CA2264021A1 - Heteroatom removal through countercurrent sorption - Google Patents

Abstract

The present invention relates to a process for heteroatom removal, particularly during process excursions, from petroleum and chemical hydrocarbon streams. The invention is comprised of at least two zones through which the hydrocarbon stream and a hydrogen containing treat gas flow. The first zone contains a bed of heteroatom hydroprocessing catalyst in contact with hydrogen-containing treat gas and the second zone contains heteroatom sorbent material(s) through which the hydrocarbon stream flows countercurrent to the up flowing hydrogen-containing treat gas.

Description

?1015202530CA 02264021 1999-02-221HETEROATOM REMOVALTHROUGH COUNTERCUFIRENT SORPTIONThis application claims priority to U.S. Provisional Patent Application No.60/024,306, filed August 23, 1996.Field of the InventionThe present invention relates to a process for heteroatom removal from apetroleum and/or chemical stream. The present invention is particularlyuseful in the process of ensuring the desired product quality by enabling theheteroatom removal process to continue in the event of a process excursion.Background of the InventionHeteroatom removal is one of the fundamental processes of the refining andpetrochemical industries. Heteroatoms are defined to be those atoms otherthan hydrogen and carbon, present in hydrocarbon streams, including but notlimited to, sulfur, nitrogen, oxygen, and halogens. These atoms are typicallyfound as organo heteroatom molecules wherein the heteroatom moleculesmake up part of the carbon hydrogen backbone. Unless otherwise specified,the expression “heteroatom" is hereafter meant to encompass the elementalform of the heteroatom itself as well as its combined counterpart species asan organic and as combined with hydrogen (i.e. organo heteroatom andhetero-hydride, respectively).The removal of such heteroatoms by conversion to the corresponding hetero-hydride (i.e. hydrogen sulfide, ammonia, water, or hydrogen halide) istypically achieved in industry by reaction of the hydrocarbon streamcontaining the heteroatoms with hydrogen over a suitable hydroprocessingcatalyst which is designed to meet the required product quality specifications,AMENDED SHEETu-| -..?1015202530WO 98/07805CA 02264021 1999-02-22PCT/U S97/ 14761or to supply a low or a substantially reduced level (hereafter low is meant toalso include essentially no heteroatoms) heteroatom stream to subsequentheteroatom sensitive processes, catalysts, or product dispositions.Typically, catalytic heteroatom removal of a stream is carried out in co-currentreactors in which both the preheated feed stream and a hydrogen-containingtreat gas are introduced to one or more beds of heteroatom removal catalyst.The liquid feed stock, any vaporized hydrocarbons, and hydrogen-containingtreat gas all flow together through the catalyst bed(s). The resultingcombined vapor phase and liquid phase effluents are normally separated in aseries of one or more separator vessels, or drums, downstream of thereactor.Conventional co-current catalytic heteroatom removal has met with a greatdeal of commercial success; however, it has limitations. For example,because of hydrogen consumption and treat gas dilution by light reactionproducts, hydrogen partial pressure decreases between the reactor inlet andoutlet. At the same time, any heteroatom hydroprocessing reactions that takeplace results in increased concentrations of hetero-hydride which stronglyinhibits the catalytic activity and performance of most hydroprocessingThus, thedownstream portions of catalyst in co-current reactors are often limited incatalysts through competitive adsorption onto the catalyst.reactivity because of the simultaneous occurrence of multiple negativeeffects, such as the low H2 partial pressure and the presence of the highconcentrations of hetero-hydride.Process excursions can occur during operation of a co-current reactor.Process excursions include events such as variation in quality or rate of theliquid feed stream or hydrogen containing treat gas stream, start-up and shut-down of the unit, emergency depressuring of the reactor to avert hazardousconditions, or other process upsets commonly experienced by commercial?1015202530CA 02264021 1999-02-223operating units. During such process excursions, there is a high probabilitythat the heteroatom removal capability of the co-current reactor will bediminished and either the heteroatoms in their original form as organoheteroatom molecules or as the hetero-hydride will come in contact with theheteroatom sensitive downstream process or catalyst. Such contact maycause temporary or permanent impairment of the sensitive process or catalystand result in unacceptable final product quality which may require significanttime and expense (i.e. replacement of a poisoned catalyst) to rectify.A bed of heteroatom sorbent can be used to protect downstream processesor catalyst but, if a bed of heteroatom sorbent is used downstream of a co-current heteroatom removal zone in co-current operation, a separation stepfor removal of the hetero-hydride is required. The sorbent bed’s capacity canbe quickly diminished if substantial heteroatom breakthrough of the upstreamheteroatom hydroprocessing catalyst occurs and restoration of capacity willtypically require olf stream regeneration.It is relatively well known that heteroatom removal can be accomplished moreefficiently in a countercurrent flow hydroprocessing system wherein ahydroprocessing catalyst system through which the liquid hydrocarbonfeedstream flows downward and the hydrogen containing treat gas is passedupward. The counter current flow system has the potential to producesignificantly lower heteroatom content streams and to do so more efficiently.While significant potential advantage exists for the application of countercurrent hydroprocessing; especially when coupled with the use of very highactivity heteroatom sensitive catalysts, it is presently of very limitedcommercial use. US-A-3.147210 discloses a two stage process for thehydrofining-hydrogenation of high-boiling range aromatic hydrocarbons. Thefeed stock is first subjected to catalytic hydrofining, preferably in co-currentAMENDED SHEET?1015202530CA 02264021 1999-02-224flow with hydrogen. then subjected to hydrogenation over a heteroatomsensitive noble metal hydrogenation catalyst countercurrent to the flow of aUS-A-3,767,562 and US-A-3,775,291disclose a countercurrent process for producing jet fuels, whereas the jet fuelis first hydrodesulfurized in a co-current mode prior to two stagecountercurrent hydrogenation. US-A-5,183,556 also discloses a two stageco-current/countercurrent process forhydrogen containing treat gas.hydrofining and hydrogenatingaromatics in a diesel fuel stream.US-A-3,940,330 discloses a two-stage process for hydrodesulfurization of ametal—containing hydrocarbon oil employing a hydrodesulfurization catalystin each stage having an activated support prepared by drying and calcining acrystalline alumina containing 1.2 to 2.6 mols of water of hydration per moleof alumina.One reason that countercurrent flow hydroprocessing has not been morewidely commercialized is that these types of reactors are more prone todeterioration in performance due to operating excursions than conventionalco-current reactor systems. Process excursions include events such asvariation in quality or rate of the liquid feed stream or hydrogen containingtreat gas stream, start-up and shut-down of the unit. emergency depressuringof the reactor to avert hazardous conditions, or other process upsetscommonly experienced by commercial operating units. During said processexcursions, there is a high probability that the heteroatom removal capabilityof the countercurrent reactor will be diminished and either the heteroatoms intheir original form as organo heteroatom molecules or as the hetero-hydridewill come in contact with the heteroatom sensitive downstream process orcatalyst. Said contact may cause temporary or permanent impairment of thesensitive process or catalyst and result in unacceptable final product qualitywhich may require significant time and expense (i.e., replacement of apoisoned catalyst) to rectify.;:,iVlEl\lDEl3 SHEETO9'0?CA 02264021 1999-02-224.1In light of the above, there is still a need for an improved cocurrent orcountercurrent heteroatom removal process that can reliably operate undercommercial plant conditions, to produce streams containing low heteroatomcontent.AMENDED SHEET?510152025WO 98/07805CA 02264021 1999-02-22PCT/U S97/ 14761Summary of the InventionIn accordance with the present invention, there is provided a process for theheteroatom removal from a hydrocarbon stream comprising:(3)(b)(C)feeding said feedstock stream to a first reaction zonecomprising a bed of heteroatom hydroprocessing catalyst incontact with a hydrogen-containing treat gas wherein said firstreaction zone is operating at conditions effective to remove a‘ first portion of the hetero-atom content of said feedstock stream,wherein said first portion removed from said feedstock stream isin the range of 20% to 100%;passing the liquid product stream from (a) to a sorbent zonecomprising a bed of heteroatom sorbent material in contact witha hydrogen-containing treat gas wherein said liquid productstream from (a) and said hydrogen-containing treat gas areflowing in a countercurrent direction, wherein said sorbent zoneis operating under conditions effective to remove a secondportion of the hetero-atom from said liquid product stream from(a), wherein said second portion removed from said feedstockstream is in the range of 0% to 80%; andrecovering a liquid product stream from (b) wherein the amountof heteroatom remaining is in the range of from 0% to 20%,basis the starting hydrocarbon feedsteam which has not besubjected to a heteroatom removal process.?1015202530WO 98/07805CA 02264021 1999-02-22PCT/US97/14761Detailed Description of the InventionWhile the heteroatom removal process of the present invention is applicableto all heteroatom bearing compounds common to petroleum and chemicalstreams, the process is particularly suitable for the removal of the leastreactive, most highly refractory heteroatom species. The process of thepresent invention can result in a product stream which contains essentially noheteroatoms. For purposes of this invention, the phrase “essentially noheteroatoms”, depends upon the overall process being considered, but canbe defined as a value substantially less than about 100 wppm, preferably lessthan about 10 wppm, more preferably less than about 1 wppm, and mostpreferably less than about 0.1 wppm as measured by existing, conventionalanalytical technology. The invention is also applicable to consistentproduction of low heteroatom content streams. That is to say that in caseswhere steady state operation of the upstream heteroatom removal catalystresults in a steady state heteroatom concentration of X ppm; the sorbent willequilibrate with the concentration of X ppm, but when a process excursionoccurs and the heteroatom concentration significantly exceeds X ppm thenthe sorbent will adsorb or absorb more heteroatom and prevent adverseeffects on downstream catalysts or processes.The feed stocks of the present invention are subjected to heteroatom removalin at least one catalyst bed, or reaction zone, wherein feed stock flows co-current or countercurrent to the flow of a hydrogen-containing treat gas.Each zone may be immediately preceded and followed by a non-reactionzone where products may be removed and/or feed or treat gas introduced.The non-reaction zone will be a zone which is typically empty and does notcontain a catalyst that is capable of removing any heteroatoms, but it couldcontain a drying agent, such as a molecular sieve bed. In a preferred?1015202530WO 98/07805CA 02264021 1999-02-22PCT/US97/1476 1embodiment, such a non-reaction zone is an empty cross-section in thereaction vessel.The liquid effluent from the reaction zone(s), is passed on to at least onesorbent zone containing one or more heteroatom sorbents in contact with acountercurrent flow of hydrogen containing treat gas. The liquid effluent, nowwith reduced low heteroatom content, wherein the initial level of heteroatomin the hydrocarbon feedstream is reduced by levels in the range of from about20% to about 100%, may be sent to a heteroatom sensitive process, catalyst,or product disposition. in a preferred embodiment, the liquid effluent containsa heteroatom content which has been reduced by levels in the range fromabout 50% to about 100%, more preferably from about 75% to about 100%,and most preferably from about 90% to about 100%. The heteroatomsensitive process may be discrete from the countercurrent system, but ispreferentially operated in countercurrent mode and may be contained withinthe same vessel.In one embodiment the hydrocarbon feed steam first passes through a co-current hydrotreating reaction zone which contains one or morehydroprocessing catalyst(s). The effluent may then be passed to at least onecountercurrent reaction zone containing a stacked catalyst/sorbent bedsystem.During normal operation of the system, the heteroatom hydroprocessingcatalyst will convert essentially all of the organo heteroatom molecules to thecorresponding hetero-hydride. The hetero-hydride partitions into the vaporphase due to its inherent vapor pressure under hydroprocessing conditionsand is carried upward by the up flowing hydrogen-containing treat gas. Thesorbent zone sees a negligible amount of heteroatom so that its capacity isnot consumed. In the event of a process upset where unreacted organoheteroatom molecules or the hetero-hydride reaction products break through?1015202530WO 98/07805CA 02264021 1999-02-22PCT/U S97/ 14761the catalyst zone they will be sorbed by the heteroatom sorbent materialthereby protecting the downstream heteroatom sensitive process or catalyst.The sorbent may irreversibly bind with the sorbent which, while protecting thedown stream process or catalyst, will result in the sorbent needing to bereplaced or regenerated at some frequency. It is preferred that the sorbentmaterial also catalyze or otherwise facilitate the reaction of hydrogen with thesorbed organo heteroatom molecules to form the corresponding hetero-hydride.and due to its inherent high vapor pressure can be stripped from the sorbentThe hetero—hydride is typically more weakly bound by the sorbentzone by the up flowing treat gas thereby continuously regenerating thesorbent bed. A third way that the sorbent bed can function is to reversiblybind with the heteroatom and slowly release it to the down stream process orcatalyst. This is allowable where the catalyst of downstream process hassome tolerance for heteroatom; the tolerance being enhanced if thedownstream system is operated in a countercurrent mode of operation. This‘third type of sorption system may also be enhanced by a small zone ofheteroatom hydroprocessing catalyst placed below the sorbent bed andoperated in contact with a countercurrent flow of hydrogen containing treatgas. The said additional catalyst zone will convert the organo heteroatommolecules to the corresponding hetero-hydride and allow them to be strippedfrom the system by the up flowing treat gas.It is to be understood that all reaction zones and sorption zones can either bein the same vessel separated by non—reaction zones, or any can be inseparate vessels. The non—reaction zones in the later case will typically bethe transfer lines leading from one vessel to another. It is also possible tomix the sorbent with the catalyst in the bottom of the heteroatom removalzone or the catalyst at the top of the heteroatom sensitive catalyst zone wheneither or both of these zones are operated with countercurrent hydrogencontaining treat gas. This mixing of catalyst and sorbent may be?1015202530W0 98l07805CA 02264021 1999-02-22PCT/US97/ 14761accomplished by mixing of the two materials prior to formulation into particlesor may be accomplished by mixing of the particles after formulation intoparticles.This would allow the construction of smaller volume reactors andlor theproduction of lower heteroatom streams than possible using conventional co-current flow reactor technology. The said low heteroatom streams can bepassed on to other catalysts or processes which are extremely sensitive topoisoning by heteroatoms. This heteroatom sensitivity is sometimessufficiently acute as to prevent the practical use of advanced catalysts. Suchcatalysts include those which promote ring opening, aromatic saturation,isomerization, and hydrocracking.If a preprocessing step is performed to remove the so—called “easyheteroatoms", the vapor and liquid are disengaged and the liquid effluentdirected to the top of a countercurrent reactor. The vapor from thepreprocessing step can be processed separately or combined with the vaporphase product from the countercurrent reactor. The vapor phase product(s)may undergo further vapor phase hydroprocessing if greater reduction inheteroatom and aromatic species is desired or sent directly to a recoverysystem. The catalyst may be contained in one or more beds in one vessel ormultiple vessels. Various hardware (i.e. distributors, baffles, heat transferdevices) may be required inside the vesse|(s) to provide proper temperaturecontrol and contacting (hydraulic regime) between the liquid, vapors, andcatalyst.Suitable heteroatom hydroprocessing catalyst for use in the upstreamcountercurrent zone(s) or co-current reaction zone(s) can be anyconventional hydroprocessing catalyst and includes hydrotreating catalysts,hydrocracking catalysts, and hydrogenation catalysts; one or more may beused in either zone depending on the starting quality of the feed and the?1015202530WO 98/07805-CA 02264021 1999-02-22PCT/US97/1476110desired product quality. Most common are those which comprise at least oneGroup VIII metal, preferably Fe, Co and Ni, more preferably Co and/or Ni,and most preferably Ni; and at least one Group VI metal, preferably Mo andW, on a high surface area support material, which preferably is zeolite oralumina.Some catalysts which tend to have some heteroatom sensitivity may be usedin the lower portion(s) of the countercurrent reaction zone(s) due to the factthat a significant amount of heteroatom will have already been removed bythe upstream catalyst and stripped out by up flowing treat gas. Catalystssuitable for said portions are those comprised of a noble or non—nob|e metal,or metals, of Group VIII of the Periodic Table of the Elements supported in ahighly dispersed and essentially uniformly distributed manner on a refractoryinorganic support.Suitable support materials for the catalysts of the present invention includehigh surface area, refractory materials, such as alumina, silica,aluminosilicates, silicon carbide, amorphous and crystalline silica—aluminas,silica magnesias, boria, titania, zirconia and the like. In one embodiment, thepreferred support materials include alumina and the crystalline silica-aluminas, particularly those materials classified as clays or zeolites, morepreferably controlled acidity zeolites modified by their manner of synthesis, bythe incorporation of acidity moderators, and post-synthesis modificationssuch as dealumination.Heteroatom sorbents suitable for use in the practice of the present inventioninclude those selected from several classes of materials known to be reactivetoward the organo heteroatom molecules and in some cases the hetero-hydride and capable of binding same in either a reversible or irreversiblemanner.?1015202530W0 98I0780SCA 02264021 1999-02-22PCT/US97/ 1476111One class of materials suitable for such use as heteroatom sorbents arereduced metals which may be employed as bulk materials or supported on anappropriate support material such as an alumina, silica, or a zeolite.Representative metals include those from Groups la, lb, lla, llb, lllA, IVA, VB,VIB, VIIB, Vlll or the Periodic Table of the Elements (as displayed inside thefront cover of the 64"‘ Edition of the CRC Handbook of Chemistry andPhysics). Preferred metals include Zn, Fe, Ni, Cu, Mo, Co, Mg, Mn, W, K,Na, Ca, Ba, La, Ce, V, Ta, Nb, Re, Zr, Cr, Ag, Rh, lr, Pd, Pt, and Sn. Thesemetals may be employed individually or in combination.Another class of metal based materials suitable for such use as heteroatomsorbents are metal oxides which may be employed as bulk oxides orsupported on an appropriate support material such as an alumina, silica, or azeolite. Representative metal oxides include those of the metals from Groupsla, lb, Ila, llb, |llA, IVA, VB, VIB, VllB, Vlll or the Periodic Table of theElements. Preferred metals include Zn, Fe, Ni, Cu, Mo, Co, Mg, Mn, W, K,Na, Ca, Ba, La, Ce, V, Ta, Nb, Re, Zr, Cr, Ag, Rh, lr, Pd, Pt, and Sn. Thesemetal oxides may be employed individually or in combination.A third class of metal based materials suitable for such use as heteroatomsorbents are metal sulfides which may be employed as bulk sulfides orsupported on an appropriate support material such as an alumina, silica, or azeolite. Representative metal oxides include those of the metals from Groupsla, lb, lla, llb, lllA, IVA, VB, VIB, VllB, Vlll or the Periodic Table of theElements. Preferred metals include Zn, Fe, Ni, Cu, Mo, Co, Mg, Mn, W, K,Na, Ca, Ba, La, Ce, V, Ta, Nb, Re, Zr, Cr, Ag, Rh, lr, Pd, Pt, and Sn. Thesemetal sulfides may be employed individually or in combination.Zeolites and zeolite based materials may serve as heteroatom sorbents forthis invention as detailed in US-A-4,831,206 and US—A—4,831,207, both of?10152025WO 98/07805CA 02264021 1999-02-22PCT/US97/ 1476112which are also incorporated herein by reference. These materials share withspinels the ability to function as regenerable heteroatom sorbents and permitoperation of this invention in a mode cycling between heteroatom capture andheteroatom release in either continuous or batch operation depending uponthe process configuration. Zeolites incorporating heteroatom active metalsby ion exchange are also of value to this invention. Examples include Zn4A,chabazite, and faujasite moderated by the incorporation of zinc phosphate,and transition metal framework substituted zeolites similar to, but not limitedto, US-A- 5,185,135 and US-A—5,283,047, both of which are also incorporatedherein by reference.Spinels represent another class of heteroatom sorbents suitable for use inthe practice of the present invention. Such materials are readily synthesizedfrom the appropriate metal salt, frequently a sulfate, and sodium aluminateunder the influence of a third agent like sulfuric acid.Various derivatives of hydrotalcite exhibit high heteroatom capacities and forthis reason serve as heteroatom sorbents for this invention. These mayinclude numerous modified and unmodified synthetic and mineral analogs ofthese as described in US-A—3,539,306; US-A-3,796,792; US—A-3,879,523;and US-A-4,454,244, all of which are also incorporated herein by reference.The high molecular dispersions of the reactive metal make them veryeffective scavengers for heteroatom bearing molecules.Also suitable are activated carbons and acidic activated carbons that haveundergone treatment, well known to those skilled in the art, to have anenhanced acidic nature. Acidic salts may also be added to the activatedcarbon, used on other high surface area support or used as bulk sorbents.?1015202530WO 98/07805CA 02264021 1999-02-22PCT/US97/1476113The weight ratio of the heteroatom sorbent to the heteroatom removalcatalyst may be in the range of from 0.01 to 10, preferably from 0.05 to 5, andmore preferably from 0.1 to 1.Preferably, the sorbent material also catalyzes or otherwise facilitates thereaction of hydrogen with the sorbed organo heteroatom molecules to formthe corresponding hetero—hydride.The countercurrent contacting of an effluent stream from an upstreamreaction zone, with hydrogen-containing treat gas, strips dissolved hetero-hydride impurities from the effluent stream, thereby improving both thehydrogen partial pressure and the catalyst performance. That is, the catalystand sorbent can be on-stream for substantially longer periods of time beforeregeneration is required. Further, predictable heteroatom removal levels willbe achieved by the process of the present invention.The process of this invention is operable over a range of conditionsconsistent with the intended objectives in terms of product qualityimprovement and consistent with any downstream process with which thisinvention is combined in either a common or sequential reactor assembly. Itis understood that hydrogen is an essential component of the process andmay be supplied pure or admixed with other passive or inert gases as isfrequently the case in a refining or chemical processing environment. It ispreferred that the hydrogen stream be heteroatom free, or essentiallyheteroatom free, and it is understood that the latter condition may beachieved if desired by conventional technologies currently utilized for thispurpose.The various embodiments of the present invention include operatingconditions consisting of a temperature in the range of from 100 to 500 °C(212 to 930 °F), preferably from 200 to 450 °c (390 - 840 °F), and more?1015202530CA 02264021 1999-02-2214preferably 225 to 400 °C (437 to 750 °F). Pressures at which the processmay be operated include those in the range of from 100 to 2000 psig (689 to13,788 kPa), preferably from 400 to 1200 psig (2758 to 8273 kPa), and morepreferably from 450 to 1000 psig (3102 to 6894 kPa). Gas rates at which theprocess may be operated include those in the range of from 100 to 10,000SCF/B (19 to 1781 m" gas/m° oil), preferably from 250 to 7500 SCF/B (45 to1336 m3 gas/m° oil), and more preferably from 500 to 5000 SCF/B (89 to8906 m3 gas/m° oil). The feed rate velocity at which the process may beoperated varies in the range of from 0.1 to 100 LHSV, preferably from 0.3 to40 LHSV, and most preferably from 0.5 to 30 LHSV.Quite often the downstream process, catalyst, or product disposition willrequire that the liquid stream be at a lower temperature than was required inthe heteroatom hydroprocessing stream; particularly when the downstreamprocess/catalyst is performing aromatic saturation that is equilibrium limitedat higher temperatures. When this is the case it may be desirable to performthe temperature adjustment prior to contacting the liquid stream with theheteroatom sorbent as most of the sorbents having higher sorption capacitiesat lower temperatures. In such applications, each of the temperature rangesdescribed above may be decreased by as much as 100 °C (180 °F).The hetero-hydrides formed across the heteroatom hydroprocessing catalysthave a finite solubility in the liquid stream. For this reason, it may at times bedesirable to include a stripping zone to remove these hetero-hydrides beforepassing the liquid stream to the sorbent zone. This stripping zone may becontained within the same vessel or a discrete vessel and may include anytype of stripper familiar to those skilled in the art.This invention will allow consistent levels of heteroatom concentration in aliquid effluent stream by utilizing a sorbent bed in countercurrent flow.33/lEl\lU.-‘.3 ea-1::l4! O0?CA 02264021 1999-02-22W0 98l07805 PCT/US97/1476115operation to sorb higher levels of heteroatoms breaking through theheteroatom hydroprocessing zone during process excursions.The ranges and limitations provided in the specification and claims are thosewhich are believed to particularly point out and distinctly claim the instantinvention. It is, however, understood that other ranges and limitations thatperform substantially the same function in substantially the same manner toobtain substantially the same result are intended to be within the scope of theinstant invention as defined by the instant specification and the claims.

Claims (30)

WHAT IS CLAIMED IS:

1. A process for heteroatom removal from a hydrocarbon feedstock stream comprising:
(a) feeding said feedstock stream to a first reaction zone comprising a bed of heteroatom hydroprocessing catalyst in contact with a hydrogen-containing treat gas wherein said first reaction zone is operating at conditions effective to remove a first portion of the heteroatom content of said feedstock stream wherein said first portion removed from said feedstock stream is in the range of 20% to 100%;
(b) passing a liquid product stream from (a) to a sorbent zone comprising a bed of heteroatom sorbent material in contact with a hydrogen-containing treat gas wherein said liquid product stream from (a) and said hydrogen-containing treat gas are flowing in a countercurrent direction with respect to each other wherein said sorbent zone is operating under conditions effective to remove a second portion of the heteroatom from said liquid product stream from (a) wherein said second portion removed from said feedstock stream is in the range of 0% to 80%; and (c) recovering a liquid product stream from (b) wherein the amount of heteroatom remaining is in the range of from 0% to 80% basis the starting hydrocarbon feedstock stream which has not been subjected to a heteroatom, removal process.

2. The process in claim 1 further comprising:
(d) subjecting said liquid product stream from (c) to further heteroatom sensitive process selected from the group consisting of a process comprising heteroatom, sensitive catalyst a second heteroatom sensitive process not containing a catalyst a heteroatom sensitive product disposition and combinations thereof.

3. The process in claim 1 wherein said reaction zone of (a) is operated with the feedstock stream and the hydrogen containing treat gas flowing counter-current to one another.

4. The process in claim 2 wherein said heteroatom sensitive processing of (d) comprises at least one reaction zone containing a bed of heteroatom sensitive hydroprocessing catalyst wherein said liquid product stream is processed countercurrent to a hydrogen-containing treat gas.

5. The process in claim 2 wherein said heteroatom sensitive processing of (d) is at least one reaction zone containing a bed of heteroatom sensitive hydroprocessing catalyst wherein said liquid product stream is processed co-current with a hydrogen-containing treat gas.

6. The process of claim 3 wherein said feedstock stream is first processed with a hydrogen containing treat gas in at least one co-current reaction zone containing heteroatom hydroprocessing catalyst.

7. The process of claim 1 wherein said heteroatom sorbent binds the heteroatom with sufficient binding energy so as to be essentially an irreversible sorption.

8. The process of claim 7 wherein said heteroatom sorbent is a reduced metal or metal oxide selected from the group consisting of bulk material and metal or metal oxide dispersed on a high surface area support.

9. The process of claim 1 wherein the feedstock stream contains organo heteroatom, molecules and said heteroatom sorbent also catalyzes the reaction of said organo heteroatom molecules with hydrogen to produce the corresponding hetero-hydride.

10. The process of claim 9 wherein said heteroatom sorbent is a reduced metal, metal oxide, or metal sulfide selected from the group consisting of bulk material and metal, metal oxide, or metal sulfide dispersed on a high surface area support.

11. The process of claim 9 wherein the binding energy for said heteroatom hydride with said sorbent is less than the binding energy of the organo heteroatom with the sorbent so that said hetero-hydride is desorbed and carried upward by the upward flowing treat gas.

12. The process of claim 11 wherein said heteroatom, sorbent is a reduced metal, metal oxide, or metal sulfide selected from the group consisting of bulk material and metal, metal oxide, or metal sulfide dispersed on a high surface area support.

13. The process of claim 12 wherein said metal of the metal, metal oxide, or metal sulfide is a noble metal or combination of noble metals.

14. The process in claim 1 wherein said heteroatom sorbent binds said heteroatom with sufficiently weak binding energy so as to be essentially a reversible sorption wherein said heteroatom sorbent releases said heteroatom at a rate so as to have a negligible impact on said downstream process.

15. The process of claim 14 wherein said heteroatom sorbent is selected from the group consisting of a zeolite alumina, clay, acidic salt, spinel, activated carbon, aluminosilicate, hydrotalcite and a combination thereof.

16. The process in claim 3 wherein said heteroatom sorbent binds said heteroatom with sufficiently weak binding energy so as to be essentially a reversible sorption wherein said heteroatom sorbent releases said heteroatom at a rate so as to have a negligible impact on said downstream process.

17. The process of claim 1 wherein said heteroatom hydroprocessing catalyst is selected from the group consisting of hydrotreating catalyst, hydrocracking catalyst, hydrogenation catalyst, hydroisomerization catalyst, ring opening catalyst, catalytic dewaxing catalyst, and a combination thereof.

18. The process of claim 6 wherein said heteroatom hydroprocessing catalyst is selected from the group consisting of hydrotreating catalyst, hydrocracking catalyst, hydrogenation catalyst, and a combination thereof.

19. The process of claim 1 wherein said heteroatom sorbent is selected from the group consisting of reduced metals, metal oxides, metal sulfides, clays, acidic salts, spinels, zeolites, activated carbon, aluminas, aluminosilicates, hydrotalcites and a combination thereof.

20. The process d claim 19 wherein the metal in said reduced metal, metal sulfide or metal oxide of the heteroatom sorbent is selected from the group consisting of Groups la, lb lla, llb, lllA, lVA, VB, VlB, VllB, Vlll, and a combination thereof of the Periodic Table of the Elements.

21. The process of claim 1 wherein the temperature of said liquid product stream passing between the first reaction zone and sorbent zone is reduced, through injection of quench or heat exchange, so as to improve the sorption capabilities of the sorbent(s).

22. The process of claim 1 wherein said liquid product stream passing between the first reaction zone and sorbent zone is passed through at least one stripping zone to remove volatile hetero-hydrides before passing into the sorbent zone.

23. The process of claim 1 wherein said heteroatom sorbent is mixed into said heteroatom hydroprocessing catalyst of first reaction zone of (a).

24. The process of claim 4 wherein said heteroatom sorbent is mixed into said heteroatom sensitive hydroprocessing catalyst of further heteroatom sensitive processing (d).

25. The process of claim 2 further comprising an additional zone of heteroatom hydroprocessing catalyst placed downstream of the heteroatom sorbent bed and operated in catalyst with a countercurrent flow of a hydrogen containing treat gas prior to said liquid product stream being passed to (d).

26. The process of claim 14 further comprising an additional zone of heteroatom hydroprocessing catalyst placed downstream of the heteroatom sorbent bed and operated in contact with a countercurrent flow of a hydrogen containing treat gas prior to said liquid product stream being passed to (d).

27. The process of claim 1 wherein the heteroatoms are selected from the group consisting of sulfur nitrogen oxygen the halogens and mixtures thereof.

28. The process of claim 4 wherein the second heteroatom sensitive process is an aromatic saturation process.

29. The process of claim 4 wherein the second heteroatom sensitive process is a selective hydrocracking process.

30. A process for heteroatom removal from a hydrocarbon stream where the heteroatoms are selected from the group consisting of sulfur nitrogen oxygen the halogens and mixtures thereof said process comprising:
(a) feeding said feedstock stream to a first reaction zone comprising a bed of heteroatom hydroprocessing catalyst in contact with a hydrogen-containing treat gas wherein said first reaction zone is operating at conditions effective to remove a first portion of the heteroatom content of said feedstock stream wherein said first portion removed from said feedstock stream is in the range of 20% to 100%;
(b) passing a liquid product stream from (a) to a sorbent zone comprising a bed of heteroatom, sorbent material in contact with a hydrogen-containing treat gas wherein said liquid product stream from (a) and said hydrogen-containing treat gas are flowing in a countercurrent direction with respect to each other where said heteroatom sorbent material is selected from the group consisting of reduced metals metal oxides metal sulfides clays acidic salts spinels zeolites activated carbon aluminas aluminosilicates hydrotalcites and a combination thereof, and wherein said sorbent zone is operating under conditions effective to remove a second portion of the heteroatom, from said liquid product stream from (a) wherein said second portion removed from said feedstock stream is in the range of 0% to 80%; and (c) recovering a liquid product stream from (b) wherein the amount of heteroatom remaining is in the range of from 0% to 80% basis the starting hydrocarbon feedstock stream which has not been subjected to a heteroatom removal process.