Handbook of Spent Hydroprocessing Catalysts PDF
Preview Handbook of Spent Hydroprocessing Catalysts
Handbook of Spent Hydroprocessing Catalysts Second Edition Dr. Meena Marafi Petroleum Research Center Kuwait Institute for Scientific Research Safat, Kuwait Dr. Antony Stanislaus Petroleum Research Center Kuwait Institute for Scientific Research Safat, Kuwait Dr. Edward Furimsky IMAF Group Ottawa, ON, Canada Elsevier Radarweg29,POBox211,1000AEAmsterdam, Netherlands The Boulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates Copyright©2017Elsevier B.V.Allrightsreserved. Nopart ofthispublicationmaybereproduced ortransmittedinanyformorbyanymeans,electronic or mechanical, includingphotocopying,recording,oranyinformationstorageand retrievalsystem,without permission inwriting fromthepublisher.Detailsonhowtoseekpermission,furtherinformationaboutthe Publisher’spermissionspolicies andourarrangementswithorganizationssuchastheCopyrightClearance Center andtheCopyrightLicensingAgency,canbefoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitare protected undercopyrightbythePublisher (otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantly changing.Asnewresearchandexperiencebroaden ourunderstanding, changesinresearchmethods,professionalpractices, ormedicaltreatment maybecome necessary. Practitioners andresearchersmust alwaysrelyontheirownexperience andknowledgeinevaluatingandusing anyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethods theyshouldbemindfuloftheirownsafetyand thesafetyofothers,includingpartiesforwhomtheyhavea professional responsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeany liabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceor otherwise,orfromanyuseoroperationofanymethods,products,instructions,orideascontainedinthe material herein. LibraryofCongressCataloging-in-Publication Data Acatalogrecordforthisbookisavailablefrom theLibraryofCongress British LibraryCataloguing-in-PublicationData Acatalogue recordforthisbookisavailablefrom theBritishLibrary ISBN:978-0-444-63881-6 ForinformationonallElsevier publications visitourwebsite athttps://www.elsevier.com/ Publisher:JohnFedor Acquisition Editor:KostasKIMarinakis Editorial ProjectManager:SarahJaneWatson ProductionProjectManager:MariaBernard Cover Designer:MarkRogers TypesetbyTNQBooksandJournals Preface Thepetroleum refining strategymay requiresomereadjustmentsinlinewith the increasing supply ofunconventionalcrude. The previouslyanticipated steadilyincreasing consumption ofhydroprocessingcatalystsneedsto bereevaluated. Somerefineriesweremodifying operationstoaccommodateincreasing volume ofheavycrude.Insomepartsoftheworld, these trends had tobereconsidered once theproductionof unconventional crude from oil shalesourcesreached commercial level.The contentofatmosphericdistillatesin unconven- tional crude may approach 80%.The paraffinic natureof these distillatesrequires catalysts with ahigh hydroisomerizationactivity. These requirementscan be met using new catalyst formulations. Therefore,notonly thequantitybutalso the typeof hydroprocessingcatalysts will change. Correspondingspent hydroprocessingcatalystsrequireadditional attention to ensure safetyand environmentalcomplianceduring allhandling stages. Insomepartsoftheworld, increased refining capacity toaccommodateheavyandextra heavycrudes tooffseta steady decline inthe supplyof conventional crudewillbenecessary. This willtranslateintoanincreased consumptionof catalyst and hydrogen unless moreactive and stable catalystsare developed.Inaddition,advancesindevelopmentofnovelmoreeffi- cienthydroprocessing reactorshave beennoted. Globally,a rathercomplex situationin the hydroprocessing catalystmarketmaybeanticipated.This makesany predictionsof catalyst consumption and generationofspentcatalystsuncertain. Spentconventionalhydroprocessing catalystshave beenclassifiedas hazardous solids because oftheirflammabilityas wellastheirability torelease toxicspeciesin theairand in water. The hazardoussoliddesignationrequires thatspecialprocedures haveto beapplied during allstages ofspent catalysthandling,includingremovalfrom reactor, temporary storage, packaging, transportation, and disposalinlandfills.Itisthe responsibility ofthe refiner thatalltheseactivitiesarecarried outinaccordancewith the relevant regulations. To ensure environmental compliance,refineriescan establish partnershipwith companiesand/or consortiaof companieswith expertiseinallaspectsof spent hydroprocessing catalysts. Compared withspentconventionalcatalysts,the environmentaland safetyaspectsofspent unconventional catalystsare lessunderstood. Because ofa higher reactivityofcoke onspent catalysts,a higher flammability compared withconventionalcatalystsmaybe anticipated. xi Preface Other characteristics ofspent unconventional catalystsare unknown. Inthisregard,anaddi- tional researchisrequired tofill thegap beforenecessarylawsand actscan beimplemented byregulatory authorities. Today,a large portionofthe spent hydroprocessingcatalystsisrecycledback tothe operation afterbeing regenerated.Regenerationiscarriedout bycompanieswhoreceivednecessary certifications from regulatoryauthorities.A rejuvenationprocess has been developed inan effort torecycle these catalysts also,which aredeactivatedbymetals.Forsuchcatalysts, regenerationas theonly step maynotensure desirable recovery ofcatalystactivity. If regenerated/rejuvenatedcatalystscannot beused inthe originalreactor,they can becascaded to either less ormore severe operation.Recently,significant advancements have been made in reprocessingspentcatalysts.In fact,performance ofthe reprocessedcatalystsexceededthat of thecorresponding freshcatalysts.Apparently, reprocessinggivesnew dimension torecy- clingof spenthydroprocessingcatalysts. A number ofnonhydroprocessing catalyticapplications for spent catalystswere identified. Thus, ahighsulfur affinityoftransitionmetalspresentinspenthydroprocessing catalysts suggeststhatafterdecokingspent catalysts may beused assorbents forgasclean-up. Attemptsto usespentcatalystsfor watertreatmenthave also been noted.Construction materials (e.g., cementandbricks)as wellasspecialtiessuch asabrasives,alloys,ceramic, andsuch representadditional outletsfor spent hydroprocessing catalysts. Spent conventional hydroprocessingcatalystshave beenattractingattention aspotential sources ofmetalssuch asMo,W, Co, Ni, and V. Inmost cases,the content ofthese metalsis greaterthan thatinoresused for theirproduction. The methodsused for themetals reclamationfrom spentcatalystsreached acommercial stage. Infact,aftersomemodifica- tions, theestablishedhydrometallurgical methodsused for metalsproductionfrom various ores and industrialby-products can bealso appliedtospentcatalysts. Inrecentyears,theef- fortstoimprove existingand/or todevelop novelmetalrecovery methods tosuitspent hydro- processing catalystshave beennoted. Itshouldbe emphasizedthattheviabilityofmetals recovery from spent catalysts isinfluencedbydemandand pricesthathave been exhibiting significantfluctuations. Platinumgroupmetals(e.g.,Pt, Pd, Ru, and Rh) areusualactive metalspresentinunconven- tional catalysts.Becauseof theirvalue,metalreclamation from correspondingspentcatalysts appears tobethe onlyoption.In thisregard, metalrecoverycanbenefitfrom decades of experiencein metalsreclamation fromnonhydroprocessing types ofcatalysts(e.g., automotiveandreformingcatalysts). Inother words,the sameand/orslightlymodifiedmeth- odologycan beappliedfor the metalrecovery fromspentunconventionalhydroprocessing catalysts. Continuous interest inallaspectsofspent hydroprocessing catalystshasbeen indicatedby vigorousresearch activities sincethe firsteditionofthisHandbook. Thus,some250 new xii Preface references were identified and incorporated intothe secondedition.The petroleum refining industryhas beenmakingeffortstoimprove theefficiency ofoperationinlinewithmore stringentenvironmentalregulations.Theavailabilityofanunconventional crude required modificationofrefiningschemes includingthe catalysts,which intheircomposition differ from thatofconventionalcatalysts.Accordingly, Chapters1, 2and3 were modifiedin line with the mostrecent informationavailableinliterature. Because ofdirect impactonspent catalyst regenerationandrejuvenation, Chapter4,dealingwith catalyst deactivation, was expandedto include fournew sections.The most recentrelevant informationonregeneration and rejuvenationwasincorporatedintoChapters5 and 6,respectively.The cascadingof spent, regeneratedand rejuvenatedhydroprocessing catalystsintodifferentoperations is highlighted inChapter7.Thepreparation ofnew catalystsbyreprocessing ofspentcatalysts isdescribed inChapter8. Thepotentialof spenthydroprocessingcatalystsinnoncatalyticapplications has notyetbeen fullyrealized. Inthisregard,new Chapters 9 and 10comprisematerialfrom the firstedition together withrecent information. Afterdecokinga numberofenvironmentally relatedoptions (Chapter9)have beenidentified. Also, the suitabilityof spent catalystsformanufacturing varioususeful materials (Chapter 10)hasbeen highlighted. Continuous effortshave been made toimprove the efficiency ofmetalsreclamation from spent hydroprocessing catalysts. This isreflected byanupdated Chapter11. Theobjectiveof Chapter12isto highlight therole ofunconventionalcatalystsinhydro- processing.This includes theformer chapteronspentdewaxingcatalysts,whichinessence are unconventionalcatalystsconsistingofplatinumgroup metals.Thisisthefirsttime that the characteristicsaswell asenvironmental and safetyaspectsofspentunconventional catalystsare discussed. Chapter 13isdevotedtoenvironmentaland safety aspectsofconventional spent catalysts includingregulatoryissues.Inaddition,the emissionswithin regulatorylevelsmustbe main- tained duringallstagesofspentcatalystgeneration and subsequent utilization. Therefore, sections onenvironment and safetywere added toChapters 3,5,and6 regardinghydro- processing technology,regeneration, and rejuvenation,respectively. The priceofmetals which arepart ofhydroprocessing catalysts dictatesthe economic viability ofspent catalyst utilization.In thisregard, thepricefluctuationonthecommoditymarkets hasbeen notedas indicatedin Chapter14. Thisadds touncertaintyindefiningfutureperspectives (Chapter15) inallaspectsofspenthydroprocessing catalysts. xiii List of Acronyms API American Petroleum Institute ARDS Atmospheric residue desulfurization AC Activated carbon CAC Clean air act CCR Conradson carbon residue CERCLA Comprehensive Environmental Response Compensation and Liability Act CUS Coordinatively unsaturated site CWA Clean Water Act DAO Deasphalted oil DOC Dynamic oxygen chemisorption DTA Differential thermal analysis EPA Environmental Protection Agency EXAFS Extended X-ray absorption fine spectroscopy FCC Fluid catalytic cracking FTIR Fourier transfer infrared FTS FischereTropsch synthesis HDAr Hydrodearomatization HDAs Hydrodeasphalting HCR Hydrocracking HDM Hydrodemetallization HDN Hydrodenitrogenation HDNi Hydrodenickelization HDO Hydrodeoxygenation HDS Hydrodesulfurization HDV Hydrodevanadization HGO Heavy gas oil HIS Hydroisomerization HSWA Hazardous Solid Waste Amendment xv List of Acronyms HWTF Hazardous waste trust fund HYD Hydrogenation KISR Kuwait Institute for Scientific Research LM LangmuireHinshelwood MSDS Material safety data sheet NAAQS National Ambient Air Quality Standard NESHAP National Emissions Standards for Hazardous Air Pollutants NPDWS National Primary Drinking Water Standards NSDWS National Secondary Drinking Water Standards PAH Polyaromatic hydrocarbons RCRA Resource Conservation & Recovery Act RFCC Residue fluid catalytic cracking SAPO Silica-alumina phosphate SDWA Safety Drinking Water Act SEM Scanning electron microscopy SMCRA Surface Mining Control and Reclamation Act STM Scanning tunnelling microscopy TCLP Toxicity characteristics leaching procedure TCM Total catalyst management TEM Transition electron spectroscopy TGA Thermal gravimetric analysis THF Tetrahydrofuran THFIS Tetrahydrofuran insolubles TIS Toluene insolubles TPD Temperature programmed desorption TPO Temperature programmed oxidation TPP Temperature programmed pyrolysis TPR Temperature programmed reduction TSCA Toxic Substance Control Act TSDF Treatment storage and disposal facility TDGA Transportation of Dangerous Goods Act VGO Vacuum gas oil XPS X-ray photoelectron spectroscopy XRD X-ray diffraction spectroscopy xvi CHAPTER 1 Introduction Petroleum refining strategies have been influenced by the gradual change in the quality of conventional crude oil. Not long ago, this change involved a declining supply of light crudes offset by an increasing volume of heavy crudes. In recent years, the world crude market has been influenced by the availability of unconventional crude oil occurring in low-permeability sedimentary formations, so-called “light tight oil.” These changes have been evident particularly in the United States, while other parts of the world are following. In addition, biomass-derived feeds have been identified as a source of fuel although their impact on the slate of commercial fuel products is anticipated to be minor. Petroleum refineries must respond to these developments with a readjustment of refining strategies. This includes modifications to hydroprocessing (HPR) operations, i.e., new types of catalysts and catalytic reactors. In a world of change, the petroleum refiner has a choice from among several types of commercial processes for the HPR of conventional and unconventional petroleum feeds. The HPR feeds derived from conventional crude via atmospheric distillation include straight-run distillates and atmospheric residue (AR). The latter can be subjected to additional distillation under vacuum to obtainvacuum gas oil (VGO) and vacuum residue (VR). The content of metals and asphaltenes in AR and VR can be decreased substantially by solvent deasphalting to obtain deasphalted oil (DAO). During HPR, it is more difficult to upgrade VR than AR, whereas fewer problems have been experienced with catalytic upgrading of VGO and DAO. Decades of refinery experience have confirmed that the atmospheric distillates can be upgraded without any difficulties. The difficulty and/or severity of upgrading via HPR increases with increasing content of contaminants (e.g., metals, resins, asphaltenes, sulfur, and nitrogen) in the feed. The increase in severity results in the increased consumption of hydrogen and catalyst. The conversion of heavy and ultraheavy crude to distillates is necessary as the first step during the production of liquid fuels. For this purpose, a number of commercial processes are available [1,2]. They include hydrocracking (HCR) with hydrogen addition to the feed and thermal conversion (coking) involving carbon rejection from the feed. The hydrogen addition processes require the presence of an active catalyst. Compared with thermal processes, HPR operations are more flexible, giving higher yields of liquid fractions. However, the costs of high-pressure equipment, catalyst inventory, and H required for 2 HPR must be offset by increased yield and quality of the liquid products. In an extreme HandbookofSpentHydroprocessingCatalysts.http://dx.doi.org/10.1016/B978-0-444-63881-6.00001-9 Copyright©2017ElsevierB.V.Allrightsreserved. 1 2 Chapter 1 case (e.g., extra-heavy feeds), carbon rejection is the route of choice compared with hydrogen addition. However, some hydrogen addition processes (e.g., slurry bed HCR) have been designed to handle heavy feeds containing as much as 700ppm of metals and more than 20wt% of asphaltenes [3e7]. The composition of distillate feeds obtained from conventional crude via distillation may differ from that of distillates with a similar boiling range produced using carbon-rejecting processes. For the latter, the constituents of primary interest (e.g., S- and N-containing compounds) are of a more refractory nature. Therefore, more severe HPR conditions are required to achieve a desirable level of hydrodesulfurization and hydrodenitrogenation. Also, these feeds have a higher content of Conradson carbon residueeforming precursors. Therefore, a higher consumption of hydrogen and catalyst should be anticipated if those trends continue. The aforementioned trends may have to be readjusted because of the availability of an unconventional crude such as light tight oil, which is now being produced commercially. Light tight oil has a boiling range similar to that of light conventional crude (e.g., Brent crude). This suggests that not only the volume but also the types of HPR catalysts may change. Other unconventional crudes may include biofeeds, FischereTropsch syncrude, and coal-derived liquids. Novel catalytic formulations will be necessary to achieve an optimal HPR operation. The catalysts used in the refining processes deactivate with time on-stream [8e12]. When the activity of the catalyst declines below the acceptable level, it must be replaced with either fresh or regenerated catalyst. However, it is not always economically attractive to conduct regeneration of spent catalysts [7,13,14]. Thus, after several cycles of regeneration and reuse, the catalyst activity recovery may decrease below acceptable levels. Therefore, further regeneration may not be economically attractive. Then, other options for the spent catalyst’s utilization have to be considered before it can be discarded as solid waste [14,15]. Currently, the market for fresh HPR catalysts approaches 120,000tons per year. About half of this amount has been used for the HPR of distillates to produce clean fuels, whereas the other half has been used for residue upgrading [7]. The demand for HCR catalysts is expected to grow at a rate of more than 5% per year. This would increase the production of spent catalysts. Obviously, the quantity of spent catalysts discharged from various processing units depends largely on the amount of fresh catalysts used and the quality of feeds. Always, the amount of spent catalyst is generally greater than that of the fresh catalyst because of the amount of deposits (coke and metals). For example, spent catalysts from distillate-upgrading units contain typically 10e20% coke and 7e15% sulfur together with some hydrocarbon carryovers [7]. Both organic and inorganic forms of sulfur are present. In the case of residue HPR operations, metals such as Vand Ni present Introduction 3 in the feed deposit on the catalyst together with coke. If dispersed solids are present in the feed, they deposit on the front of catalyst fixed bed. The spent catalysts discarded from these units usually contain 7e20% VþNi, 15e25% coke, 7e15% sulfur, and 5e10% residual oil together with active metals (Mo and Co or Ni) and Al O originally present in 2 3 the catalyst. However, the amount of deposit on the catalyst may be decreased on the refinery site by applying de-oiling and drying procedures before unloading spent catalyst from reactor. According to the estimate made by Dufresne [7], the total quantity of spent HPR catalysts generated worldwide is in the range of 150,000 to 170,000tons per year. In addition to HPR, fluid catalytic cracking (FCC) and re-forming units may be another source of solid spent catalysts on the refinery site. The feeds for these processes must be subjected to HPR to minimize catalyst poisoning by nitrogen bases and metals. Because of the hazardous nature, the procedures applied for handling of spent HPR catalysts may differ from those used for the other types of catalysts. For example, the particle size of spent FCC catalysts is much smaller than that of spent HPR catalysts. Therefore, all precautions have to be taken during the handling of the former catalysts. The reasons for a significant increase in the production of spent HPR catalysts in recent years may be summarized as follows: 1. A rapid growth in the distillate hydrotreating capacity to meet the increasing demand for ultralow-sulfur transportation fuels. 2. Reduced cycle times due to higher-severity operations in diesel hydrotreating units to meet stringent fuel specifications. 3. A steady increase in the processing of heavier feedstocks having high sulfur, resin, asphaltene, and metal contents to distillates by hydrogen addition technology. 4. Rapid deactivation and unavailability of reactivation processes for residue HPR catalysts. With respect to (3), it is anticipated that the volume of heavy feeds entering refineries will level off or even decline. Consequently, the consumption of HCR catalysts should decrease. The amount of novel catalysts required for the HPR of unconventional feeds may not offset the decreased amount from the HPR of heavy feeds. Therefore, overall, it is not expected that the consumption of HPR catalysts will continue to grow. Of course, these trends will vary from region to region. Disposal of spent catalysts requires compliance with stringent environmental regulations. Spent HPR catalysts have been classified as hazardous wastes by the Environmental Protection Agency (EPA) in the United States. The EPA added spent hydrotreating catalyst (K171) and spent hydrorefining catalyst (K172) to its hazardous waste list in August 1998 [16] because of their self-heating behavior and toxic chemical content. Spent HCR catalyst was added to the list in 1999 [17,18]. Metals such as Co, Ni, and V that are present in spent HPR catalysts from dual operations (e.g., simultaneous hydrotreating and HCR) are
The list of books you might like
