«2 United States Patent ‘USUO63767. BI (0) Patent No: US 6,376,733 BL Ferraro et al. (45) Date of Patent: *Apr. 23, 2002 (5!) PROCESS FOR PRODUCTION OF 60) References Cited PARAXYLENE, USS. PATENT DOCUMENTS (75) Inventors: John Michael Ferraro; Robert : : A 31970 Rost aeayns Michael Osman; John Di-Yi Ou, all of Seca aaga aera eae Houston, TX (US); Graeme lan Cox, parentage niga semad Beas Doneaster East (AU); James Aious0s A + "71078 Chen etal 585/301 Richardson Latiner, Seabrook; I0L597 A T97R Breckeniige 588/321 Kenneth Ray Clem, Humble, both of Sioig2ea A * 5/1091 Haag eta Siais00.25 1X (US) Si9.704 A * 12/1001 Haag etal 210/680 Sue0.590 A * 3/1992 Haag eta 26442 (73) Assignee: ExxonMobil Chemical Patents Ine. S047 8+ 5/1902 Haag ta 2101530 Houston, TX (US) SH74081 A * 121095 Feblner etal = 210500.25 Sfigass A * 4/1007 Fehlne eta 21g) (4) Notice: This patent issued on a continued pros 53116527 A * 21988 Deckman ea 210/651 ccution application filed under 37 CFR 1.53), and is subject to the twenty year Soe ers pateat term provisions of 35 USC. wo ss006i2—_10)1989 1544@)02). wo oypsis) Lye wo segues 1/1980 subject any disclaimer, the tem ofthis patent is extended or adjusted under 35 * cited by examiner US.C. 154(b) by 0 days, Primary ExaninerWaltee D. Gritin ‘Appl. No. 08/591,064 a Rearien Filed: Jan. 25, 1996 co7e 7/144; COTE ‘585/805; 585/819; 585/477, 585/478; 585/481; 585/321 585/805, 819, 585/477, 478, 481, 3215 50D/4 Field of Search ‘This invention relates to a process and a chemical plant for the production primarily of paraxylene. In particular the process and chemical plant utilise zeolite membranes for ‘enhanced paraxylene production a ims, 6 Drawing SheetsU.S. Patent Apr. 23, 2002 Sheet 1 of 6 US 6,376,733 BL [-8 6 4 PARAXYLENE | RECOVERY UT Py | an 5 5 FRESH XYLENE ISOM FEED S| SPLITTER Cy UNT ' 1m 3] | fs c STAB 10 ual i | -12 peTOL + — | -13 L-15 FIG. 1U.S. Patent Apr. 23, 2002 Sheet 2 of 6 US 6,376,733 BL 25 FRESH OK FED 37 23° (PARAKVIENE i | RECOVERY 5 j 1 wt 26 fy 24 L-27 FRESH XYLENE FEED —\ "| SPLITTER ce 20 a2. 21 29 30 |-28 ¢5 STAB. 31 35. i [-33 DETOL ~~ [- 34 [36 FIG. 2U.S. Patent Apr. 23, 2002 Sheet 3 of 6 US 6,376,733 BL 45 FRESH c= PK FEED 1-60 43 PRAKYIBE 1 RECOVERY < } a a 46 ty 44 L-47 FRESH XYLENE |SOM rep 7) seurter 7] WNT 40 42} DETOL /#——~ FIG. 3U.S. Patent Apr. 23, 2002 Sheet 4 of 6 US 6,376,733 BL "7 Px 103 PARE f | | Sn 105 101 18 Y t 15 LI — FRESH XYLENE | a ne | isom [-104 FEED “S| SPLITTER | -n9 oy WT 100 i oe 4 ! ! 102] [-t4 | 116 | | -106 ¢ Cr 1 107 | 1 MAY i ' T 1 109 |] eto. 5 | 113 I pone I I S FIG. 4U.S. Patent Apr. 23, 2002 Sheet 5 of 6 US 6,376,733 BL 205 2. x 203 PARAXYLENE < RECOVERY 7087 wT 201 206 204 207 FRESH XYLENE 1SOM FEED ~\] SPLITTER WNT 200 202 FIG. 5U.S. Patent Apr. 23, 2002 Sheet 6 of 6 US 6,376,733 BL PEXYLENE 302 M EBMENBRANE 304 303 SEPARATION PARTIE] = PERNEATE RECOVERY WT 305 q 301 ®B ISOM RECYOLE REACTOR XYLENES 315 oe \ baits A , | L~ 309 L | > | =| ! XYLENE a ISOMERIZATION —| ! REACTOR 314 — ! LQUDD PHASE i wine ~ 312 — 310 FRESH REA dt FEED 0) LERACTINATION 3n 300 [313 HEAVIESUS 6,376,733 BL 1 PROCESS FOR PRODUCTION OF PARAXYLENE BACKGROUND OF THE INVENTION ‘This invention relates to a prooess and a chemical plant {or the production of paraxylene. In panticular the process nd chemical plant tilise Zeolite membranes for enhanced paraxylene production In the petrochemical production chain one of the most important streams isthe Cito Cy aromatics steeam which is 4 source of raw materials for high value dowastzeam prod= ucts. From this stream, benzene, toluene and the C, aromat- ies which are particularly valuable may be obtained. The Cy aromatics are orthoxylene, metaxylene, paraxylene and eth ylbenzene. Paraxylene is often the most desirable of the xylenes; however because the boiling points of eibylbenzene, ortho-, meta- and paraxylene (hereinafter col- leetively referred to a8 “Cy aromatics") are close, they sre difficult to separate by fractional distillation. As'a conse- {quence various alternative methods of separating paraxylene irom C, aromaties have been developed, The most common ‘of sueh methods are fractional erysallisation which ilses the difference in freezing points between ethylbenzene, ortho, meta and paraxylene, and selective adsorption which commonly utilises zeolite materials 10 selectively adsorb paraxylene from C, aromatics streams; the adsorbed paraxylene is recovered after desorbing from the zeoli ‘When either of these processes are used paraxylene can be recovered in high yields from the Cy aromaties stream. The resulting filtrate from the erystallisation process or the ralfinate from the adsorption process are depleted in par- axylene and contain relatively high proportions of ethylbenzene, ortho-, and metaxylene. These sireams are typically subjected to further processing downstream of the crystallisation or adsorption process. “Typically one of the additional downstream processes is an isomerisation process. which is used to increase the proportion of paraxylene in paraxylene depleted streams rom such processes as fractional crystallisation or selective adsorption. The xylenes, which are predominantly ortho-and ‘metaxylene, can be contacted with an isomerisation catalyst ‘under appropriate temperature and pressure which results in the conversion of some of the ortho- and metaxylene to paraxylene. It is also usually necessary to convert some of the ethylbenzene to prevent it from building up to high ‘concentrations. A catalyst can be selected to enable conver- sion of ethylbenzene to benzene, andlor to orthoxylene through a C, naphthene intermediate andlor to Cy, aromatics and benzene via transalkylation. It may be that the catalyst or conversion of ethylbenzene 10 orthoxylene is also a xylenes isomerisation catalyst in which ease the orthoxylene from the ethylbenzene is converted to an equilibrium mix- ture of xylene. Prior art processes for making paraxylene have typically included combinations of isomerization with fractional erys- tullisation andlor adsorption separation. The problem with this combination is that despite improvements in catalyst performance the isomerisation technology is only able to procluce equilibrium or nesr-equilibrium mixtures of xylenes and may also be relatively inefficient for the conversion of | eliylbenzene to benzene or xylenes. The consequence ofthis is that big reeycles ofthe xylenes stream back through these processes are needed to ensure the conversion of the Cy ‘romaties siteam to paraxylene is maximised with or with= ‘out the additonal recovery if desired of orthoxylene andlor ‘metaxylene. There is a need therefore for improved pro- s “ 2 ‘cesses and chemical plants for the production of paraxylene from C, aromaties streams, whieh in particular address the problems associated with lange recycles andior low ethyl- benzene conversions. Zeolite membranes have been described in the prior at, for example in USS. Pat. No. 4,699,892, US. Pat. No. 5,100,596, EP 0481658, EP 0481659, EP 0481660, WO 93/13631, WO 93/0155, WO 94101209, and WO 94/2515]. However the prior art does not describe how 10 "use such membranes in actual C, aromatics processing inthe petrochemical eycle nor does the prior ant describe how to use such membranes in combination with existing processes to significantly enhance their paraxylene production capa- bility SUMMARY OF THE INVENTION ‘The presot invention is therefore diected to & chemical plant and process which olfers an impeovement over the prior art forthe production of paraxvlene from C;, aromatics Sreams. The present invention resides inthe specific appli- Cation ofa eolite membrane ait and process in a paraxy- lene or paraxylene with orthoxylene andor metaxvlene recovery process. Tis invention uilises zeolite membranes to contizuously separate paraxylene andior ethylbenzene from xylenes, oF 10 isomerise ortho- and metaxvlene 10 paraxylene andior ethylbenzene to xylenes and simultie neously or subsequently separate paraxylene. from the xylenes mixture. The use of a zeolite membrane unit and process in for example 4 process for paraxylene eccovery provides for a significant improvement in paraxylene pro dluction when compared to conventional paraxylene recov ery processes. “Accordingly the present invention provides a process for recovering paraxylene from a C, aromatics ream contain ing paraxylene and at least one thee isomer of xylene, ethylbenzene, or mixtures threo which process comprises {@) recovering by means ofa paraxyiene separation process ina paraxylene recovery ait & potion of said paraxylene from at least a portion of said Cy aromatics stream 10 produce s fist sream having 4 reduced paraxylene coa {ent and containing a less a portion of sid other isomers of xylene, said ethylbenzene, or mistues theteol, (©) passing at last a portion of said first steam dresly or ingieetly to a zeolite membrane unit comprising a zeolite ‘membrane and optionally isomersation catalyst under isomerization conditions, such that the permeate with- drawn through the zeolite membrane and from the zeolite ‘membrane unit is enriched in is paraxylene when com pared tothe feed to the zeolite membrane unit and (©) feeding the permeate directly or indirectly back to the paraxylene separation process. Preferably tere isan ational step between (a) and (b) ‘wherein at least a portion of said first stream is subjected 10 an isomeristion process in an isomerisation unit to produce fn Romerate having an enriched paraxylene content come pared to that of the first streams and itis atleast a portion of this isomerate siream whichis passed tothe zeolite mem- brane unit. Most preferably the permeate withdrawn from the zeolite membeane unit is enticed in paraxylene com- pared to the equilibrium concentration of paraxylene in a xslenes equilibrium mixture. ‘The preseot invention further provides for a paraxylene recovery plant comprising @) paraxylene recovery unit, and (6) a zeolite membrane uit comprising a zeolite membrane ‘nd optionally isomerisation catalyst. Preferably the paraxylene recovery plant comprises an isomerisation unit in addition to the paraxylene recovery ‘unit and zeolite membrane uni