation ten- dencies; whereas, the particle method detects the amount and size of coke particles generated in ebullated-bed hydrocracker reactors and downstream units For both methods, a target value was determined. The ebul- lated-bed hydrocracking process was driven by using target con- ‘rol values close co the fouling threshold where rapid exponential fouling occurs Different indices can be calculated from these methods to ‘evaluate unit performance and to develop mitigation strategies that minimize fouling impacts and adverse Fue il specifications "The methods can be used to determine the best economical oper ating window for the unit. Process changes affecting fouling can be rapidly seen with these methods. An antifoulanc program was introduced after setting the baseline. The antifoulants immedi- ately decreased the AP ofthe fractionation section bortom-stream hheat exchangers and the heat exchanger run length was clearly increased. MP LITERATURE CITED Edwards BR Thil and L, de Bray, "Maximizing High Quality Diss rom LC-Fining” Sth BBTC 2007, Athens Sundaram, KM, U. Makheree and M. Baas, "Thermodynamic Mockl of Sediment Deposition in the LC Bining Proce,” Energy ar Fu Seprember/ caer 2008. > Patek, S and A. Gtagoani “Fise Reid Hydrocrack meeting, Vienna «Sherr Jer D-E, "Baris High Convenion Operations As Fouled Bel Uni Relaionship. Besween Sedimentation and Opec,” NCUT Workshop, Edmoncoa 2000, 5 MeNano, D. JD £, Sherwood Je and O. K. Bhas,"Gaving More Our | (of Your Resid Uprading Uni” rh BBTC 2008, Barcelona « Barcoldy J. and'S. Lv Andersen, "Changes in Asphaltene Sabiity Doing Hirdeoteng” Energy and Purl, 2000 ? Spanus Us A. Secelego, M. Respal and G. Jones, sginering. November 2005. Reducing Fouling in Delayed Coker Hewes to Produce Sable i ERTC iGch annua ing Fou! Ply “Whghe 8. Brgeering, Octobe Joni Kuna i: 3 development manage athe Neste Oi Pano einen Fr and He has yeas of experience nthe chemical and fing ndstes. tnt hr Kunnas focuses onthe Porvoo rfnery pdacton fe 4 RMU, LCR MHC) ‘recess dvlopment wor, and ranages the each ajc, Hehaspecaied: InLC-Fiee slated erste the constrocton and startup of roducon ine Me of Technology wth an MS eae LE Runnas graduated fom the Henk Unie renal engineting Marco Respini is » ker Hushes technology & faker Petite nds Tecrlogy Group n Europe, specaling i foulng conto He fas £2 yeas of rebring experience and curent i esopng new technologies for Norte fuing end sey area ton and etetng, Aneto oS pate D ntrrce panes on tes ion Unrate whe felsotrgaometaiecl ‘eric, neha ben a reset el Sa regstered profesional chemist in tly