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    12 493 374 Integrated Processes for Prop

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    Etileno

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    8 views13 pages

    12 493 374 Integrated Processes For Prop

    Uploaded by

    Italo Vargas Olivera
    Etileno

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    of 13
    ‘US 2010033158941 cu») United States cz) Patent Application Publication co) Pub. No.: US 2010/0331589 Al ZIMMERMANN et al. (54) INTEGRATED PROCESSES FOR PROPYLENE PRODUCTION AND RECOVERY Inventors 6) Joseph E. ZIMMERMANN, Arlington Heights, IL (US); Larry - Briekson, Arfington Heights IL (US): Gregory 4. Nedohin, Des Plsines, TE ‘COLUMBIA DRIVE, P © BOX 2245 MAIL STOP ABB. MORRISTOWN, NJ 07962 (US) (43) Pub. Date: Dec. 30, 2010 (22) Filed Jun. 29, 2009 Publication Classification (1) Ince Core 5438 200601) (2) US.CL sasia1d on ABSTRACT Processes utilizing the integration of (i) processes andl the associated equipment used to purify and recover propylene from propane- and/or C,e-containing refinery hydrocarbon scams, with (i) catalytic dehydrogenation are disclosed. This integration allows for elimination of some or al ofthe conventional frctionation section of the dehydrogenation process, normally used o purify propylene from tnconvertd Propane i the reactor effvent, Sigaficaat capital and wility (21) ApphNos—r24paan4 Jivngs oe therefore sane 2 4 ae —lL+| s0 ; ~ ree 20 ' 1, ' 16 ' Lao Ll, 26 ' 200 14 ee eee te 6 8 Patent Application Publication Dee. 30, 2010 Sheet 1 of 4 US 2010/0331589 AI 10 = 18 16 pt» 200 14 a 12 EIGh US 2010/0331589 AI Dec. 30, 2010 Sheet 2 of 4 Patent Application Publication US 2010/0331589 AI Dec. 30, 2010 Sheet 3 of 4 Patent Application Publication 08 US 2010/0331589 AI Dec. 30,2010 Sheet 4 of 4 Patent Application Publication US 2010/0331589 Al INTEGRATED PROCESSES FOR PROPYLENE PRODUCTION AND RECOVERY FIELD OF THE INVENTION 10001] The invention relates to processes for propylene production and more particularly to the dehydrogenation of propane recovered from catalytic eracking processes such as foi catalytic eracking (FCC), DESCRIPTION OF RELATED ART 0002} Propylene demand! in the petrochemical industry has grown substantially largely dueto its use asa precursorin the production of polypropylene for packaging materials and ‘other commercial products, Other dowsnsircam uses of pro= pylene incade the mantfacture of aerylonitrle acrylic aid, ‘acrolein, propylene oxide and glycols, plasticizer oxo aleo- hols, cumene, isopropyl alcohol, and acetone. Currently, the majority of propylene is produced during the steam eracking ‘or pyrolysis of hydrocarbon feedstocks such 3s natural as, petroleum liquid, and carbonaceous materials (e3., coal recycled plastics, andorganic materials), to produceethylene Additional significant sources of propylene are byproducts of ‘uid eatalytic cracking (FCC) and resid Mid catalytic crack Jing (REC), normally targeting gesoline production. PCC is described, for example, in US. Pat. No. 4,288,688 and else where. mixed, oetinie CJC, byproduet stream of FCC may be purified in propylene to polymer grade specifications by the separationofC, hydrocarbons, propane, ethane, andther ‘compounds [0003] - Much of the current propylene procicton is there- Tore aot “on purpose” but as a byprodct of ethylene and ‘gncoline production. This leads to difficulties in coupling propylene production capacity with its demand inthe mar- ketplace. Moreover, mich of the new steam cracking capacity will be based on using ethane as leedstock, which typically produces only ethylene as a final product. Some hydroear~ bons heavier than etiylene are present, but generally notin _quantties suficent to allow for their recovery in an econo ‘cal manner. In view of the eurrent high growih rate of ropy” Jene demand, ths reduced quantity of co-produced propylene rom steam cracking will only serveto accelerate the value of propylene in the marketplace. 0004) More recently the dese for propylene and other Tight olefins from altemive, non-petroleum based feeds has Jed to the use of oxygenates such as alcohols and, more particularly, methanol, ethanol, and higher aleohols or theie ‘rivatives. Methanol in particular, is usefal ia a methanol to-olefin (MTO) conversion process described, for example, in US. Pat, No. 5.914.433. The yield of light olefins from suel a process may be improved using olefin cracking (© ‘convert some or all of the C+ product of MTO in an olefin, ‘racking reactor, as described in U.S. Pat. No, 7,268,265, ‘Other processes forthe targeted production of light olefins involve high severity catalytic eracking of naphtha an other hydrocarbon factions. A catalytic naphtha cracking process ‘ofeommercal importance is deseribed in US Pat. No. 6.867, 34, [0005] Paralfin dehydrogenation represents yet another dicated route to light olefins and is deseribed in US. Pat No. 3.978 150 and elsewhere. However, the significant capi tal cost of a propane debyelrogenation plant is normally js- tified only in eases of lante-scale propylene production wits Dee. 30, 2010 (ex, typically 250.000 metric tons per year or more). The substantial supply of propane feedstock required to mai this capacity is typically avaiable from propane-rich Tiguetied petroleum gas (LPG) streams from as plant sources. [0006] Despite the variety ofboth dedicated and non deat fated routes Tor generating Hight olefin industrially, the {demand for propylene in particulars outpacing the capacity fof sch conventional processes. Moreover, farther demand arowth for propylene is expected. A need therefore exists for fost-elfective methods that can increase propylene yields rom existing refinery feed sources that are not necessaily of the scale of commercial LPG sircams from natural gas pro- ‘ction SUMMARY OF THE INVENTION [0007] Te invention is associated with the discovery of ‘contmical processes for propylene production, and partiew- larly those in which impure propane in refinery streams is separated from a purified propylene fraction, as the main product, aed optionally other components. [0008] "The separated propane is deiydrogenated, offen to ‘extincion oF near extinction ina recycle oop (i.e. 10 effect ‘complete or nearly complete propane conversion). parien- Jar refinery stream of interest, which often forms at least part ofthe hydrocarbon feed to the processes described herein, is ' propylene- and propane-conlaining product of a catalytic cracking process such as lui eatalytie cracking (FCC) or resid catalytic ercking (RFC). For example, a byproduct faction containing C, and C, hydrocarbons is: normally ‘oblained from an FCC gas concentration section thats fed by ‘overhead vapors from the FCC main fretionaion eofuin, ‘This byproductisrichinC,andC, olefins due to theupstream cracking reactions being carried out in the absence of added hydrogen. 0009} Aspects ofthe invention relate to the integration of | ( processes and the associated equipment used to purify and recover propylene from propane- andor Cy¢-contsining refinery hydrocarbon streams, with (i) catalytic debydroge- ration. This integration allows for elimination ofthe conven- ‘ional fractionation seetion ofthe dehydrogenation process, ‘normally used to purify propylene fom unconverted propane ‘and other components in the reaetor effvent, Signifieant ea ‘al and lity savings are therefore attained, de to the sub- stantial energy and equipment requirements essociated with ‘his separation. The“shating”of major separation equipment, whieh may include a depropanizer, a deethanizer, andlor & propane’propylene splitter, between propylene recovery and catalytic dehydrogenation processes provides important cost bbencits relative to carrying ont these processes separatcly {0010} In particular, combining process stream that ben- fit, in the inteyrated processes described here, fom being treated ina similarmannerallows forthe realization of econ- anies of scale. Tha i, the added costs for larger capacity equipment (e., distillation columns) and is operation in processing combined propylene-containing streams is sig- pifcantly less than that of duplicating at least some of the same or similar equipment in separate processes. Moreover, the use of integrated processes can, in some cases, reader smaller capacity catalytic dehydrogenation units ecoomi cally feasible when coupled with existing or planned propy- Tene recovery processes, [011] According to particular embodiments, therefore intograted methods for propylene production comprise p= cessing, ina propylene recovery unit (PRU), a hydrocarbon US 2010/0331589 Al ‘eed comprising propylene-containing products ofboth eata- Iytic racking and catalytic dehydrogenation processes Prod- Uels of the propylene reeovery. or PRU produets, include @ purified propylene fraction and a puriied propane Iraction Advantageously, the purified propane is passed tothe eata- Iytie dehydrogenation proces to conver least portion of the separated propane to higher-value propylene. This con- verted propylene i therefore contained in the catalytic deby= Jatin stags) to separate products on the bass of differences in relative volatility, 0032] Forexample, the main column can separate gasoline boiling range hydrocarbons from the reactor effluent as a Dee. 30, 2010 [PCC gasoline product steam along with other products. The FCC gasoline product may be debutanized, such that it eon- ‘ains, for example, less than about 3%, aad often Tess tha shout 1%, by volume of C, and lighter hydrocurbons. AC,” hydrocarbon stream can therefore be separately recovered ‘om the reactor effluent, with this stream typically being further fractionated into fuel gas and more valuable CC, fydrocartons as an LPG comprising a significant amoust of propylene and, olefins as discussed above. This propylene- ‘ontining prodactof FCC is therefore a desirable component ‘ofthe hydrocarbon fed that is processed inthe PRU aceord- ing to embodiments ofthe iavention, [0033] Other products of catalytic cracking, and FCC in particular, nelude actions containing higher boiling hydeo- carbons, compared t those ia an FCC gasoline product steam. Examples of such produets are heavy naphia and Tighteyele ol. According to some embodiments, unconverted hhydrocarbons exiting the main column, for example in the bottoms stream, may be recycled to the catalytic eacking ‘zone to enhance the overall conversion. Resid iid catalytic ‘racking (RFCC) isa catalytic cracking process thats similar to FCC as discussed above, but modified to target heavy lhydrocarhon feedstocks wilh a greater coking tendency’ by ling to catalyst regeneration tages and eatalyst cooling {fo aocommodate the enhanced regeneration requirements, including high heat of coke combustion, Other related cata. Iytic cracking processes ae also known inthe art and inelude RCC, MSCC™, PewoF CC and others, from which pro- rylene-contaiaing catalytic racking products may’ be ‘obtained and uilized in integrated processes socording fo the ‘present invention, A common feature of sich processes isthe tse ofa hydrogen deficient atmosphere in the restion zone, resulting inthe generation of one or more catalytic racking products containing propylene and normally other olefins. [0034] flow scheme according to aspects ofthe invention is shown in FIG. I In this illustrative embodiment, heavy bhydrocarhon feedstock 2 such as VGO is passed to catalytic tacking process 300 to provide propylene-containing prod- vet, which generally also comprises C, olefin (¢.,normal 1 and 2-butenes and/or isobutylene). Propylene-containing produc 4s therefore catalytic eacking product that may be ‘oblained, for example, from contacting heavy hydrocarbon ‘eedstock 2 with a catalyst of aud catalytic racking (FCC) process as discussed above, Propylene-contsining product 4 Is processed together with faction 6 (ea liquid fraction) of neffivent from a dehydrogenation reaction zone of catalytic Sehydrogenation process 100, Dehydrogenation reaction ‘zoe ellivent fraction 6 is propylene-contining product of catalytic dehydrogenation process 100, and hydrocarbon feed § to propylene recovery unit (PRU) 200 comprises both of these propylene containing products 4.6. As discussed above. ‘dehydrogenation reaction one effluent fretion 6 is normally ‘oblained asa igud Traction, containing propane and prop lene, of te total effhient from the eacton zone of dehydro- szenztion process 100, The net hydrozen produced incatalyt ‘elyydrogenation process 100 is contsined in net off gas 20, whieh is 4 non-reeyeled portion of a vapor fraction of the {dehydrogenation reaetion zone effluent [0035] PRU 200, processes hydrocarbon feed 8 comprising catalytic cracking product 4 and a catalytic dehydrogenation product, namely dchydrogenation reaction zone eftent mc- tion 6 to provide PRU products comprising purified propy- lene fraction 10 and purified propane fraction 12. in the ‘normal case where catalytic eracking produet 4s. Fiquefied US 2010/0331589 Al petroleum gas (LPG) comprising C olefins in addition t0 propylene. an addtional PRU proht is generally aC, olefin- ‘enriched fraction 14 that may be sent for Turher processing (ex inthe production of methy tertiary butyl ether, MTBE). AA further PRU product is C= hydroearbon enriched frae- tion 16 (ie. enriched in methane, edune, and ethylene). The designation of a fraetion as being eariched in various com= ponents means thatthe fraction contains a higher eoncentra- tion (e.g, measured in pereent by volume) of those compo= nents, relative to the hydrocarbon fed 8 to the PRU 200. Likewise, fractions 10, 12, 14, and 16 also contain higher ‘concentrations of propylene, propane, C, olefins, and C,— hydrocarbons, respectively, than the feeds to the individual Jactionation or distillation columns used to provide the fne- tions, as discussed in preater detail below 10036] | PRU 200 generally includes a selective hydrogena- tion process for the comversion of diolefins (ex, butadiene) sand other highly unsaturated byproducts (eg, acetylene) of ‘catalytic dehydrogenation process 100 to more desirable (and, Jess reactive), comesponding monoolelins. A representative selective hydrogenation process for converting diolefins 10 monoolefins is described, for example, in US. Pat. No. 4695, 560, with respect toa selective hydrogenation catalyst com Prsing nickel and sulfur dispersed on an alumina support material having a high surface area 10037] Selective hydrogenation is normally performed swith a selective hydrogenation zane being maintained under relatively mild hydrogenation condition, ineluding an abso- Jt pressure from about 280 kPa (40 psi) to bout $500 kPa (800 psa), with ange from about 350 kPa (50 psia) to about 2100 kPa (300 psia) being preferred. Relatively moderate elective hydrogenation zone temperatures, for example, from about 25° C. (77°F. to about 350° C. (662° F.), prefer ably from about $0° C. (122° Fo about 200° C, 892° F), fare representative. The liquid hourly space velocity (L1ISV) js typically greater than about I hr, and preferably greater than about Shy"! (e.g. between about § and about 35 he") The LHSV, closely related othe inverse of the reactor resi dence time, is the volumetric guid flaw rateover the catalyst bd divides by the bed volume and represent the equivalent ‘numberof catalyst bed volumes of guid processed per hou. An important variable in seletive hydrogenation is the ratio ‘of makeup hydrogen to dioefins in the hydrocarbon feed t0 the selective hydrogenation process. To avoid the undesired saturation of a significant proportion of the monooletins, ‘eneally less than about 2 times the stoichiometric hydrogen Fexjirement for olefin saturation is used 10038], Sclectivehydrogenation therefore requires theaddi- tion of makeup hydrogen 18 that can have varying levels of purity, depending on the Source. An optional feed stream to the integrated processes described herein is propane-rich LPG stream 28 obtained, for example, from a natural gas plant that soften an industrial source of propane fr catalgtic Uchydrogenation process 100 to produce propylene. Such 8 propane-rich LPG stream generally comprises at least about 50% by weight propane with only # minoe amonat (e, Tess than about 5% by weight) of propylene. As shown in FIG. 1, propane-rich LPG stream 28 may be combined with hydro- ‘carbon feed & that is processed in PRU 200 ot with other process streams orapparatuses of PRU, as discussed in more tail below. Alternatively, optional propanc-rich PG. stream 28 ean bea component of the feed to catalytic dehy- “drogenation process 100, together with purified propane frac tion 12 Dee. 30, 2010 [0039] As is apparent in FIG. 1, purified propane fraction 12, catalytic dehydrogenation product 6, and hydrocarbon eed 8 PRU 200 provide recyele loop that advantageously allows, in a continuous manner, @) recovery of propylene rom the propylene-containing produet4 of catalytic racking (ea, LPG recovered from FCC and comprising predomi- ‘antly propylene and C, olefins) and (i) reeyele of propane from this propylene-containing prodict to extinction or near extinction by eonversion to propylene in catalytic dehydro- ‘enation process 100, In representative embodiments, for ‘example, the overall conversion of propane inthe LPG from FCC, comprising propane. propylene, and C, olefins, is at Jeast about 96%, and often at leat about 95%. Moreover, the integration of catalytic dehydrogenation process 100 with PRU 200 provides significantly improved economies over the case ofa conventional, stand slone dehytdrogenation process izing propane from FCC as a feed, In many eases, this source of propane would not provide suficent capacity 10 render catalytic dehydrogenation economically feasible at all [0040] FIG. 2 depicts representative catalytic dehydeoge- ‘ation process 100 that may'be used in the integrated process illustrated generally in FIC. 1. As noted above, purified pro- pane fraction 12 and optionally propane-rich [PG stream 2 tre passed as feeds o catalytic dehydrogenation process 10. Punied propane fraction 12 is nommally combined with a recycled portion 102 of vapor fraction 104 of effluent 106 of the reaction zone of dehydrogenation process 100. A non- recycled portion ofthis vapor fraction 104 is net off pas 20, ‘whieh contains the net hydrogen produced in catalytic dey rogenation process 100, The combined dehydrogenstion eed 108 is then passed to dehydrogenation combined feed! effluent heat exchanger 12S and further heated with preheater 135 prior to entering the dehydrogenation reaction zone com prising four dehydrogenation reactors 150a-150d in series, as ‘epicted in the specific embodiment of FIG. 2 [0041] In operation, dehydrogenation reactors 1800-150 ‘often contain moving beds of catalyst. The dehydrogenation catalysts passed serially through the reactors 1804-180dand spent or coked catalyst exiting the last reactor 180d is then regenerated by knowamethods for eontiavous calalystregen- eration (CCR) before being retumed as menerated catalyst to the fist reactor 180a in the series, The catalyst cireuation Joop is not shown forsimpliety nterstage heaters 4S0-145c between actors 150-150 compensate forthe temperatire drop across each reactor due to the main dehydrogenation action (Le. the conversion of propane to propylene) being endothermic. EMuent 106 of the reaction zone of debydeo- ‘genaton process 100s then cooled with the combined deby- dogenation feed 108 in combined feediefluent. heat ‘exchanger 125, The effleat 106 from the dehydrogenation reaction zone is introduced to eryogenie separator 160 t0 ‘obtain fraction 6 of dehydrogenation reaction zone effluent 106 comprising propane and propylene, which is normally foblained asa liquid fraetion, [042] Deliydrogenation process 100 therefore ineludes a reaction zone (eg. comprising multiple reactors and inter- stage heaters) anda separation zone (eg, comprising a eryo- ‘genic separation separator 160) that provides, respectively, CC hydrocarbon-rich fraction 6nd hydrogemrich vapor fac tion 104, respectively, of the total dehydrogenation reaction zone event 106. According to embodiments ofthe inven- tion, dehydrogenation process 100 docs not include the capi fal costand energy-intensive fractionation towers used 10 US 2010/0331589 Al purify product propylene and reeover propane from action 6 for reeycle back o the dehydrogenation reaction zane. These separation funetions are advantageously performed using PRU 200 that i usually necesary ia any event for recovery of propylene from propylene-containing product 4 of catalytic ‘racking process 300. Integration of PRU 200 with catalytic ‘dehydrogenation process 100 therefore provides economic tlfciencies as disctsed above, even recognizing that the ‘capacity of PRU 200 is increased, relative t the case of Separate (ie. nom-integrated) cracking and dehydrogenation processes. According to particular embodiments of te inven- tion, therefore, catalytic dehydrogenation process 100 con- sists essentially of a dehydrogenation reaction zone and ‘eryouenie separation zone, without fractionation towers. [0043] A PRU 200 according to an embodiment of the Jnvention is illstated in FIG. 3, PRU comprises a faction- jon section that includes depropanizer (eg. Cy/C, spite) 310, deethanizer 320, and propane/propylene spiter 330. As “discussed above, propylene-containing products 4,6 of cata Ivtic cracking and catalytic dehydrogenstion are combined as 4 hydrocarbon feed 8, optionally with propane-rich LPG stream 25, and passe to depropanizer 310 to provide low- boiling depropasizer Ircton 302 that is enriched ia propy- Jens, propane, and. hydrocarbons, rlaiveto hydrocarbon feed 8. Also, C, olefin-enriched fraction 14 (having a higher (C, olefin concentration than hydrocarhon feed 8) i removed ‘38 ahigh-boiling fretion from depropanizer 310. Low-boi ing depropanizcrSraction 302 is then passed to deen 320 (0 provide a low-boiling deethanizer fraction tbat is ‘enriched in C,~ hydrocarbons relative to the feod 10 dewtha- nizer, namely low-boiling depropanizer fraction 302, The fow-boiling desthanizer fraction is therefore namely C- hydrocarbon enriched fraction 16 as a product of PRU 200. Also obtained from deethanizer 320 is high-boiling deetha- nhizer fraction 304 enriched in propylene and propane relative to the food to the deethanizer 320, High boiling deethanizer Jraction 304 is then passed toa tied fractionation column, namely propane!propylene splitter 330 that provides purified propylene Iraction 10 and purified propane fraction 12 as Jow-boling and high-boiling fractions, respectively, of pro- pane/propylene splitter 330, which are aso net products of PRU 200. [0044] In addition tothe fractionation section of PRU 200, FIG. 3 alo illustrates an optional treating section comprising 1 conventional carbonyl sulfide (COS) removal system 325 that utilizes a suitable solvent to reduce the level of this ‘contaminant ifnecessary. Other possible treating section sys- ‘ems include water removal oradsorbent drier system 315and metals removal system 335 for reducing amounts of metals (ea, antimony), which ate often present as metal hydrides such as arsine and phosphine. As illustrated in FIG. 3, driee system 315 may be used to dry purified propylene fection 10 ‘alone andlor may optionally be positioned upstream of pro- ppane/propylene splitter 390 in order to adlitionay dey pui- fied propane fraction 12 and thereby potentially obviate the need for driers on the feed to catalytic dehydrogenation pro- ‘ess 100, According to particular embodiments ofthe inven- tion, COS removal system 328, drier system 318, and metals removal system 338 together provide purified propylene fac- tion 10 thats teated propylene produc, preferhly having a purity of at least about 99% by volume, and often atleast abut 99.5% by volume tomeet polymer gnde specifications. [0045] In other embodiments, the propylene purity may be Tower, depending on the end use ofthis product, Fr example, Dee. 30, 2010 a purty of at least about 97% by volume (ein the ruse {rom about 97% to about 99% by volume) or at least about 98% by volume (eg, in the range from about 98% to about 99% by volume) may be acceptable fora non-polyamertech- nology such as aerylonitrile production, or otherwise for polypropylene production processes that can aecommodste a Jower purity propylene. In yet further embodiments in whieh the propylene purity is below 97% (eg, in the mange from about 90% to about 95% by volume) it may be desirable to include selective hydrogenation (not shown) ofthe purified propylene fraction 10, in the manner discussed above with espoct to converting highly unsaturated byproducts of dehy

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