2) United States Patent Brown et al. (54) PROCESS OF MANUFACTURING PARA-XYLENE (75) Inventors: Stephen Harold Brown, Annandale, NJ (US); John Seott Buchanan, Lamberwill, NJ (US) (73) Assignoe: ExxonMobil Chemleal Patents Ine, Houston, TX (US) (#) Notice: Subject to any disclaimer the tem of this pateat is extended of adjusted under 35 USC. 154(b) by O days (21) Appl. Nos 12/603,986 (22) Filed: et. 22,2009 6s) Prior Publication Data US 2010004051741 Feb. 18, 2010 Related Application Data (62) Division of pplication No, 11/823,384, filed on Jun. 28, 2007, now Pat. No 7,629,498 (1) neck Bois 00 (2005.01) Bol sod (2005.01) cure 1/00 (2006.01), (52) US.C1 . 4221600; 422/187; 422/630, 585/319; 585/322; 585/923; SRS/NOS: 208/61 (58) Field of Classification Search 422/187, 422/189, 600, 630; 585/319, 322, 323, 805: 208/61 ‘See aplication ile for complete search history. ‘USO08048388B2 (10) Patent No. 4s) Date of Patent: US 8,048,388 B2 Nov. 1, 2011 66) References Cited US. PATENT DOCUMENTS 4101895 A 71978 Chenet at S308 A * 61994 Chang etal asians Soaes72 A” 42000 Brown etal Sats Be 12004 Brown ToIwAST B2* 32005 Powers sass 7419299 210260 Johnson eal 73176339 B2 22007 scene eta Fise87S 2 32007 Fenget a 2ood0HSSLLL AL 82004 Johison et annsto7sse4 AL 42008 Feng etal FOREIGN PATENT DOCUMENTS COTTIER PUBLICATIONS ‘ashima etal, “Allyltion on Syaetc Zeolites, L. Alkylation of Toluene with Methanol, unl of Catalysis 16, (1970) p. 273 * cited by examiner Walter Gritin Lessanework Seif Andrew B. Grits Primary Examiner Assistant Examiner (4) Attornes, Agent, or Firm 57) ABSTRACT This disclosure relates 0 a process of manufacturing pa xylene, comprising (8) contacting a pygas feedstock and ‘methylating agent with catalyst under reaetion conditions to pradlce & prodict having para-xyee, wherein the product has higher para-xylene content than the para-xylene content of the pygas feedstock: and (b) separating the para-xylene fom the product of the step (a), wherein the eatalyst com> rises a molecular sieve having « Diffision Parameter for 2.2-dimethylbataneo about 0.1-15 see"! when measured at femperatire of 120° C, anda 2,2-dimethyTbutane pressore oF '8 kPa-a andthe pygas eomprises from about | Yo about 65 wt Ye benzene and fom shout § 1035 wt % toluene 3 Claims, 3 Drawing SheetsUS 8,048,388 B2 is} » U.S, Patent Nov. 1, 2011 Sheet 1 of 3 ry <_| Cc ane 2 & N N T (| Oe 5 [2 & fs ch eh | T oa ey co L N a N 4 o Fig. 1U.S. Patent Nov. 1, 2011 Sheet 2 of 3 US 8,048,388 B2 ge 2 > @ Go ee5F orFZE onde wo s a g a Be a < 2 B 2 zie ga 6 D af Ge 3 e 3 . A “ a a e Rl ° x #£ 8 8 # 8& Ss & &§ 8 & & 8 £¢ 8 & & eue|A\yaU.S. Patent Nov. 1, 2011 Sheet 3 of 3 US 8,048,388 B2 2 3 #2 ou 8 ® re 5 2 | be 88 oD on a O° $s ¢ 7 ¢ T o sx xs Ss SF SF 8 § 8 & & 6 eue|AuaUS 8,048,388 B2 1 PROCESS OF MANUFACTURING PARA-NYLENE (CROSS REFERENCE TO RELATED "APPLICATIONS, ‘This application isa Divisional Application of US. appli- ‘cation Ser. No. 11/823,584, iled Jun. 28, 2007 now US. Pat No, 7,629,498, now allowed FIELD OF THE INVENTION ‘This disclosure relate oa method of making para-xylene, ‘optionally co-production of light olefins, from pyrolysis, tasoline feedstock. In particular, this disclosure relates 10 method of making pars-xylene, optionally eo-prodvction of Fight olefins, from a caide oF resid-contaning. fraction thereof BACKGROUND OF THE INVENTION Of the xylene isomers, part-xylene (PX) is of particul value since its useful in the manufacture of terephthalic ac whici is am intermediate in the manufacture of synthetic fibers. Para-Xylene is presently produced almost exclusively ‘rom naphtha by catalytic reforming process, The aromaties produced are used as feedstock vo aromatis plans, Aromal- tes plants purify tolvene and mixed xylene. Purified toluene may be selectively oF non-seloctively disproportioaated 10 produce para-xylene and benzene. Para-xylene may also be produced from mixed xylenes by isomerization/Separations shod! for producing xylenes involves the alkylation of toluene with methanol over a solid acid catalyst. “Thus the alkylation of toluene with methanol over cation: ‘exchanged zeolite Y has been deserbed by Yashima eta. in the Journal of Catalysis 16, 273-280 (1970), These workers reported selective prediction of pantoxylene over the approximate temperature range of 200 to 275° C,, with the ‘maximum yield of para-xylen inthe mixture of xylenes, i. about $0 wt % of the xylene product mixture, boing observed 225° C, Higher temperitures were reported to result in increase inthe yield of meta-xylene and a decrease in pro- ‘duction of para and ortho-xylenes USS. Pat, Nos. 7,119,239 and 7,176,339 diselose a process {or the production of xylenes from reformate. The process is carried out by methylating under conditions effective forthe methylation, the benzene'toluene present in the reformate ‘outside the reforming loop, fo produce a resulting product having a higher xylenes content than the reformat. Greater than equilibrium amounts of para-xylene can be praduced by the process. US. Pat.No. 7,186,873 discloses process forthe production ofxylenes from reformate by reactive dstilation. ‘Theprocess is carried out by methylating the benzene'toluene present in the reformate in a reactive distillation zone and Under reactive distillation conditions to produce a resulting product having a higher xylenes content tha the reformat rater than exuilibyuim amounts of para-xylene ea be pro ‘duced by the process. ‘As firs the present inventors aware, ithas previously not boon suggested to methylate a pyrolysis gasoline (pyz05), t0 rmanuficturing paraexylene nor has been suggested to inte- ‘arate a catalytic system comprising a steam cracker and 3 methylation unit to produce para-xylene, and optionally €o- produce light olefins. There is no prior art disclosing the production of paraexylene from resid and methylating agent 0 o 2 eedstocks by any means, There is ao prior art teaching the use of methylation technology ta convert ehylbenzene to para-xylene and ethylene USS. Pat. No 6,046,372 discloses a process for converting ‘methanol and/or dimethyl ether toa preluet containing C0 Cy olefins which comprises the step of contacting & food ‘whieh contains methanol andior dimethyl ethee with a cata- ys comprising a porous erystalline material, said contacting sep being concocted in the presence of an aromatic com potnd under conversion conditions including a temperature (0f350°C. 10480" C, andametlanol partial pressure in excess ‘of 10psia (70 KPa) said porous erystlline material having @ pore size greater than the critical diameter of the aromatic ‘compound and the aromatic eompound being capable of alky- Jation by the methanol andr dimethyl ether under said con- version conditions, USS. Pat. No. 6,680,418 discloses a process for converting ‘methanol andor dimethyl ether toa product containing C, 10 olefins, which comprises the step of contacting reaction nixture containing methanol andor dimethyl ether and at Teast 10 wt % of @ polymethylbenzene component select {rom rimethylbenzenes,tetramethylbenzenes and mixtures thereof with a catalyst comprising a porous erystalline mate- ‘iol. The contacting sep is conducted under conversion eon- ditions including temperature of about 250°C. toabout 500° CC. and a methanol andlor dimethyl ether partial pressure of about 5 to about 250 psia (35 t0 1725 KP). The porous ‘erystalline material usedin the catalyst basa pore size greater than the erica diameter of the aromatic compound and a Diffusion Parameter for 2,2-dimethyTbutane of at feast $00 soo"! when measured a @ temperature of 120° C. and a 2.2- dimethylbutane pressure of 0 tore (8 KPa), ‘All methylation processes use relatively pure tolene, mix tures of tolene ad benzene, or reformate as feedstock for ‘manufacturing xylene, preferably pars-xylene. The sources of toluene/benzene feedstock for the methylation process ‘ay be reformate or pygas. However, othe best knowledge ‘of the inventor, there is no disclosure of using pygas a the fromatie feedstock for the methylation process. It is well ‘known toa person of ordinary skill that pygas contains large amount of non-aromatics, some olefinic hydrocarbons, and a high ethylbenzene content in the C., aromatics. Both non- aromatics and olefinic hydrocarbons are koown for catalyst ‘deactivation and aging. Fibylbenzene is known as a bad feed- lock for pars-xylene production, Furthermore, there is 0 disclosure using pygas without extraction as the aromatic ‘eedstock forthe methylation process. ven more, there is n0 disclosure using pygas oblained from steam ereeking a hydrocarbon feestoek made with hydroprocessed resid with’ ‘without extraction 2s the aromatic Feedstock forthe methya- tion process There is, thorefore, a need 10 dovelop a technology 10 produce paru-xylene in high yield from pyas feedstock, ‘nother technical challenge related to wse of py feedstock Tor para-xylene prodiction is rapid catalyst deactivation becatise the pygas feedstock contains certain amount of non- ‘romaties which may deaetvate the catalyst. Therefore the pygas feedstock normally is subjected to an extraction pro- fess fo remove most of the aon-aroaiates before further processing. However, the extretion proces is expensive and ‘pital intensive. There is also a need to produce aromatic prodicts fom pygas without extraction, We surprisingly discovered a process of manufacturing PX, optionally eo-manufecturng light olefins, fom a pygas ‘eedstock by methylaing the pygas with a methylating agent using a molecular sieve catalyst. Furthermore, the para-xy- Tene i produced with higher than thermodynamic equilib-US 8,048,388 B2 3 ium amouat when a selectivated 2 ‘catalyst forthe methylation step ocular sieve is used as SUMMARY OP THE INVENTION ‘This disclosure is directed to a process of manufocturing para-xylene, optionally co-manufacturing light olefins, with Press feedstock and methylting agent In some embodiments, this disclosure relates toa process ‘of manufacturing pars-xylene, comprising: (@) contacting a pygas feedstock and mediytating agent ‘with « catalyst under reaction conditions to produce & product having para-xylene, wherein the product has higher part-xylene content than the para-xylene content of the pygas feedstock; and () separating the parasxylene from the product of the step h ‘wherein the catalyst comprises a molecular sieve having 2 Diflusion Parameter for 2.2-dimethylbutane of about 0.1-15 see™' when measured ata temperature of 120°C. > and a 2.2-dimethylbutane pressure of 8 kPa-a and the ‘pyzas comprises from about 1 to about 65 wt % benzene find from about Sto 35 wt toluene, In some aspects ofthis dislosure, the eaalyst is produced by a method comprising steps of: (1) providing a porous erystalline material having a Dif sion Parameter for 2,2-dimethy butane in excess of 15 see"! when measured ata temperature of 120° C, and 2,2-dimothylbutane pressure of 8 kPa-a; and (@) contacting the material of step (1) with steam at 9 temperature in excess of 950°C. to rehice the Diffusion Parameter thereof for 2,2-dimethyTbutane to about 0.1 15sec"! when measured ata temperature of 120° C.and 42,2-dimethylbutane pressure of 8kPt-a, the mieropore ‘volume ofthe steamed material being atleast $0 vo % of the unsteamed material. In ther embodiments, this disclosure relates toa process ‘of eo-manufeeturing Tight olefins and para-xylene, compris ing: (@) contacting a pygas feedstock and methylating agent ‘with a catalyst under reaction conditions to produce a product having. the Tight olefins and paraxylene, ‘wherein the product has higher pare-xylene content than the para-xylene content ofthe pyges feedstock: and (scp epee the prods ep ‘wherein the catalyst comprises a molecular sieve having 3 Diffusion Parameter for 2,2-dimethylbutane of about (0.1-15 see™! when measured ata temperature of 120°C. and a 2,2-dimethyibutane pressure of 8 KPa-a and the Pass comprises at least 1 wt % non-aromatic compo ‘ents, from about 15 toabout 6S wt % benzene, and from about § to 3§ wt % toluene, wherein the light olefins comprise ethylene and propylene, and ‘wherein the catalyst is produced by a method comprising steps of: (1) providing a porous crystalline material having a Dit. sion Parameter for 2,2-dimethylbutane in excess of 15 see"? when measured at temperature of 120°C. and 2.2-dimethylbutane pressure of 8 kPa nd (2) contacting the material of step (1) with steam at a temperature in excess of 950°C. to educe the Diffusion Parameter thereo for 2,2-dimerhyThutane to about O.1- 1Ssee™! when measured ata temperature of 120°C. and 42,2-dimethylbutane pressure of 8kPt-a, the micropore ‘volume ofthe steamed material being atleast $0 vo. % of the unsteamed material, 0 o 4 In the embostiments of co-manufacturing light olefins and para-xylene, a east portion ofthe light olefins is made by a process comprising the following reactions: (oI) reacting methylating agent to form light olefins (62) de-tiylating of ethylbenzene or polymethylated eth slbenzene: andioe (63) cracking of noa-aromatic compounds in the pyeas feedstock. Tn some aspocts ofthis disclosure, at least a portion ofthe para-xylene is made by a process comprising the following reactions (al) methylating atleast a portion ofthe ethylbenzene to form polymethylated ethyThenzene(s) (22) de-ethylating at least a portion of polymethylated eth- sllenzene(s) to form paraexylene; and (28) meshylating toluene to form paraxylene Tn some aspects of this disclosure, the pytas Feedstock further comprises frm about | to 15 wt % C, aromatic come pounds and atleast 20% of the C, atomatie compounds is etiylbenzene Tn yet other embodiments, his disclosure relates to light olefins and para-xylene co-manufacturing system comprs- ing: (@) @ steam cracking unit adapted for steam cracking a hydrocarbon feedstock to ight olefins and pygas; (©) fist separating unit adapted for separating the light ‘olefins from the pyes (©) 4 methylation unit adspted to methylaing at least a portion of the pyzas frm (b) to produce a product con- taining para-xyiene; and (8) a second separating unit adapted for ssparting the ppartexylene from the product of step (). ‘The light olefins and para-xyleneco-manufacturing system may further comprise hydroprocessing unit adapted for bhydroprocessing ene andor resid feedstock to fort noph- tha suitable as a feedstock for the steam eracking unit. "The light oleinsand para-xyleneco-manfacturing system ‘may further comprise a transalkylation unit adapted t trans- late C+ atomaties to xylene. In other embodiments, this disclosure relates to a process of co-manufacturing light olefins and para-xylene,compes- ing: () stoam cracking a feedstock comprising at least one of ‘vacuum gas ol, atmospheric wa oi, ight naphtha, full ‘ange naphtha, etiane, propane, butane, naphtha made ‘bya process using resid feed, orany combination thereof 10 forma product comprising pyzas and ight olefins: (separating said light olefins from said pyyas () contacting sad pygas and a methylaing agent with a ‘catalyst under reaction conlitions to provioce a product having parasxylene, wherein said product has higher pparaexylene content than the paraexylene content of the yz feedstock: and (pening sd pray fomtbeprseto ep ©, ‘wher said catalyst comprises a molecular sieve having Diffusion Parameter for 2.2-dimethylbutane of about (011-15 see“! when measured ata temperature of 120°C. and a 2,2-dimethylbutane pressure OF 8 kPa and said _ygais comprises at Jast wt % non-aromati compo ‘hens, rom about 15 to about 651% benzene ad from out § 40 35 wt Mo toluene, wherein said light olefins ‘comprise ethylene and propylene, and ‘wher said catalyst is prodiced by a method comprising steps of (1) providing a porous crystalline material having » Dit son Parameter for 22-dimethylbutane in exeess of 1SUS 8,048,388 B2 5 see" when measured ata temperature of 120° C. and 2.2-dimethylbutane pressure of 8 kPa and (2) contacting the material of step (1) With steam at a temperature in excess of 1000° C. to reduce the Dilte sion Parameter thereof for 2.2-limethTbutane to about (011-15 see“! when measured ata temperature of 120°C. and a 2.2-dimethylbutane pressure of 8 KPa, the "mieropore volume of the steamed materia being at east ‘50% of the unsteamed material Insome aspects, the pygas separated in step (b) supplies fo the methylation step without any processing. Inter aspects, the pygas separated in step (b) is subjected toa de-benzene process to remove at least a portion of the benzene ia the PyB8s prior tothe contacting step. In yet other aspects, the Yess Separated in step (b) is subjected to a hydrotreating process to remove at last a portion of the muli-olefins i the YEAS prior to the contacting step. In yet other aspects, the Pybas separated in step (b) is subjected to a hydrotreating process to removeat east portion ofthe mulki-olefinsandat Jeast a portion of mono-olefns in the pygas prior t the ‘contacting step. In yet other aspects, dhe pygas separated in sep (b) is subjectad to any combination of a de-benzene process, a hydrotreating process fo remove at least a portion ‘of the multi-olefins, atleast a porion of the mano-oefins, ‘andlor optionally without an extraction proces to remove at least a portion ofthe benzene andiorat lest a portion ofthe paralins, in the pypas prior to the contacting step These and other objects, features, and advantages will become apparent as reference is made (© the following detailed description, prefered embodiments, examples, and appended claims BRIE DESCRIPTION OF THE DRAWINGS. FIG. 1 isa process flow diagram ilustrating one embod ments ofthe disclose simulated in Example 1 FIG. 2 plots ethylene selectivity s a function of methanol ‘conversion for Examples 3 and 4, FIG. 3 plots ethylene selectivity as a function of methanol ‘conversion for Example 5, DETAILED DESCRIPTION ‘This disclosure provides a means to produce para-xylene Jom pygas. Ina preferred embodiment, pars-xylene i pro- “duced from pygas without extraction, In some embodiment, yess and methylating agent are converted in high selectivity ‘o ethylene, propylene and para-xylene. In some embod mens, the pygas useful for this diselosure is produced hy ‘racking hydroteested polyeyelie napthenes and aromatis, ‘which i ich in benzene, toluene and Cy aromatics. In other ‘embodiments, py use for ths disclosure s subjected to ‘a benzene removal process prior wo the methylation step. The process of this dislosure provides a novel means of produc- para-xylene using pyss and methylating agent, espe- ily pygas made from steam erackingof naphha from ere ‘and/or resi. In a preferred embodiment, this disclosure relates tosmethod of selectively producing para-xylene from Press ‘As used in this specication, he term “framework type" is used in the sense described inthe “Atlas of Zeolite Frame- ‘work Types,” 2001 ‘As used herein, the numbering seheme for the Periodic “Table Groups is used a in Chemical and Fngincering News, 645), 27 (1985), ‘The term “wpm” as used herein is defined as parts per nillion by weight. 0 o 6 All weights of molecular sieve, wei weights catalyst composition, oe used in herein, are calew- Jated or measured based on the ealeined weight basis (ie, calcined at 510° C. in ar fora least one hour). ‘The term “hydroprocessing” as used herein includes fnydrofining and hydrocracking. The teem "steam cracker” a used herein is also known sore generally as a thermal pyrolysis unit: both terms are ‘well-known inthe ar. Steam, although option, is typically ‘added among other reactants to reduce bydroearboa partial pressure, (© control residence time, and to minimize coke Tormation, In preferedembodiments the steam may be super ‘atod, such inthe convection section a the pyrolysis tn andr the steam may be sour or treated process steam ‘Crude, as used herein, means whole erude oil asi issues ‘rom a wellhead, optionally including a step of desalting andior ther stops as may be necessary to render it acceptable {or conventional distillation ia a refinery. Crude a8 uscd hperein is presumed o contain resi ‘Residas used herein refersto thecomplex mixtureofhewy petroleum compounds otherwise known in the art as residuum or residual. Atmospheric resid isthe bottoms prod ‘et pmduced in atmospheric istilation when the endpoint of the heaviest distilled produet is nominally 650° F. (343° C) and is refered 10 as 650° E+ resid. Vacuum resid is the bottoms product from a column under vacuus when the heaviest distilled product is nominally 1050" F.(366"C.), and is referred to as 1050” Fy resid. (The teem "nominal ‘means here that reasonable experts may disagreeon the exact ct point for these tems, but probably by no more than 280° Fo at most =100° F), This 10S0° F-+ portion contains asphaltenes, which (oditionally are considered to be an fnitema to the steam cracker, resulting in corrosion and ‘ouling ofthe apparatus. Th term “resid” herein means 650° P+ G43" Cut) resid and 1050" Fs (566" C.+) resid unless ‘otherwise specie; note that 650° F.+ (343° C.+) resid com- prises 1050" F+ (366° C-+) resid “The tem “C, hydrocarbon wherein nisa positive iteger, eg. 1,2.3,4,5, 6, 7,80, 10,11, 12, asused herein, means a hydrocarbon having n numberof earbon atoms) per mol- ‘cule. For example, aC, aromatic compound means an afo- ‘matic compound having n number of carbon atom(s) per molecule: likewise C, parafin compound and C, olefia com- pound. The term “C, +" hydrocarbon wherein 1's a positive integer, eg. 1.2.3.4, 5,6,7,8,9,10, 11, 12,0 used herein, means a hydrocarbon having at feast number of carbon toms) per molecule. The term “C, =" hydrocarbon wherein ‘isa postive integer, og. 1, 2,3, 4,5, 6,7, 8,9, 10,11, 12, as used herein, means a hydrocarbon having no more than 8 ‘numberof carbon atom(s) per molecule The term “C, feedstock", wherein a isa positive integer 8, 1,2,3,4,3,6,7,8,9, 10,11, 12, as used herein, means that greater than 50'wi % of the C, feedstock comprises hydrocarbons having 1 number of catbon atom(s) per mol- cule, The tenn “C+ feedstock”, wherein n is a positive intoger,eg.,1.2,3,4,5,6,7,8,9, 10,11, 12,a8 usod herein, ‘means that preater than $0 wt 9 ofthe C,+ feedstock com- prises hydrocarbons having at least n_tamber of carbon atoms) per molecule. The tenn “C,~ feedstock” wherein nis apositiveintoger.e.1,2,3,4,5,6,7,8,9, 10, 1], 12,asused Fhrein, means that ureair thaa 50 W°% ofthe C,~ festock comprises hyelroearbons having. no mote than number of carbon atom(s) per molecule, The tem °C, aromatics ‘whorein nis a postive integer, 1,2,3,4,576,7,8,9, 1 11,12, as used herein, means tht greater than 50 wi % of the aromatics comprises aromatics having n mimber ofearbon atoms) per molecule, Theterm "C,+ aromatics”, wherein aisUS 8,048,388 B2 1 ‘apositive integer. 12.3.4, 5.6,7,8,9, 10,11, 12, as sed herein, means that greater than 50 wi of the C+ aromaties ‘comprises aromaties having at least n number of carbon. (6) per molecule. The tem", aromaties” whersin nis ‘apositve integer, 12.3.4, 5,6,7, 8,9, 10,1, 12, assed herein, means that greater than 50-wt ofthe C,~aromaties ‘comprises aromatics having no more than n number of earbon, om(s) per molecule, The term “shape-selective catalysis” describes catalytic. sclectvities in zeolites. The principles behind shape selective ‘catalysis have been reviewed extensively, ex, DYN. Y. Chea, W.E. Garwood and F. G. Dwyer, “Shape Selective Catalysis Jn Industal Applications.” 36, Marcel Dekker, Ine. (1989). ‘Within a zeolite pore, hydrocarbon conversion reactions such 8 paraffin isomerization, olefin skeletal or double bond isomerization, oligomerization and aromatic disproportion- ation, alkylation or transatkylation reaetions are govemed by ‘constraints imposed by the channel size, Reactant selectivity ‘occurs when a fraction ofa feedstock is too large to enter the zeolite pores to react: while product selectivity occurs whea 2 some ofthe products cannot leave the oolite channels. Prod: uct distributions ean also be altered by transition state sel tivity in which certain renctions cannot occur becanse the reaction transition sates to large to form within the zeolite pores orcas. Another typeof selectivity results from con- Figurational constraiats on ditfision where the dimensions of the molecule approach that of the zeolite poresystem. A small ‘change inthe dimensions of the molecule or the zeolite pare ‘ean result in large difsion changes leading a different prod uct distributions. This type of shape selective catalysis is demonstrated, for example, in selective toluene dispropor- tionation to para-xylene. Pygas Feedstock Thermal cracking of hydrocarbons is a petrochemical pro- ‘cess that is widely used to produce light olefins, «elven, propylene and butylenes, and aromaties, eg, benzene, old ‘ene and xylenes. Typically feedstocks for thermal eracking process are naphtha, gas oil or other fractions of whole crude Oil The steam hydrocarbon minture is preheated in the radi ‘ant section ofa pyrolysis unit prior to entering the convection section, where tis very quickly heated, sch as ot pressures Fanging from about 100 kPaca (kilopascal absolute) to about 350 kPa, toa severe hydrocarbon cracking temperature ia the range from about 600° C. to about 900° C. ‘Ailer cracking. the effluent from the pyrolysis furnace ‘contains gaseous hydrocarbons of great variety, eg. same rated, monounsaturited and polyunsaturated and ean be ali- phatic andior arontatc, as well as significant amounts of hydrogen. The cracked product is then further processed in the olefin produetion plat to produce the variows separate individual steams of, Le. hydrogen, the light olefins elhyl- ‘ene, propylene, butenes, and aromatic compounds, as well as ‘other proluts such as pas “The starting feedstock fora conventional olefin production plant has been subjected to processing before it reaches the plant. Normally, whole crude is fist subjected to desalting Prior to being distilled or otherwise fractionated into phi- ‘ality of pars (factions) suchas gasoline, kerosene, naphtha, as oil (Vacuum or atmospherie)and the like including thigh boiling residuum (“resid”) Thereafter, conventionally. any of these fractions, other than the resid are passed to an olefin production plantas the feedstock for that plant. “The pyzas is a byproduct of olefins production by’ steam ‘racking hydrocarbons such as naphtha of gas oi feedstocks, The pygas contains a high proportion of aromatics, primarily benzene and toluene, and a smaller amount of Cy aromatics that contains up to 40 percent by weight of ethylbenzene. 0 o 8 Pyuas yields and compositions are determined by the severity of the eracking operation and the composition of feedstocks ‘othe cracking process. Normally. pygas comprises 150 65 set % benzene altematively 20-60 wt benzene, oF 30-50 wt % benzene; 5-35 Wi % toluene, alternatively 10-25 wt % toluene, or 15-25 wt % toluene; 1-15 wt % Cy aromatic compounds, altematively 3-101 %C, aromatic compounds, fr 49 wt % C, aromatic compounds: 0.16 wt % elhylben- ‘zene, alternatively 0.5-3 wt % ethylbenzene, or Io1.5 8 % ethylbenzene: 1-15 wt % nos-aromatics, alternatively 2-10 \W1% non-aromaties, of 5-10 wt % non-aromatis, and about (0.1 o 5 v1 % unsaturted non-aromatis,ateratively 0.1 to 2 wt % unsaturated non-aromaties, or 0.2 10 1 wt % unsatur- ‘ted non-aromaties; optionally 0.001 to 2 wt % multi-unsa ‘rated non-aromatics, such 8 d-olefins. Prior to recovering benzene and toluene, a pyzas is normally subjected to hydrotreating process to remove olefinie components and extraction process to remove non-aromiaties, The pysis afer extraction normally comprises less than I wt % non-aromat- ies, preferably less than0.5 wt %enon-aromaties. Thebenzene And toluene may be separated by conventional method of separation such as distillation Tn some embodiments ofthis disclosure, the pygas sf {orthis disclosure has benzene concentration ranging. rom about 15 w1% to about 65%. Inother embodiments of his isclosure, the pygas useful for this disclosure has been sub- jected io a benzene removal step wherein the benzene con- ‘centration is ess than 15 wt %, eg. from about L wt % 10 bout 14 wt %, The following benzene concentrations are ‘usefl lower heazene concentration limits fr all disclasnre processes: 1,2, 5, 10,15, 20,28, 30,38, 40, 48,50, 5S and 60 \w1%, The following benzene concentrations are useful upper benzene concentration limits forall disclosure processes” 5 10,15, 20, 25, 30, 35, 40, 45, 50, $5, 60 and 65 wt %, The benzene concentration fallsin.a range between any one ofthe above-mentioned lower limits and any one of the above- ‘mentioned upper limits, so long asthe lower limits less than ‘orequal tothe upper limit, The benzene concenteation maybe present ian amount ranging fim 15 wt Yet 6S wt % in one embodiment, atematively 1 wt % to 5 wt %, alternatively rom 30 wt Yoto SO wt %, and alternatively 3$ wt % to 40 wt °% in another embodiment. In some embodiments ofthis disclosure, the pygas efi {or this disclosure has a toluene concentration ranging rom shout § w1% to about 35 wt 9%, The following toluene con- ‘centrations are useful lower toluene concentration mits for all disclosure processes: 5, 10, 15,20, 25 and 30 wt %. The following toluene concentrations are useful upper toluene concentration imits forall disclosure processes: 10, 15,20, 25, 30 and 35 w1%, The toluene concenttation falls in arange between any one ofthe above-mentioned lower limits ad ay ‘one othe above-mentioned upper limits, so longas the lower limit is less than or equal tothe upper limit. The toluene ‘concentration may be present in in amount ranging from 5 wt 61035 wt%in one embodiment, altematively 10 we % to 30 +84, altematively from 15 w1% 1025 w%, and alternatively 15 wi%e to 20;wi% in another embodinsent In some embodiments ofthis disclosure, the pygas usefol {or this disclosure has a C, aromatic coneeotration ranging from about 1 wt % to about 15 wt %. The following Cy ‘aromatic concentrations areuseful lower C,aromatieconcen- tration mits fr al disclosure processes: 1, 2,3, 4, 5,67, 8, 9, 10, 11, 12, 13-and 14 wt %. The following C., aromatic compounds concentrations are usefl upper, aromatic con- centration limits forall disclosure processes: 2,34, 5,6, 7.8, 9,10, 11,12, 13, 14 and 15 wt %. The C, aromatic concen: ‘ration fills in @ range between any one Of the above-men-US 8,048,388 B2 9 tioned lower limits and any one ofthe above-mentioned upper limits, so long as the lower limit is less than or equal to the upper limit. TheC, aromatic concentration may be present in fn amount ranging fom 1 wt to 15 wt % in one embod ‘ment, alternatively 31% to 10 1% alteratvely from 4 wt % 10 9 it %, and altematively 5 wt Ye to 8 wt 9% in another ‘embodiment. In some embodiments ofthis disclosure, the pygas useful forth disclosure has an ethylbenzene concentration ranging fom about 0.1 wt % ta about 6 wi %, The following elhyl- benzene concentrations are usefilJower ethylbenzene con- ‘cenraton limits forall disclosure processes: 0.1.0.2, 0.5, 1 15, 2, 25, 3,35, 4,45, 5 and 5:5 wt % The following ceihytbenzene concentrations are useful upper ethylbenzene ‘concentration limits forall disclosure processes: 0.2, 05,1, 15,2,25,3,3.5,4,45,5,5,5 and 6%, The ethylbenzene ‘concentration falls ina range between any one ofthe above~ ‘cntioned lower limits and any one of the above-mentioned "upper limits, so long asthe lower limits less than or equal t0 the upper limit. The ethylbenzene concentration may be 2 present in an amount ranging from 0.1 wt Yeto 6 wt % in one ‘embodiment, altematively 0.5 we % to 3 wt %,altematively from Iw to LS wt %, and alternatively 0.1 Wi% ta 24% in another embodiment In some embodiments ofthis disclosure the pygas useful {orth disclosure has a non-aromaties concentration ranging from about 1 wt % to about 13 wt °%. The following non- ‘aromaties concentrations age uselul lower non-aromates ‘concentration limits for all disclosure processes: 1,2,3,4,5,, 6,7, 8, 9,10, 11, 12, 13 and 14 wt %, The Following non romaties concentrations afe useful upper non-aromaties ‘concentration mits for all disclosure processes: 2,3, 4, 5,6, 7,8,9, 10,11, 12,13, 14 and 15 wt %. The non-aromaties ‘concentration falls ina range between any one ofthe above ‘mentioned lower limits and any one of the above-mentioned ‘upper mits, so longa the lower limits fess than or equal © the upper imi. The non-aromaties concentration may be present in an amount ranging from I wi % t 15 w1% in one ‘embodiment, altematively 3 wt % to 10 wt %,altematively from 4 wt 4610 9 wt %, and altomatively 5 wt % to 8 wi Mein nother embodiment, ‘In some embodiments ofthis disclosure the pygas useful {or this disclosure hasan unsaturated non-aromatics concen- teation ranging from about 0.1 wt % to about 5 wt °%. The {ollowing unsaturated non-aromaties concenralions are use- {ul lower unsaturated non-aromaties concentration limits for all disclosure processes: 0.1.02, 0.5, 1,1.5,2,2.5,3,3.5,4, and 4.5 wt The following unsaturated non-aromaties con: ‘centrations are useful upper unsaturated non-aromaties con- ‘centration limits forall disclosure processes: 0.2, 05,1, 1 2,25,3,3.5,4,4Sand5 wt%. The unsaturated non-aromal jes concentration falls in range between any one of the ‘above-mentioned lower limits and any one of the above mentioned upper limits s long asthe lower limits less than ‘or equal to the upper limit. The unsaturated non-aromaties, ‘concentration maybe present in an amount ranging fom 0.1 \wt% to wi% in one embodiment, altematively 0.1 Wr % 0 2 wi %,altematively fom 0.2 wt % to 1 wt %, and alterna tively 0.1 18% 0 L Wt %o in another embodiment Optionally, the pygas useful for this disslosure asa multi= unsaturated non-afomaties concentration ranging fom about 10,001 wt % 0 about 2 wt, The following malt-unsatursted ron-aromaties concenteations are nsf lower multi-unsat- trated not-aromatics concentration limits fr all disclosure processes: 0.001, 0.005, 0.01, 0.05,0.1,0.5, {and 1.5 wt %. ‘The following multisnsaturated non-anomaties concentra tions are useful upper mult-unsaturated non-aromaties con 0 o ceatration 005, 0105, 1, The mulieunsaturated on-atomatics concentration falls ina ange between an one ofthe above-mentioned lower limits and aay one of the thovesmentioned upp limits, so lon. the lower Knit is lews than or equal tothe upper limit The mmalinsatrats non-aromatcs concentration may be preset in an amount ‘ging from 0.001 wt 9% to 2 wt Yn ome etbodiment aitematively 0.01 wt 96001 w%,lteatively from 0.1 61% to 2 wt %, and alieratvely 08 wt % to 1 1% ia anther embodiment Pygis Made from Resid Fesdbtock thas previously been proposed to upgrade certain enue fetions, prior to steam eracking. by fist hydeoprocessing te fed. For instance, US. Pat. Nos. 3,885,115 and 6,190, 533 are directed oan neat process compsing passing the fed to ahiydoteating zane allowed by a steam cracking ‘onc n air case, however, is whole cra or faction comprising resid passed directly othe hydrotreating one Secalso GB 207113 and Fedoe & Keble, Enuss,Pawoche- rie (1981), 341), 448-6 (Ones references of interest include U.S. Pat Nos. 3.885, 113; 4087 490 4.199385; and 6,743,961 Resid lydroroecssing is «known process for uperading resido fuels suchas fell diesel heating ol jet kerosene, asolin, LPG, and fel gas. Bach of these i use per seas Hels andior as intermediates for the production of, for instance, petoshemicals By way ofexample fel olay be cracked to produce the lghtr boiling fuels gasoline, LPG an fie gas andor the pevochenicalsetslene, propylene, nd bans Typically resid droprocessingiscaried out tatempers ture from abot 260 to 482" preferably 34349 ANZ" C. A presse fom about 3500 to 68008 kPa preferably 58000 27300kPaa is usd, with aliquid hourly space velocity fom 6.110 She prefobly 0.2510 1 The hydrogen supply rate (makeup and rocyele hydrogen) tothe hydroconversion Zone isin the range from about 14.16 to aba $66 standard Gabie mete por 158.9 liters (barrel) of hydrocarbon fd preferably about 56.610 142 standard cube moe po 1389 Iter (bare, The hydroprocessing may’ be case ot Jing two or more hiydropecesing zes. For example, in cone embodiment fst one ith fit catalyst ean be designe to aecumnlate mos of te neta removed rom the Teediock a sevond zone wilh sevond caulyst can be designed for maximum heteroatom removal and aromatics hydrogenation. In another embodiment, a fist eaalst canbe designed to aecumulate mos ofthe nota remeved rom the Feedstock, a second zone with sevond catalyst can be designed for maximam heteroatom removal anda hid zone ‘with a third catalyst can be designed to increase aromatics Inydogenaton. “The eallyst employed in the typical commer ydeo- conversion ones) is comprised of material having hylogs- ‘aton- dehydrogenation stvity together with an amorphous carrer Exemplary amorphous earns clade slunina, Siis-aming, silica, zreoia,c ani. Hydrogeationde- Inydgenation components ofthe catalyst prelerably com: prise at least one hydrogenation compenent select Group 6 metals compounds of Group 6 metasandat east cone lyogenation component selected from Groups 8-10 tetas and compounds of Groupe 8-10 metals. Prefered Combinations of hydrogenation components ince ngkel Sule with molyemom slide, cobalt slide with molyb- denuny sulfide, cobalt with molysdenum, and nickel with tungsten, The catalyst omployed inthe disclosure ay also be comprised ofa material having hydrogenation-deydrogens-US 8,048,388 B2 ul tion atvity formulated without an amorphous cartier. Bxem ply catalysts include Nebul In a prefered embodiment, the eluent selected to be steam erieked comprises a fraction boiling from about 37140 about 482° C, In another preferred embodiment, the hydro> processor efloent, if it contains any resid, is first treated to remove the resi prior to feeding the material into the con- vection scction of the thenaal pyrolysis unit (or steam cracker) Tn another embodiment of the disclosure, a resi-contain- ing crude oF fraction thereo's twated by a process including ‘first step of hydroprocesting and a sevond sep of theamal cracking, Crude fractions are typically obtained from the refinery pipes. Ashoughany ere ration obtained rom the refin- ‘ey pipestl is useful inthe present disclosure, thes advantage offered by the present disclosure is that crude {actions sill containing all or a portion ofthe original resid present in the whole rade obtained from the welnead maybe processed. Ina preferred embodiment, whercin the feed comprises ‘enide or atmosphere ress that contain appreciable amounts of 1080° F+ (566°C. +) resides, eg, 10wt "Gor moreo resid, ‘or 20 wt % or more of resid, the resid-contsning feed, alter hydroprocessing, is passed into the convection section of @ pyrolysis unit, where itis preheated. Then itis passed to @ fash drum, which may be optionally integrated with the pyrolysis unit to drop out the heaviest faction (eg, substan- tally all the asphaltenes) The terms “lash drum”, “ash “knock-out drum” and "kooek-out pot” are use inter- ‘changeably herein: they are per se wel-kaowa i the at. In preferred embodiment, the composition of the vapor phase Jeaving the flash drum is substantially the same as the com- position of the vapor phase entering the Hash drum, and [ikewise the composition ofthe liquid phase leaving the Bash ‘drum issubstantally the sameas the composition ofthe iguid phase entering the flash dum, ihe separation in the flash ‘drum consists essentially ofa physical separation ofthe two Phases entering the dram. In a more preferred embodiment the material is treated by visbreaking or mild thermal erack- Jing ta increase the proportion of vapor phase a the expense of bottoms product. Visbresking and mild thermal eracking are per se well-knowa in the at “The preferred flash deums andl their inteyration with pyrolysis units hae previously been deseribed in U.S. Patent Application Publication Nos, 20040004022, 20040004027, ‘and 20040004028, and more recently in U.S. application Ser No, 11/068,615 filed Feb. 28, 2005, Ser. No, 151,486 filed May 21, 2004, Ser. No, 10/851,546 fled on May 21, 2004, Ser. No, 10/851,878 filed May 21, 2004, Ser. No, 10'851,494 filed on May 21, 2004, Ser. No. 10/851,487 filed May 21 2008, Ser. No. 101851434 filed May 21, 2004, Ser. No: 10/851,495 filed May 21, 2004, Ser. No. 081,730 filed May 21, 2004, Sor. No. 10/851,500 filed May 21, 2004, Sor. No. 11/134,148 fled May 20, 2005, Ser. No. 10°975,708 led (Oct. 28, 2004, Ser No. 10/891,795 filed Jul. 14, 2004, Ser No, 105891,981 filed Ju. 14, 2004, Se. No 10/998,716 filed Jul 16, 2008, Ser. No. 11/009,661 filed Dec. 10, 2004, Sor No. 11/177,076 filed Jul. 8, 2005; and Ser. No. 11/231.490, filed Sep. 20, 2005. Another preferred apparatus elective as «flash pot for purposes ofthe present disclosure is described in US. Pat. No. 6,632,381 asa “vaporfiquid separator” In the process of the present disclosure, the lash dram preferably operates ata temperature of between about 425°C ‘and about 455° C. Passing material through the flash drum to ‘obtain an overhead vapor and liquid otloms is refered t0 herein a “ashing” 0 o 12 Crude or resid-contsining fraction thereof, particularly aumosphecie resid, vacuum resid, or any asphaltene-contain- ing refinery oF chemical intermesiate steam is also a pre- {ered feed. When the food comprises greater than about O.1 \W1%, or preferably greater dhan about 5.0 wi % asphaltenes, flash pot is advantageously sed to remove the asphaltenes prior entering the radiant section ofthe pyrolysis unit. The ‘ash drum may be integrated withthe pyrolysis unit as ‘cused above so that the feed is preheated in the convection section ofthe pyrolysis unit prior to entering the Mash pt. the alternative, it may bea separate unit s0 that removal of asphaltene occurs substantially prior to entering the pyrolysis ‘Other prefered feds include a hydrocarbon sian having a high concentration of polycyclic aromatics, particularly those high in heterocyclic rings, tar, and topped caude (topped crude” being the eut roughly from about 260-315° . and higher eu, but below temperatures wire significant cracking occurs, €, about 340-370° C.; often topped enude js used asa synonym for atmospheric resid), This preferred ‘eed may or may not contain appreciable amounts of resi. ‘Upgrading of cri and ere fractions containing resid ‘and also an appreciable amount of polyeyelie aromatics, par ‘icularly those high in heteroeyelie rings, is one of the par sicular advantages provided By the present disclosure. Aa exampleis VGO (Vacuum Gas Oil upgrading. Hydrotesting alone provides for some breaking ofthe ring stuctures ofthe fromatie heteroeyeles, however, a veny large portion of the polyeyelic ring stractre islet ntact. Steam cracking alone proves for product comprising significant yields of fel oil, tar, and non-aromaties in addition to the desired ethylene propylene, butanes, C olefins and dienes, and single-ring frome products, However, in a process according to the present disclosure, hydrotreating followed by steam eracking simultaneously reduces the yields of ful oil tar, and non- fromaties while increasing the yield of the aforementioned desirable petrochemieal produeis, In addition to resid, resid- ‘erived VGO, feeds comprising crides, ight catalytic eycle oil (LCCO or distilate from a catalytic cracker), coker gas- oils, FCC eyele oils, steam cracker tar and lube extracts are preferred feeds to arrive ata produet rch inthe aforemen- tioned preferred aromatics Thus, hydroprocessing feedstocks rich in polynuclear aro- matics, particularly those high in heterocyclic rings, are @ preferred feedstock for producing Hight olefins and single- ingaromatis ina steamcracker Polynuclear aromatics com- prise both aromatic and napthenie ring structures. Without ‘ishing to be bound by theory. such fecdstocks, when fed to a steameracker, undergo hydrogen transfer reactions, ‘whereby naphthenic rings are converted to aromatic rings Te hydrogen atoms removed from the naphthenes typically ‘emerge from the steamcracker as CHT bonds in light paral fin molecules such as methane, ethane, and propane. In mole °% methane is the dominant paraffin produced in steamerack- ing. Thus, feedstocks rich in polynuclear aromatics, paniew- larly those high in heterocyclic rings, tend to produce high yields of methane and tar upon steameracking. The present inventors have surprisingly discovered that high severity hhydroprocessing of these feestreams results in the produc ‘ion of high quality steaneracker feedstock, Tn. preferred embodiment, inereasing the severity ofthe steam cracker using atleast one ofthe aforementioned feeds ‘nereases the yield of benzene toluene and xylenes. Reaction Severity isaterm known perse intheart and ean bemeasured forinstance, by the ratio of propylene versus methane exiting the steam crackerUS 8,048,388 B2 13 The pygas obtained from steam cracking a hydrocarbo Jeedstock made with hydroprocessed resid contains at east 1 1% (based on he total weight of the pyzas), altematvely 2 st %, 3 wt Ye more aromatics than the pygas obtained fom ‘conventional hydrocarbon feedstocks, eg ight naphtha, C: (C,, AGO, VGO. and LCCO. The pygas obtained from steam ‘racking hydrocarbon feedstock made with hydroprocessed, resid or combined wih the pygas olained from conventional hydrocarbon feedstocks, eg, light naphtha, C. Cy, AGO, \VGO, and LCCO isa preferred feedstock forthe metiylation process o tis disclosure. ‘While the above embodiments have bee illustrated using ‘2 feed, atmosphere resi, the feed advantageously may be abo be selected from heavy erude oil, atmospheric and vacuum resid uel il, FCC eyee oils, coker gasols, cracker tar, topped ene, and any other feed containing resid andor high concentration of multcycli heteroatom aromatic spe- ‘ies. Mixtures of such feeds, uch as provided by crude, are sso prefered Tn some preferred embodiments, the feed to the stew ‘racking process comprises at least one of vacuum gas oil, ‘atmospheric gas ight naphtha, full ange naphtha, ethane, propane, butane, naphtha made by a process using resid feed ‘or any combination thereof Methylation Process The production of PX is typically performed by toluene dlisproportionation over a catalyst under conversion condi tions, Examples include the toluene disproporioastion, as described by Pines in “Phe Chemistry of Catalytic Hydrocar- bon Conversions", Academie Press, NY, 1981, p. 72, Such methods typically result in the production of = mixture including PX, OX, and MX. Depending upon the depree of scloctvity of the catalyst for PX (parescloctvity) and the reaction conditions different percentages of PX are obtained. ‘The yield. Le. theamountofxylene produced as.a proportion ‘of the Feedstock, is also affected by the catalyst and the reaction conditions. “The equilibrium reaction forthe conversion of toluene to xylene and benzene products normally yields about 24 wt % PX, about 54 wt % MX, and about 22 wt % OX among sylenes. ‘US. Pat, No. 6,423,879 discloses process forthe selec tive production of para-xylene which comprise reacting ole ‘ene with methanol inthe presence ofa catalyst comprising 3 porous crystalline material having a illusion Parameter for 2,2 dimethylbntane of about 0.1-15soe~ when measured ata temperatuee of 120° C. and a 2,2 dimerhylbutane pressure oF 8 Pha, The porous crystalline material is preferably & medium-pore zeolite, panicularly ZSM-5, which has been severely steamed at a temperature of at least 950° C. The porous crystalline material is preferably combined with at Jeast one oxide modifier, preferably ineloding phosphors, to ‘control reduction of the micropore volume of the material ‘during the steaming sep. Ina preferred embodiment, a pypas feedstock, eg. pyeas ‘made steam cracking of naphtha is supplied toa methylation reaction zone together with methslating agent, e., metha- nol, the mixture of pygas and methylating agent is contacted with a catalyst to produce a product having para-xvlene, Cx benzene, toluene, and C+. The pygsswseful forthe process ‘of this disclosure comprises at least one of steam eracking vacuum gas oil pygas, steam cracking atmospheric gas oil pyzes, steam cracking Tight naphtha pyzas, steam eracking full range naphtha pygas, steam cracking ethane pygas, team ‘racking propane pygas, steam cracking butane pyyas, and ‘eam cracking naphtha made by a process using resid feed pyuas. The producti further subjected to a separation step (0 0 o 14 separate atleast portion of C,-, benzene, toluene, or ben- zeneitoluene, C+, and pars-xylene. In one embodiment, at least a portion of the benzene, toluene, or benzenetoluene separated is recycled to the methylation reaction zone. in another embodiment, the Cs separated from the methylating pradct is sent oa translation reaction zane, wherein the Cyt and a benzeneltohuene feedstock is in contact with @ transalkylation catalyst to prodict more pars-xylene The methylation reaction conditions comprises a tempera ture between about S00 and about 700" C.. preferably between about 500 and about 600° C,.a presure of between bout 100 1 about 7000KP a, a weight hourly space velocity ff herween about 0.5 and 1000 hi, and molar ratio of {oluene to methylating gent (in the reictor charge) of at least about 0.2, eg. from about 0.2 to about 20. The process is preferably conducted in the presence of added hydrogen and! fr added water such thatthe molar rato of hydrogen andor ‘water to toluenetmethylating agent in the feed is between about 0.01 and about 10. ‘The tansalkylation resetion can be conducted in any appropriate reactor including a radial flow, fixed bod, con- ‘invoulsdavsn flow oe Mud hed reactor. The trasalkyation reaction conditions typically include a temperature ringing rom about 343°C. to about $10° C, such as fom about 400° C.to about 454°C. pressure from about 380 to about 4240 ‘Pas, stich as from about 480 fo about 3550 KPa: hiydro- gen to hydrocarbon molar ratio from about 1 1 about 5, such as from about L toabout 3 and a WESV of about 0.20 about 20, such as from 1 to about S. The transalkylaton reaction conditions nee suifiient to convert the heavy aromatic feed 10 ‘product containing substantial quantities of C,-C, aromatic ‘compounds, suchas benzene, tolleneand xylenes, especially benzene and xylene The isomerization reaction conditions are selected so a to be elfectve to isomerize the xylenes in the leedstock. Sui able conditions include conditions include a temperature of bout 120° C. to about 260° C., a pressure of about 448 10 bout 7000 kPa-a and WHSV of about 1 to about 100 hr ‘More preferaly, the conditions include a temperature of about 160° C. to about 232° C., a pressure of about 790 40 bout 3850 kPa and WHISV of aout Ito about 30 BF. in tener, the processes in the second reactor are conducted in the absence of added hydrogen, “The product stream from the methylation step comprises para-xylene, Cy aromatics, optionally light gas, benzene, folvene and C,+. The prodhict may subject to stop of sepa. ‘ating east portion of ight gas to forma ight gas presi, at Teast a portion ofthe benzene and toluene to form a BT product having atleast # wt % benzene and at least # Wt % folvene and atleast portion the Cyto forma C4 product. In some prefered embodiments, atleast a portion of the BT product separated is recycled back to the methylation sep. ‘The C,+ product may be tansalkylated with benzene andior toluene to form xylenes. ‘The methylating agent useful fortis disclosure comprises at feat one of methanol, dimethyl ether, halogenated meth- ‘nee. chloromethane, syngas, ¢,CO and Hof CO, and Hy Preferably the catalyst useful forthe methylation com- prises porous crystalline materalshaving specific andelosely ‘define diffusion characterises, such as can be obained by severe steaming of ZSM-5 containing an oxide modifior, exhibit improved selectivity forthe xylene product contains atleast about 30 wt %, preferably atleast 50 wt %, more preferably at least 70 wi %, even more preferably atleast $0 ‘Wt %, yet even more preferably at least 90 wt %, of the para-xglene seletvity defined as the para-xylene concentUS 8,048,388 B2 15, tion in the xylene product measured at the conditions such that a toluene methylation conversion of 15% (based on ol- ‘ene) per pass when pure toluene is fed. Tn one aspect, this disclosure resides in @ process forthe selective proiotion of para-xylene which compises reacting benzene, toluene, ethylbenzene in pygas with » methylating agent, ¢, methanol, dimethylether, and/or chloromethane, ‘under alkylation conditions in the presenceaf a catalyst com prising & porous erystalline material having @ Diffusion Parameter or2.2-dimethylbutane of about 0.1-15 see" when measured at a temperature of 120° C, anda 2.2-dimethyIbu- lane pressure of § KPa Preferably, the porous crystalline material has a Diffosion Parameter of about 0.5-10 see"! Preferably: the catalyst contains at least one oxide modifier and more preferably t least one oxide modifier selected fom. ‘oxides of elements of Groups 2,3, 4,5, 6, 13, l4and IS ofthe Periodic Table. Most preferably the oxide modifier is selected from oxides of boron, magnesium, esleium, laufhanum and ‘most preferably phosphors. Preferably; the catalyst contains about 0.08 to about 20, more preferably about 0.1 to about 10 aad most preferably about 0.1 1 about 5, wt % ofthe oxide modifier based on ‘elemental modifier Preferably, the catalyst hasan alpha value ess than SOand preferably less than 10, Ina farther aspect, this disclosure resides in a method for producing @ catalyst for se in the selective prodoction of pari-xylene by eating tolnene with methylating agent, the method comprising the steps of: (0) stating witha porous ‘eqstaline materia having a Diffusion Parameter for 2.2- ‘imethylbutane in excess of 15 see“! when measured at & temperstre of 120° Cand 2,2-imethylbutane pressure of kPa; and (b) contacting the material of step with steam temperate of atleast about 980° C. to rede the Die fusion Parameter thereof for 2,2-dimethylbutane 10 about (01-15 se"! when measured at «temperate of 120" C. and 44 2,2-dimethylbntane pressure of 8 KPa, the mieroporevol- tume of the steamed material being at leat 50% of the Unsteamed material Preferably the porous crystalline material use instep ( ‘comprises an aluminosilicate zeolite having a silica to al tina molar ratio of at least 280. “The present invention provides @ process for alkylating toluene with methylating azet to selectively produce pars- xylene in high yield and with a high perpass conversion of Toluene. The process employs catalyst Which comprises 8 oro erystalline material having a Diffsion Parameter foe 2.2limethytbutane of about O.1-15 see“! and preferably (015-10 see", when measured ata temperature of 120° C.and 8 2.2edimetiylbutane pressure of 8 KPa-a ‘As used herein, the Diflsion Parameter of particular porous ensalline materials defined as Dir'<10", wherein D ‘the diffsion coefficient (cm/sec) and isthe crystal radius (Gi), The required diffusion parameters can be derived from sorption measurements provided the assumption is made that the plane sheet model desribes the diffusion process. Thus foragiven sorbate loading Q. the value QQ... where. iste ‘equilbsium sorbate loading, is mathematically elated (DV FV where isthe time (se) required to reach the sorbate Joading Q. Graphical solutions forthe plane sheet model are given by. Crankin“The Mathematis of Diffosion”, Oxford University Pres, Ely Howse, London, 1967 “The catalyst usefal forthe methylation comprises a porous ‘estaline material having o Constraint Index of 1-12 suchas 2SM-S, 7SM-L1ZSM-22, 7SM-23, 7SM-48, and TTQ-13. The porous erystlline material employed inthe process of o 16 {his disclosure is preferably a medium-pore size aluminosl cate zeolite. Medium pore zeolites are generally defined as thosehaving poresize of about 5 to about 7 Angstroms, sueh that the zeolite freely sorbs molecules such as n-hexane 3emethylpentane, benzene and para-xylene, Another com- ‘on definition for medium pore zeolites involves the Con- stiaint Index test which is described in U.S. Pat. No. 4016, 218, which is incorporated herein by reference In this cus, ‘medium pore zeolites have a Constraint Index of about 1-12, fa measured on the zeolite alone without the introduction of ‘oxide modifiers and prior o any steaming to adjust te diff sivity of the catalyst. In addition to the medium-pore size aluminosilicate zoltes, other medium pore aciie metallo- siliates, suchas silicoaluminophosphates (SAPOs), can be ed in the process of this dislosure. Particular examples of suitable medium pore zeolites {include 75M-5, SMI], ZSMcI2, ZSM-22, 7SM-23, 2SM- 35, SMS, end MCM-22, with ZSM-5,11Q-13 and 2SM-11 being paniculrly preferred, Zeolite ZSM.-S and the conventional preparation thereof are desctibed in U.S. Pat. No. 3,702,886, the disclosure of whieh is incomporated herein by reference. Zeolite ZSM-11 and the conventional preparation thereof are described in IS. Pat, No, 3,708,979, the dielosure of which is incorporated herein by reference. Zeolite ZSM-12 and the conventional reparation thereof are described in U.S, Pat, No, 3832449, the disclosure of which is incorporated herein by relerence Zeolite ZSM-23 and the conventional preparation thereof are eseribod in U.S. Pat. No. 4,076,842, the disclosure of which js incorporated herein by reference, Zeolite ZSM-35 and the conventional preparation thereof are desctibed in US. Pt. No. 4,016,245, the disclosure of whichis incorporated herein by reference. 7ZSM-48 and the conventional preparation thereolis taught by U.S, Pat, No. 4.375.573 the disclosure of ‘which is incorporated herein by rlerence. MCM-22 is ise closed in US. Pat, No. 5,304,698 to Husain; U.S, Pat No. 5,250,297 wo Kresge et al; US. Pat. No 5,095,167 to Chis tensen; and US, Pat, No” 5,043,508 to Del Rossi eta, the disclosure of which patents are incomporated by reference The synthetic porous crystalline material ITQ-13 is scribed in U.S. Pat No. 671,941, which ie hereby incor porated by reference. TQ-13 isa single crystalline phase that basa unique 3-dimensional channel system comprising three setsof channels, In particular, ITQ-13 comprises frst set of zenenlly parallel channels each of which is defined by a TO.membered ring of tetrahedrally coordinated atoms, a see~ ‘ond set of generally parallel channels which are also defined by 10smembered rings of tetrahedrally coontinated toms ‘nd which are perpendicular to and intersect with the chan- ‘els ofthe first set, anda third st of generally parallel chan- ‘els which intersect with the channels ofthe fist and second sets and each of whieh is defined by a 9-membered ring of ‘etrahedrlly coordinated atoms. The fist setof 10-ing chan- nels each has cross-sectional dimensions of about 4.8 A by ahout 5.5 A, whereas the sscond set of 1O-ring channels each has eross-seetional dimensions of about §.0 Aby about 5,7 A. The third set of O-ring channels each has cross-sectional 95 wi % C,~ hydrocarbons, About 16 weight units af the total 22 weight units of the pygas are C,~ Ieedstock, ‘mainly C,~ aromaties, ad about 6 Weight units ofthe total 23 ‘weight units of the pygas are C,+ fecdstock, mainly Coa aromatics, Beeause the pygas was produced from a resid Todstock, the yield of the pygas from the steam cracker ‘effluent is high as comparing with other feedstocks, such as rapliha, under similar steam cracking conditions. The pyzas rade from steam eracking of a resid feedstock normally has ‘high toluene and C, aromaties content as comparing witha pywss made from steam cracking other feedstocks, such as raphtha, under similar stoam cracking conditions. The pygas produced from the hydroprocessing steam cracking unit 3 ‘vas supplied toa fist separation unit 7 va line Abo 16 ‘weight units of the pygas were separated as a C,~ feedstock ‘and supplied fo a methylation unit 1 via line’? About 8 eight unit of methylating agent, eg., methanol, were sup- pli othe methylation nit Hvis ine 13 The producto the methyfation unit 11 comprising Tight olefins, e., ethylene and propylene, pars-xylene lights, and heavies, was supplied tw a second separation unit 17 . The C,~ aromatis were separated and optionally recycled to tae methylation nit 11 vil Tine 19 . About 6 weight units of Cy feedstock was Separated from the pygas proluet at the separation unit 7 and are supplied to a transalkylation unit 23 via Tine 21. The product ofthe tansalks ation unit 23 was subjected to further Separation atthe second separation uit 17 The Cy aromat- Jes were separated and optionally recycled to the transalky= Tation unit via line 27 . The lights were withdrawn from the separation unit 17 via line 29 as «lights product. The light ‘olefins were withdraw fom the separation unit 17 via line 31 asa light olefins product. The para-xylene was withdrawn, from the separation unit 17 vin line 38 as a para-xyleae product. The heavies were withdrawn from the separation ‘nit 17 va line 38 as a heavies product thus not been reported or renlered obvious in any prorat, that parylene ean be produced from resid feedstock with 20 wt yield. The state of the art technology today for produc- Ing p-xylene integrates naphila reforming with an aromaties plant. Typical p-xylene yield on naphtha feed is 351040 wt 1s suepesing that napa canbe subsite with mine less costly residual ol feedstock and produce p-xylene in simile ‘yields using a similar number of processing steps Pxample 2 A phosphorus stabilized ZSMCS with an alpha value of 1 ‘and 22 dimethybutane Diffusion Parameter of | see“ (mea 0 o 26 sured at a temperature of 120° C. and a 2,2-dimetby butane pressure of SkPaca) was used fo convert an 80 wi% medal, 20.wi% petiyltoluene feedstock. The reaetion was run in fixod-hed eactorat 0.7la-" WHSV, 101.3kPa-a pressure and ‘temperature of 390° C. The products of the reaction are listed in the following table, Nene ‘Ween Prost Compton C-cypuntos iene ope Inthe example, methanol conversion to hydrocarbon prod vets is 67 wt %, P-ethyliofuene conversion is 25 wt %, The ‘example suprisingly shows that an ethyltoluene can be eon- verted to p-xylene and ethylene with high selectivity. Those slilled in the art will recognize that when ethylbenzene is reacted with methanol over the same catalyst, the primary product isan ethyltoluene. The example proves that ethyl- foluenes are readily converted to ethylene and p-xylene. The examples prove that mixtures of ethylbenzene, toluene, and benzene will eat with methanol to produce p-xylene and Tight olefins, Example 3 A 65 wt % ZSM-S (Si0A1,0, molar ratio of 450:1) catalyst ad been steamed at 310°C. for | hour, The steamed catalyst has an alpha value of about 1, 2.2 dimethyToutane Diffusion Parameter of about 0.5 see“ (measured ata tem- perature of 120° C. and a 2,2-dimethylbutane pressure of 8 KPa, and a nehexane sorption of 65 mgig, was used 10 convert methanol at 430° C. and 101.3 kPa Ethylene selec- tivity a8 function of methanol conversion is eportd in FIG. 2 Example 4 The catalyst of example 3 was used to convert 55:1 molar ‘mixtures of methanol and aromatic cofeeds at 430° C. and 101.3 kPava, Three aromatic cofeeds were used: toluene, comtho-xylene, and metaxylene. Pihylene selectivity asa une ‘ion of methanol conversion is reported in FIG. 2 Example 5 “The catalyst of example 3 wasused io convert 12:1 molar mixture of methanol and para-thyltoluene or toluene at 380° C. and 101.3 kPa-a, Ethylene selectivity as a funetion of ‘methanol conversion is reported in FIG. 3 forboth feedstocks. Trade names used herein are indicated by s™ symbol or symbol, indicating that the names may be protected by eertaia trademark rights, eg, they may be registered trademarks in various jurisdictions "The meaningsof termsused herein shall ake theirondinary ‘meaning inthe ar; reference shall be taken, in particular, to Handbook of Petroleum Refining Processes, Third Fulton Robert A. Meyers, Editor, McGraw-Hill (2004). In addition,US 8,048,388 B2 27 all patents and patent applications, test procedures (such as ASTM methods). and olher documents cited herein are filly Incomporated by reference to the extent such disclosure is not ‘inconsistent with this disclosure and forall jurisdictions in ‘which such incorporation is permite. Also, when numerical lower limits and numerical upper limite are listed herein, ranges from any lower limit to any upper limit are conten = plated, Note further that Trade Names used herein are indi ‘cated by a ™ symbol or ® symbol, indicating that the names may be protected by certain trademark rights, eg, they may be registered trademarks in various jurisdictions “The dsclosurelas been described above with reference to ‘numerous embodiments and specific examples. Many’ varia- tions will suggest themselves to those skilled in this art in tof theahove detailed description. Allsuch obvious varia- tions are within the Tull intended scope of the appended claims. ‘We claim: 1. A system for manufacturing pars-xylene comprising: (9) a steam cracking unit adapted for steam eracking & Fnydrocarbon feedstock to provide a stream comprising Pyzas 28 (®)a separating unit adapted for separating said stream into ‘an overheads comprising pygas and a bottoms compr ing A: (©) amethylation unit lady connected with said separat- ing unit and adapted to methylate at Teast a portion of said py from (b) to prodice a product comprising prraxyene; and (8) trasalkylation unit Muidly connected with said sepa rating unit and adapted to tansalkylate at leasta portion of said A+ from (b) to produce a product comprising parcxylene. 2. The system of claim 1, wherein said methylation unit ia (©)and sai ransakyation unit in (4) are tuidy connected 10 4 common separation unit adapted for separation of the respective precucts comprising paraxylene as a side stream {rom said common separation unit 3. Thesystem of claim 2, wherein sad common separation ‘uit has @ conduit adapted to provide recycle back to sid ‘methylation unit and a conduit adapted to provide recycle back to suid tansalkylation unit