2) United States Patent Clark ALKYLAROMATICS PRODUC ON Inventor: Michael C, Clark, Pasadena, TX (U ExxonMobil Chemieal Patents Inc, Houston, TX (US) Assignee (*) Notice: Suibjoct to any disclaimer, the term of this patent is extended of adjusted under 35 USC. 154(b) by O days (21) Appl. Nos 12/188,503 (22) Filed: Aug. 4, 2008 6s) Prior Publication Data US 200810287720 A1 Nov. 20, 2008 Related US. Application Data (62) Division of application No, 11/343,868, filed on Jan. 31, 2006, now Pat. No. 748,659 (2006.01) I 55/467 Fleld of Classification Search 585/467 Se application file for complete search history. 650) References Cited US. PATENT DOCUMENTS Sa71310 A * 12/1994 Bennet etal seer 6512183 BI* 12003 Cappllazen eal S856 * cited by examiner ‘US007652184B2 (10) Patent No. 4s) Date of Patent: US 7,652,184 B2 Jan. 26, 2010 Primary Examiner (74) Attorne Tan Dinh Dang Agent, or Firm—D. M. Tyas on ABSTRACT Aprocess for alkylation of analkylatablearomaticcompound to producea monoalkylated aromatic compound, comprising the steps of (a) providing at least one reaction zane having a ‘water content with atleast one alkylation catalyst having an activity anda selectivity for said monoalkylated benzene, sid alkylation catalyst comprising a porous crystalline molecular Sieve of a MCM-22 family material, said MCM.22 family ‘material is characterized by having an X-ray diffraction pa- ‘em including d-spocing maxima at 12.4025, 3.5720.07 and 3.422007 Angstroms; (b) supplying the reaction zone ‘with at least one alkylatable aromatic compound and atleast ‘one alkylating agen; (e) operating the reaction ane under Suitable alkylation or transalkylation conditions, to produce atleast one effluent which comprises a monoaliylated aro- ‘matie compound aad a polyalkylated aromatic compound(s) (@) monitoring the amount of the monoalkylated aromatic ‘compound or the amount ofthe polyalkylated aromatic com: pound(s) inthe eluent; () adjusting the water content inthe reaction zone o sure a desired amount ofthe monalkylated ‘aromatic compound or the polyalkylated aromatic ‘compound(s in the effluent, the water content inthe reaction ‘anc being in srange fom about | wppm to about 900 wpm: ‘and wherein the polyalkylated aromatie compound(s) pro- duced is reduced as compared to the reaction zone having 2 ‘water content of about O wppm witen the reaction zone is ‘operated under equivalent conditions. 10 Claims, No DrawingsUS 7,652,184 B2 1 ALKYLAROMATICS PRODUCTION (CROSS-REFERENCE OF RELATED [APPLICATIONS ‘This application is divisional ofS. application Sex. No 11/343,868 filed Jan. 31, 2006, now U.S, Pat. No. 7,425,659 nw allowed and is ull incorporated herein by reference FIELD OF THE INVENTION The present invention relates ta process for producing alkylated aromatic produets, particularly ethylbenzene and BACKGROUND OF THE INVENTION Ehylbenzene isa key raw material in the production of styrene und is produced by the reaction of ediylene and ben- zen in the presence ofan acidic alkylation or transalkylation ‘catalyst. Pthylbenzene production plants built before 1980, used AICI, oF BF, as the acidic alkylation or transalkytation ‘catalyst, Plats built affer 1980 have in general use zeolite based acidic eatalyss asthe alkylation andor transalkylation catalysts. Liguid phase ediylation of benzene using a catalyst com= prising eolite beta iscisclosedin US, Pat. No. 4:891,458and European Patent Publication Nos, 0432814 and 0629849. “More recently it has been disclosed that MCM-22 and its structural analogues have ity in these alkylation transalky- Jation reactions, for example, U.S. Pat. No. 4.992,606 (MCM- 22), U.S. Pat. No. 5,258,565 (MCM-36), US. Pat. No. 5.371, 310 (MCM-49), U'S. Pat. No. 5,453,554 (MCM-56), US. Pat. No. §,149.804 (SS7-25); US. Put No. 6,077,408 (ITQ- 1); Intemational Patont Publication Nos. WO97/17290 and WoOt/21562 (TQ-2, In the prior act alkvlation/irnsalkylation processes, the desired moncalkylated compound is produced slong with, polyalkylated impurities by contacting an alkylatable ar. matic compound and an alkylating agent in the presence of 3 ‘catalyst. During the alk lation/tansalkylation processes, the ‘etalyst ages die tothe deposition of coke and other delete rious materials on the catalyst. Such catalyst aging causes @ ‘decrease inthe catalysts activity forthe conversion of reac ats to products. To restore a catalyst’ saetivity, the catalysts, ‘often regenerated by controlled oxidation in ar, or by other means. Following regeneration, the catalysts activity is restored toa certain degree However, theregeneratedcatlyst fofien has a reduced selectivity to produce the desired monoalkylated compound, and increased amounts of the more undesirable polyalkyloted impurities are produced. ‘Therefore, there is a need for improved alkylation andor teansalkylation processes that inerease andlor control the activity and selectivity of such catalysts to produce the sige monoalkylated aromatic compound in 8 reaction zone. This invention moet this and other noes SUMMARY OF THE INVENTION In one embodiment, ths invention relates toa process for the alkylation or transalkylation of an alkylatable aromatic ‘compound to produce a moncalkylated aromatic compound, ‘comprising the steps of (providing atleast one reaction one having a water content ‘with at least one eatalyst; (b) supplying the esction zane with atleast one alkyl ‘aromatic compound and a least one alkylating agent, 0 o ble 2 (©) operating the reaction zone under suitable alkylation or ‘wansalkylation conditions © produce at least one ellluent ‘whieh comprises a monoalkylsted aromatic compound and polyalkylated aromatic compound(s): (4) monitoring the amount of the monoalkylated aromatic ‘compound or the amount of the polyalkylated aroma compound(s) in the eluent: (6) adjusting the water content in the reaction zone to secure ‘desired amount ofthe monalkylated aromatic compound forthe polyakylated aromatic eompound(s) in the effluent, the water content inthe reaction zane being in arange fos bout I wpm to about 900 wpm: an ‘wherein thepolyalkyltedaromatic compounds) produced is reduced as compared to the reaction zone having & water content of about 0 wppm when the reaction zone is operated ‘under alkylation or trnsalky ation equivalent condition. In another embodiment, this invention re {or alkylation of an duce a monoalkylated aromatic compound, comprising the steps of () providing atleast one esetion zone having awater content ‘with an amount of atleast ane catalyst; (b) supplying the rection zone with at Jeast one alkylatable ‘aromatic compound and a least one alkylating azent (6) operating the rection zone under suitable alkylation oF ‘ransalkylation conditions, to produce at Teast one effluent ‘whieh comprises a monoalkylated aromatic compound and polyalkylated aromatic compound); (2) monitoring the amount of the monoalkylated aromatic ‘compound or the umount of the polyalkylated aromatic ‘compound() in the effluent, () adjusting the water content in the reaction zone to secure ‘desired amounts ofthe monoalkylated aromatic compound and the polyalkylsted aromatic compound(s) inthe ef ent, the water content inthe reaction zone being ina range from about 1 wppm to about 900 wppm: and ‘wherein the amount of sid catalyst required to produce said sired amounts of monoalkylated aromatic compound and polyalkylated aromatic compound(s) is redueed as compared {o said reaction zone having a higher water content than step (e) and the reaction zone is operated under equiva alkylation or transakylation conditions. Tn yet another embodiment, this invention relates to a pro- cess for alkylation oF transallylation ofan alkylatable aro- ‘matie compound, to produce a monoalkylated aromatic com- pound, comprising the steps of (@) providing atleast one reaction one having awater content ‘withatleastonecatalyst, thecatalysthaving an activity and a selectivity for the monoalkylated aromatic compound: (b) supplying the reaetion zane with atleast one alkyatable ‘aromatic compound and a least one alkylating agent (©) operating the reaction zone under suitable alkylation or ‘ransalkylation conditions © produce at least one eluent ‘whieh comprises monoaliylated aromatic compound and polyalkylated aromatic compound(s); (2) monitoring the amount of the mosoalkylated aromat ‘compound or the amount ofthe polyalkylated aromatic ‘compound() inthe effluent; and (controling the water content inthe reaction zane to secure a desired combination ofthe activity and the selectivity of ‘the catalyst, the water content in the reaction zone being in ‘range from about | wppm to about 900 wpa, Instill yet another embodiment, this invention relates to an appar for the production of an monoalkylated aromatic fompoud, comprisingUS 7,652,184 B2 3 (a) a reactor having at least one inet, a Jest one reaction zone, and at least one outlet, the inlet adapled to introduce feed Steams) into the reaction zone, the feed stream(s) comprising a leat one an alkylating agent and at feast one alkylatablearomatie compound, the reaetion zone having ‘water content and adeptelto contain at least one alkylation for tansalkylation eatalyst, wherein at least one efvent ‘may he prodiced when the alkylating agent snd the sky latable aromatic compound arecoatacted inthe presenceot the alkylation or tansalkylation catalyst under suitable alkylation or transalkylation conditions, the effluent which comprises the monoalkylated aromatic compousd and polyalkylated aromatie compound(s), the outlet adapted to remove the ellis (b) ameans for monitoring the amount ofthe monoalkyted ‘aromatic compound andr the amouat of the polyalky= lated aromatic compound(s) inthe effluent, (6) 4 means for adjusting the water content from about 1 ‘wppm to about 900 wpm in the reaction zone, an whereby a desired combination of the monoatkylsted aro- matie compound andthe polyalkylated aromatic ‘compound(s) may be produced inthe eaetion zone. In another embodiment, this invention relates to a method Jor retofiting an existing alkylation or transalkylation unit having a reactorasdesribedin step (a) above, comprising the sep oF adapting said reactor with means for monitoring the amount of said monoalkylated aromatie compound oF the amount of said polyalkylated aromatic compounds) in said ‘ellluent;a means for adjusting suid water content from about 1 seppm to about 900 wppm in said reaction zone, and wherchy a desired combination of said monoallylated aro- matic compound and said polyalkylated aromatic ‘compourds) may be produced in said reaction zone. These and other facets of the present invention shall become apparent rom the following desiled description and appended claims, DETAILED DESCRIPTION OF THE PREFEI EMBODIMENTS, Feedstocks ‘The reactants used inthe process ofthe invention include an alkylatable aromatic compound and an alkylating agent AAs used herein, an “alkylatable aromatic compound” is a ‘componra that may receive an alkyl group andan “alkylating fagent” is a comporind which may donate anally group to an alkylotablearomatie compound. “The tem “aromatie” os used herein is to be understood in socordance with its art-recognized scope which inclides alky] substitted and unsubstituted mono- and polynvelear ‘compounds. Compounds of an aromatic character, whieh possess a heteroatom, are also useful provided sulicent activity ean be achieved if hey act as eatalyst poisons under the reaction conditions selected ‘Substituted aromatic compounds which may’ be used for the invention should possess atleast one hydrogen atom sdirecly bonded to the aromsatie nucleus, The seoasatic rings may be substituted with one or more alkyl, ary alkary, alkoxy, aryloxy, cycloalkyl, halide, andor other groups ‘which do not interfere with the alkylation rectin. Suitable aromatic compounds that may be used for this Jnention include benzene, naphthalene, anthracene, nxph- thacene, perylene, coronene, and phenanthrene, with benzene being prefered 0 o 4 Suitable alkyl substinuted aromatic compounds that may be used fr this invention include toluene xylene. isopropylben- ‘zene, normal propylbeazene, alpha-methy naphthalene, eth- ylbenzene, mesitylene, durene, eymenes,_butylbenzenc, pseudocumene, o-diethylbenzene, m-dieybenzene, pedi ethylbenzene, isoamylbenzene, isohexylbenzene, pentacth- ylbenzene, pentamethylbeazene; 1,2,3,4-ttracthylbenzene: 1.23,Stetamethylbenzene; 1,2 4tiethylbenzene: 12,3tre ‘ethylbenzene, m-but tl S-diethyl- toluene; o-ethyltoluene; p-ethylioluene; m-propyltoluene: 4-cthyl-m-xylene; dimethylnaphitaenes; ediylnapluhalene: 23udimethylunthracene; 9-elhylanthracene; 2-methylan- ‘hracene; o-methylanteacene; 9; 10-dimethy phenanthrene: ‘nd 3-methyl-phenanthrene. Higher molecular weight alky- Jaromatic hydrocarbons may also be used 3s starting materi als and include aromatic hydrocarbons such as are prodiced by the alkylation of aromatic hydrocarbons with olefin oligo- mers Such products are frequently refered to in the art as alkylate nd include hexylbenzene, nonylbenzene, dodecyl- benzene, pentadceylbenzene, hexyltoluene, nonylioluene, dodeeyltoluene, pentadeeytoluene ete. Very often alkylate is joblained 2s a high boing freton in which the alkyl group fttached tothe aromatic nucleus varies in size from about C, toabout C,. Reformate streams that may contain substantia quantities ‘of benzene, toluene andlor xylene may be particularly suit able food for the process of this invention. Although the process is particularly directed to the production ofelben- ‘zene from polymer grade and dilute ethylene, i is equally applicable to the production of other Cy-C.p alkylaromatic compounds, such as eumene, as well 2s C¢alkylaromatcs, such as C.-C). linear and nea Tinea alkylbenzenes. ‘Suitable allylating agents) that may be used inthis iven= tion comprise alkene jund(s) and/or aleobol compound(s) and mixtures thereo! Other suitable alkylating agents that may be uselul in the process of this invention ‘generally include any aliphatic of aromatic organie com pound having one or more available alkylating aliphatic ‘groups capable of reaction with thealkylstable aromatic com: pound. Examples of suitable alkylating agents are C.-C olefins such as C.-C; olefins, viz, ethylene, propylene the butenes, and the pentenes; C,-C,, alkanols (inclusive of sronbalcobols dialeahol,trialeohols, ete.) preferably C|-C, alkanols, such as methanol, ethanol, the propanol, the ‘butanols, and the pentanols: C,-C ethers, ep, CC, ethers ‘including dimethylethr and dietiylether: aldehydes such as ormaldehyde, acetaldehyde, propionaldehyde, butyralde- hnydo, and n-valeralehy de; and alkyl halides suc as methy! chloride, ethyl chloride, the propyl chlorides, the butyl chlo- rides, and the pentyl chlorides, and so forth. It is generally prefered thatthe alkylating agent has no preter than § car bon atoms, more preferably no greater than 3 carbon atoms. ‘Thus thealkylating agent may preferably be selected from the roup consisting of CC, olefins and C,-C. alkanol. The alkylating agent includes a concentrated alkene feedstock (ea, polymer grade olefins) and a dilute alkene foodstock (ex. catalytic cracking off-g). ‘A concentrated alkene alkylating agent that may be wef a the process of tis invention includes an alkene feed com prised of at least 65 mol. % ofthe alkene and preferably at Teast 99 mol. 9% 10 100 mol, % ‘A dilute alkylating agent that may be useful in the process ‘ofthis inveation incindes cite alkene foed which contains atleast one alkene and a diluent, optionally comprising st Jeqst one alkane. For example, where the alkene is ethylene the alkane may be ethane andlor methane. Preferably, the ute lkene feed comprises atleast 10 mol. % ofthe alkene,US 7,652,184 B2 5 preferably from 20 10 80 mol, % ofthe alkene. One partieu- Jarl useful feed isthe dilute ethylene stream obtained as an ‘off was Irom the uid eatalytie cracking unit ofa petroleum, refinery, ‘The term “wpm” as used herein is defined as parts por nillion by weight. The feed comprising reactants of the present process may contain eaalyst poisons. ‘The tenn “poison” as used herein means such compounds that sre present in race amounts in the feed(s) comprising the alkylatable romatie compound(s) or te alkylating agent(s) ‘which may eause deactivation ofthe alkylation or transalky~ lation catalyst overtime. Catalyst poisons which are strongly sorbed tothe allylation ortransallyation catalyst under lky- Jation or tansalkylation conditions inelude nitrogen com- pounds, sulfur compounds, and oxygea compounds of low molecular weight, preferably no preater than $00, preferably no greater than 300, Such catalyst poison compounds may ‘include ammonia, alkylamines, eg, methylamine and n-pro- pylamine, Nfoms! morpholine and N-methylpyrroldine. ‘These catalyst poisons may make up to 100 wppm ofthe total {ed tothe process, €g..0.001 to 100 spp. none embodiment, the feed(s) comprising the alkylatable ‘aromatic compound(s) andor alkylating agent(s)_ may ‘include water. The amount of water in the feed() is sc that the reaction zone is substantially free of an aqueous phase under the alkylation oe transalkylation conditions. The tem “substantially five of an aqueous phase”, as used hen ‘means that the reaction zone has less than $ wt. %, preferably lesstha I wi %, even more preferably ess than 0.5 wt. %, oF an aqueous phase under te lkylation or translation con- ditions. In another embodiment, the amount of water ia the eed(s) comprising the alkylatable aromatic compound and! ‘oralkylating agent such thatthe reaction zone has less than 900 ppm of water, preferably less than S00 wppm of water, more preferably less than 200 wppm of water, more prefer ably less than 100 wppm of water, even more preferably less than 5O wppm of water, most preferably less than 10 wppa oF In another embodiment, the water content ia a reaction zone may be adjusted andlor controlled by the addition of ater. Inone aspect, feed comprising liquid water, team, or ‘a mixture thereof, may be co-fed with the alkylutale aro- matic compound andor alkylating agent to the reation zone. The amount of water contained in the alkylatable aromatic ‘compound andor alkylating agent with a co-feed of liquid water andor stern andor a mixture thereof is such that the ater content in a fesction zone is less than 900 wppm oF ter, preferably less than 500 wppm of water, more prefer- ably Tess than 200 wppm of water, more preferably less than 100 wppm of water, even more preferably less than SO wpm ‘of water, most preferably less than 10 wwppm of water. The ‘amount of water contained inthe alkylatable aromatic com- pound and/or alkylating agent together with the co-fed water ‘and/or steam is such that the reaction zone is substantially ree ‘ofan aqueous phase under the alkylation or transalkylation ‘conditions In another emboiment, the water content ofthe reaction zone is adjusted andor controlled by removing water Irom the alkylatable aromatic compound and/or alkylating agent that is fed tothe reaction zone. For example, the alkylatable aromatic compound andor alkylating agent may be dried by ‘molecular steve bed before feeding to the reaction zone. In still yet another embodiment of this invention, the ‘amount of catalyst required to produce a desired amount of ‘monoalkylated aromatic compound andor palyalkylated aro- matic compound(s) is reduced as compared t the aout of 0 o 6 catalystina reaction zone having higher water content when the reaction zone(s) are operated under equivalent alkylation or transalkylation conditions. ‘The amount of catalyst requined « produce a desired amount of monoalkyluted aromatic compound and/or poly- alkylated aromatic compound(s) in a rection zone having lower water content is reduced by at least | wt. %, preferably atleast 5 wt, %, more preferably at leat 10 wt. %, even more preferably at east 15 wt. %, and most preferably at east abot 20 wi. %, as compared to the amount of catalyst requted 10 produce such desired amount of monoalkylated aromatic ‘compound andlor polyalkylated aromatic eompoundts) in a action zone having 900 wppm Walter content When the reve- ‘ion zones are operated under equivalent alkylation or tran- salkylaion conditions, such a, feed composition, temper ture, pressure, or weight hourly space velocity (WHSV”). It is believed that the activity of the catalyst increases when ‘water eontent in the reaction zone decreases. The term “activ~ ty" as used herein refers tothe amount of the moncalkylated aromatic compound preduced ina reaction zoneunder certain ‘concitions per unit aenount of time per wait volune and may be measure by a reaetion rate constant under suitable con- ions. Dy adjusting and/or coarolling the amount of water in a combined feed of the allrylatable aromatic compound andor alkylating agent to Test than 500 spp of wate, preferably less than S00 wppm of water, more preferably less than 200 ‘wpm of water, more preferably less than 100 wppmof water, even more preferably less than $O wppm of water, most pref. erably less than 10 wppm of Water, the activity ofa porous fenstalline molectlar sieve catalyst or the amount of monoalkylated aromatic compound may be controlled and ‘maintained to a desired range. In sill yet another embodiment of this invention, the amount of the polyalkylated aromatic compounds) produced Jina reaction zone having a water content af above 0 wppm is reduced as compared f0 the reaetion zone having a water ‘content of about O wppm when the reaction zone is operated ‘under equivalent alkylation or wansalky ation conditions. The selectivity ofthe catalyst increases when water conteat inthe eed inereases. The term “selectivity” as used herein with respect to monoalkylated aromatic compounds reers to the ‘weight ratio ofthe amount of the monoalkylated aromatic compound produced over the total d-alkylted aromatic ‘compound(s. For example, one measure of the selectivity of the catalyst for cumene may be measured by the weight ratio of the amount of cumene produced over the amount of di ‘soppy benzene pred ne otal propylene come Instill yet another embodiment ofthis invention, the selec- tivity Tor the monoalkylated aromatic compound is ineeased fas the amount of the polyalkylated aromatic compounds) produced ina reaction zone having a water content of above ‘O wppm is reduced by atleast 1%, preferably at least 5%, ore preferably’ at least 1, even shore preferably atleast 15%, and most preferably at least 20%, as compared to the -eaetion zone having a water content of about O wppm when the reaction zone is operated under equivalent alkylation or ‘ransalkylation conditions By adjusting andior controlling the amount of water in combined feeds) of the alkylatable aromatic compound and ‘oral ating agent to less than 990 wppm of water, preferably Jess than 500 wppm of water, more preferably Tess than 200 ‘wpm of water, more preferably less than 100 wppmof water, {even more preferably less than SO wppm af water, most pret erably less than 10 ppm of water the selectivity of a porousUS 7,652,184 B2 1 ‘eqalline molecular sieve catalyst or the amount of poly alkylated aromatic compound(s} may be contolledand main- tained to a desired range, Instill yet another embodiment, this invention eates to a process foralkylationafan alkylatable aromatic compound to produce 4 moncalkylated aromatic compound, comprising the steps of: (@) providing atleast onereaction zone having a water content Withatleastonecatlys, de catalyst having an activity and selectivity forthe monoalkylated aromatic compound; (b) supplying the resetion zone with atleast one alkylatable aromatic compound and at least one alkylating agent; () operating the reaction zone under suitable alkylation oF ‘ransalkylation conditions, to produce atleast one effluent ‘whieh comprises a monoalkylated aroma compoundand polyalkylated aromatic compound(s); (2) monitoring the amount of the moncalkylated aromatic ‘compound or the amount of the polyalkylated aromatic ‘compound(s in the effluent; and (€} controling the water content inthe regetion zone to secure ‘desired combination ofthe activity and the selectivity of the catalyst, the water content inthe reaction zone being in ‘range from about 1 wppm to about 900 wpe, Prodets Suitable alkyl substiuted aromatic compounds which may be prepared from the alkylation process af the presen inven- tion include toluene, xylene, isapropylbenzene (cumene), ‘normal propylbenzene,alpha-methylnaphihalene, ethylben: ‘zane, mestylene, durene,eymenes, buylbenzene, pseudoc- lumene, o-dietbylbenzene, m-diethyTbenzene, p-liedylben- zane, isoamy benzene, isohexylbenzene, pentacthylbenzene, pentamethyTbenzene; 1.2,3.4-tetrethylbensene; 12.3.5-tel ramethylbenzene; 1,2.4trethyTbenzene; 1,2,3-trimethylben- ‘zene, m-butytoluese: p-butyltolene:,3.5-diethyltoluen: ‘oretiltoluene;p-ethyitoluene: m-propylioluene; dt xylene; dimethylngphtbalenes; ethylnaphihalene; 2,3 ‘ethyl, anthracene; 9-ethylanthracene: 2-methylaathracene: ‘o-methylanthracene;9,10-dimethiyiphenanthrene; and 3-me- thyl-phenanthrene. Preferably, the alkylated aromatic prod- uct comprises monoulkylbeavene, Higher molecular weight alkylaromatic hydrocarbons may also be wed as staring materials and include aromatic hydrocarbons such as are produced by the allylation of aromatic hydrocarbons with ‘olefin oligomers. Such products are frequently refered to the art as alkylate and include hexylbenzene, nonyTbenzene, \dodecylbeazene, pentadeeylbenzene, hexylioluene, nonyl- toluene, doecyltoluene, pentadscyholuene, etc Very often alkylate is obtained 2s a high boiling fraction in which the alkyl group attached to the aromatie micleus varies in size from about C, 0 about Cg The feed(s) andl eMfents ofthe present process may con- tain produets and eatalyst poisons. The poisons in the feeds) fr effluents may be the poisons introduced to the raetion| ‘zone inthe feed but not sorbed on the catalyst, or the poisons ‘desorbed from the catalyst alter contacting with the feed, Ia ‘one embodiment of this invention, the molar ratio of the poison compound(s) inthe effivents over the poison com pound(s) inthe food i equal oles haa 1 Poisons in the feod may deactivate catalyst which results in ‘decrease inthe catalyst bed temperature while operating at ‘constant process conditions. Poisons in the feed andlor ef ‘ent may’ he measured by conventional techniques, sch a8, ‘GC, GCIMS, nitrogen analysis, and sulfur analysis, or other suituble techniques to measure polar compounds and other poisons known toa skilled artisan, The poisons adsorbed on the catalyst may be measured by the difference ofthe poison 8 ‘compounds on fresh and spent catalyst samples using tech- figues such as xray flourescence (XRF) and inductively coupled plasma (ICP) that ae capable of measuring poison ‘compounds on solid samples or other techniques known to a stalled anisan, Resetion Conditions “The alkylation reaction is carried out with the alkylatable ‘aromatic compound and the alkylating agent in the reaction ‘one under conditions to secure atleast parially in liquid phase. The alkylation or transalkylation conditions include a ‘temperature of 100 to 285° C. (212 0 545° F) anda pressure ‘of 689 (0 4601 kPa-a (100 to 667 psia, preferably, a pressure ‘of 1500 to 3000 kPa-a (218 o 435 psia), a WHSV based on alkylating agent (eg, alkene) for overall reactor of 0.1 1910, 1b”, preferably, 0.210 2h, more preferably, 0.50 1", or ‘a WHSV based on both alkylating agent and alkyltable aro- is for overall reactorof 1010 10h", preferably.2010 50, 1b" The alkyltable aromatic compound isalkyated withthe alkylating agent (alkene) inthe presence of an alkylation or translation estalyst in a reaction zone ora plurality of reaction zones. The reaction zone(S) ae preferably located in ‘singe reactor vessel, but may inhi another reaction zone having an alkylation or transalkyation catalyst bed, located inseparate vessel which may bea by-passableand whieh may perate as a reactive guard hed. The catalyst composition ed in the reactive guard bed may be different fom the catalyst composition used in the reaction zone. The catalyst ‘composition used inthe reactive guard bed may havemultiple catalyst compositions. Atleast one reaction zone, and nor- ‘mally each reaction zone, is maintained under conditions effective to cause alkylation ofthe alkylatable aromatic com- pound with the alkylating agent in the presence ofan alkyl ‘ion or transalkylation eaalyst. ‘The fluent fom the reaction zone comprises the desired alkylated aromatic product, unreacted alkylatable aromatic ‘compound, any unreacted alkylating agent (eg. alkene, alk- ene conversion is expected to be at least 90 mol. Yo, prefer ably, about 98-99.9999 mol. 9) and the alkane component ‘andthe ther impurities. Inoncembodiment, at east portion ‘ofthe eflvent is fed to another resetion zone where an ak lating agen is added for reaction withthe unreacted alkyat- ablearomatic compound with an alkylation or raasalkyation catalyst, Furthermore ot least a portion the efluent fom any of the reaction zane(s) may be fed direely o indirectly to a ‘eansalkylation unit “The term “at east pty in liquid pase” ss used herein isunderstood as amixturehavingat least 1 wt. % liquid phase, ‘optionally at east S wt, %lghid phaseata given temperature, pressure, and composition In addition to, and upstream of, the reation zones, by passable reactive or unreactive guard bed may normally be located in. reactor separate om the alkylation reactor. Such guard bod may also be loaded with an alkylation or transally- Jation catalyst, which may be the same or different from the catalyst used in the reaction zone() Such guar bed is main- tained from under ambieat conditions, or at suitable alkyl ‘on or transalkylstion conditions.‘ Teast a portion of alky~ Jatable sromsatic compona, snd optionally at east a portion of the alkylating agent, are passed through the unreactive or -wetive guard bed prior to entry into the reaction zone. These guard beds not only serve to affect the desired alkylation reaction, bit is also Used to remave any reactive impurities in the feeds, such a8 nitrogen compounds, which could other- ‘wise poison the remainder ofthe alkylation or transalkylation catalyst, Thecatalyst inthe reactive unreactive guard bed is therefore subject (0 more frequent repeneration andlorUS 7,652,184 B2 nder of thealkylationortransalky jon catalyst, and hence the guard bedi typically provided with a by-pass cizcuitso thatthe alkylation feed(s)may'be fed directly tothe series connected reaction zones in the reaetor ‘while the guard bed is out oF service. The reactive or unneae> tive guard hed may be operated in co-cuent upows oF down flow operation The reaction zone(s) used in the process of the present invention is typically operated so as to achieve essentially ‘complete conversion ofthe alkene, However, for some appli ‘ations it may be desirable to operate at below 100% alkene ‘conversion. The employment of «separate finishing reactor ‘downstream of the reaction 7one(s) may be desirable under ‘certain conditions. The finishing reactor would also contain alkylation or transalkylation catalyst, which could be the me or different from the catalyst used in other reaction ‘zones in te alkylation or transalkyltion reactor) and may be maintained under at least partially liguid phase or alter nately vapor phase alkylation or tansalkylation conditions. ‘The polyalkylated aromatic compounds inthe effluents may be separated for transalkylation with allylatable aromatic ‘compounds. The alkylated aromatic compound is made by tronsalkylation between polyalkylated aromatic eompownds ‘andthe alkylatable aromatic compound. The alkylation or transalkylation reacor(s) used in the process ofthe presen invention may be highly selective tothe sired monoalkylated product, such as ethylbenzene, but ‘ypically prnducesat least some polyalkylated species, Inone ‘embodiment, the efuent from the final alkylation reaction ‘zone is subjected toa separation stp to recover polyalkylated fromatie compound(s) In another embodiment, at least & portion ofthe polyalkylated aromatic compounds supplied toa transalylation reactor which may be separate fom the alkylation reactor. The tansalkylation reactor produces an ‘elllueat which contains additional monoallylated product by reeting the polyalkylated species with an alkylatable aro- ‘atic compound. At ket a portion ofthese efflents may be separated to recover the alkylated aromatic compound (otonoalkylated aromatic compound andior polyalkylsted ‘aromatic compound). Particular condition forcarrying out the alkylation af hen= zene with ethylone at least partially in liquid phase may have a temperature of from about 120 to 285° C., preferably. a temperature of fom about 150.0 260°C, apressureof 689 10 44601 kPa-a (100 o 667 psi), preferably a pressure of 150010 4137 kPasa (218 to 600 psia), a WASV based on total ethyl- ‘ene and total catalyst for overall resetor of 0.1 to 10 Br preferably, 0.2 t0 2h”, more preferably, 0.5 to 1 1r!, or & WHSV based on both total ethylene and benzene, and total catalyst for overall reactor of 10 10 100 h, preferably, 200 50h" and a molar ratio of benzene to ethylene from about 1 tw about 10, Particular conditions for carrying out the atleast partially in iguid phase alkylation of benzene with propylene may ‘incluso temperature of from about 800 160°C. a presse ‘of about 680 0 about 4800 kPa-a;profeably from about 100, to 140°C. and pressureof about 200 19 3000KPa-a, a WHISV based on propylene of from about 0.1 about 10 hi, and & molar ratio of benzene to ethylene from about 1 1 about 10. ‘Where the alkylation system includes a reactive guard bed, ‘tis maintained under atleast partial in liquid phase eondi- tions. The guard bed will preferably operate at a temperature ‘of from about 120 to 285° C., preferably, a temperature of from about 150 t0 260° C.,a pressure of 689 10 4601 kPs-2 (100 t0 657 psia), preferably. apressure of 1500 104137 kPaca (G18 to 600 psia) a WHSW based on total etiylene and the ‘otal amount of eaalyst forthe overall eaetorof0.1 to 108, 0 o 10 preferably, 0.2 10 2 0", more preferably, 0.5 to 1 A', ora WHSV based on both total ethylene and total beazene, and the total amount of eatalyst for the overall reactor of 100 100 1h”, proferably, 200 50 h, and a molar ratio of benzene to ethylene from about 1 0 about 10, ‘The transalkylation reaction may take place under atleast, partially in liquid phase conditions. Patieular conditions for ‘carrying out the at least partially in guid phase taasalkyla- ‘ion of polyalkylated aromatic compound(s), eg, potyethyl- Denzene(s) oF polyisopropylbenzene(s) with benzene may ‘include a temperature of fom about 100° to about 300°C. a pressure of 696 (0 4137 kPa (101 to 600 pia), a WHSY based on the weight of the polyalkylated aromatic compound(s) feed to the alkylation revetion zone of Irom bout 0.510 about 100 hr and a molar ratio of benzene to polyalkylated aromatic compound(s) of from 1:1 t0 30:1 preferably, 1:1 to 10:1, more preferably, 1:1 10 5: In another embodiment, the tansalkylation reation may take place under spor phase conditions. Particular condi- ‘ions forearrying out the vapor phase transalkylation of poly- alkylated aromatic compotind(s), eg. palysthylbenzene(s) or polyisopropylbenzene(s), with benzene may include a temperature of from about 350 to about 450°C. presture of £696 to 1601 kPaa (101 to 232 psa), a WEISV based on the ‘weight ofthe polyalkylated aromaticcompound(s) eed tothe reaction zone of from about 0 to about 20 he", preferably, {om bout | toubout 10h, anda mola ato oF benzene polyalkylated aromatic compound(s) of from 1 05:1, pre erably, 2:1 10 3:1, Catalysts In one embodiment of this invention, the alkylation or ‘ransalkylaton catalyst that may be used in this invention isa porous erystalline molecular sieve having a zeolite frame- ‘work type of at least one of MWW, FAU, *BEA, or any combination thereof, In another embodiment, the porous enystalline material comprises at Teast one of zeolite bet, zeolite Y, Ultastable Y (USY), Dealuminized ¥ (Deal Y) monienite, ERB-1, ITQ-1, 1TQ-2, 1TQ-30, rare earth exchanged Y (REY), PSH-3, SS7-28, MCM-22, MCM-36, MCM-49, MCM-S6, or a MCM-22 family material In one embodiment, the eatalyst ofthis invention may or may not Fhave metal funetion, such a8 hydrogenation funetion pro- vided by noble metal(s) eg, metal(s) of Groups Il IV.V, VI. VIL. and Vill of periodic table. In yet another embodiment, the catalyst oF tis invention may or may not have a zeolite having a zeolite ramework type of MFI, eg, silialite or ZSM-S ‘The tern “MCM-22 family material", as used herein, includes ‘molecular sieves made fom # common frst degree ery talline building block “unit cell having the MWW framework ‘opology”.A mit cell isa spatial arrangement of atoms which is tiled in three-dimensional space to deseribe the erystal as described in the “Atlas of Zeolite Framework Types", Fifth Elion, 2001, the entire contents of whieh i incorporated as reference; (b) molecular sieves made from a common second degree ‘building block, a 2-dimensional ting of such MWW framework type unit ells forming a "monolayer of one ‘unit call thickness”, preferably one cant eel thickness (©) molecnlar sieves made from common second degree building blocks, “layers of one of more than one wit eel thickness”, wherein the layer of more than one unit eel thickness is made from stacking. packing. or binding at Jeasttwo monolayers of one unit cell thick. The stacking ofUS 7,652,184 B2 ul sueh second degree building blocks ean be in a rexular fashion, an iregular fashion, a random fashion, or any combination thereof, and (@) molecular sieves made by any 1-dimensional, 2dimen- sional or 3-dimensional combination of unit cells having the MWW framework topology. will be understood by a person skied inthe art that the MCM-22 family material may contain impurities, such as amomphous materials; unit cells having non-MWW frame- work topologies (eg, MFI, MIW); andr other impurities (eg, heavy metalsand/or organi hydrocarbons). The MCM- 22 family materials of this invention have mor proportion (less than 50 wt. %), preferably less than 20 wr, %, more preferably lest than 10 Wt, 6, even more preferably les than 5 wt. 9%, and! most preferably less than 1 wt. %, of such ‘impurities in the MCM.22 family materials, which weight percent (wt 96) values ae basecl on the combined weight of ‘impurities and pure phase MCM-22 family material, Tin one embodiment, the MCM-22 family: materials are ‘haructeized by having an X-ray dilliaction pattem includ jing d-spacing maximaat12.420.25,3,5720.07 and 3240.07 Angstroms (either calcined or as-synthesized). In another ‘embodiment, the MCM-22 family materialsarechamseterized by having an X-ray difraction patter including d-spacing riaxima at 12620-25, 6920.15, 3.572007 and 3.4220.07 siroms (ether calcined or as-synthesized), The X-ray “diffraction data used to charseterize said molecular sieve are ‘obiained by standard techniques using the Kalpha doublet of ‘copper asthe incident radiation andadifractometer equipped ‘with a scintillation counter and associated computer as the collection system. Materials belong to the MCM-22 family Include MCM-22 (described in US. Pat. No. 4.954.325), PSHL3 (described in US. Pat. No. 4839,400), SS7-25 (de scribed ia U.S, Pat. No. 4826,667), ERB-I (desribed i Europenn Patent No, 0293032),IT(-I (described ia US. Pat. No. 6,077,498), 1TQ-2 (described in International Patent Publication No. WO97/17200), ITQ-30 (described in Inter- national Patent Publication No. WO20051 18476), MCM-36 (described in US. Pt. No, §.250,277), MCM-49 (described in US. Pat, No, $236,575) and MCM56 (described in US. Pat, No. $362,697). The entire contents of said patents are ‘ncomporated herein by reference. isto be appreciated the MCM.22fuily molecularsiewes described above are distinguished from conventional large pore zeolite alkylation or ranslkylation catalysts, such as ‘mondenite, in that extalysis in MCM-22 materials oecurs in 12-rng surface pockets which do not eommunicate with the {Oring intemal pore system of the molecular sieve ‘The zeoitic materials designated by the IZA-SC as being of the MWW topology are multi-layered materials which have two pore systems arising from the presence of bot 10 and 12 membered rings. The Atl of Zeolite Framework ‘Types clases five differently named materials as having this same topology: MCM-22, FRB-1, ITQ-1, PSH-3, and SSZ- 25. The zeolites ofthe MWW type are described as having varied uses. US. Pat. No. 4,826,667 describes elite SS7-25 ‘8 usefol primarily for catalyzed hydrocarbon conversion reactions, seh 3s catalytic cracking, hydrocracking, hydrodevaxing, olefin and aromaties formation resetions sucl as xylene isomerization, but also as an adsorbent, 38 8 ‘ter and asa water-sofRening agent. US. Pat. No, 4954,325 lists 16 diferent uses forthe material now known as MCM- 2 ‘Altematvel; the alkylation andor tansalkylation catalyst ‘may further comprise n medium pore molecular sieve having Constraint Index of 2-12 (as defined in U.S. Pat.No. 4 218), including ZSM-S, Z8M-11, ZSM-12, ZSM-22, 2SM- 0 o 12 23, ZSM.3S, and ZSM-48. ZSM-S is described in detail USS Pat No. 3,702,886 and Re. 29.948, 2SM-1 i described in dealin US, Pat, No, 3.709.979. ZSMc12 is deseribed ia USS. Pat. No. 3,832,449. 7SM-22 isdoseribedin US. Pat. No. 4,556,477, ZSM-23 is describ in US. Pat. No, 4,076,842. 7SM-35 is deseribed in U'S. Pat. No. 4.016.248. 7SMA8 is ‘more particularly described in US. Pat. No. 4,238,231. The entire contents all hesbove patent speci porated herein by reference. Tn another embodiment, the alkylation andor transalkyla- sion catalyst may comprise a lage pore molecular sieve hav- ing a Consirint Index of less than 2. Suitable large pore ‘molecular sieves inchide zeolite beta, zeolite Y, Ultrastable Y (USY), DealuminizedY (Deal ¥), mordeaite, 7SM-3, 7SM- 4, ZSM-I8, and 7SM-20. Zeolite ZSM-14 is described in US. Pat. No. 3.923,636. Zeolite ZSM-20 is described in US. at. No. 3972,985, Zeolite beta is deseribed in U.S. Pt. No. 3,308,069, and Re. No. 28.341. Low sodium Ultrasable ¥ ‘molecular sieve (USY) is deseribed in US. Pat. Nos. 3,293, 192 and 3,449,070, Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Pat. No. 3,442,795. Zeolite UHP-Y is described in US. Pat. No. 4,401,556. Rare arth exchanged Y (REY) isdescribed in US. Pat. No. 3.524 820. Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (ie, synthetic mordenite prepared from a reaction mixture com- prising a tetraethylammonium directing agent). TEA- ‘mronlenite is disclosed in U.S, Pat, Nos, 3,766,093 and 3,894, 104. The entire contents ofl the above patent specifications are incorporated herein by reference. "The Constraint Index is convenient measure ofthe extent to which an sluminosilcate or moleculae sieve provides con- trolled secess to molecules of varying sizes to is intemal highly restricted access to and egress fom its intemal strue- ‘ure have a high value forthe constraint index, and alumino- silicates of this kind usually have pores of small size, eg less than 5 Angstroms, On the other hand, aluminosfietes whieh provide relatively free acces to the internal aluminosilicate Structure havea fw value for the constraint index, and us ally pores of large size. The method by which Constraint Index may be determined is described Fully in U.S. Pat. No. 4.016.218, which is incorporated herein by reference ‘Meleculae sieves andlor zeolites that may fad application in the preset invention include any of te naturally occurring ‘or synthetic erystalline molecular sieves. Examples of these zeolites include large pore zeolites, intermediate pore size ‘zeolites, and small pore zeolites, These zeolites and their isotypes are described in “Atlas of Zeolite Framework Types", eds. Ch, Baerlocher, W. H. Meier, and D. H. Olson, Elsevier Filth Edition, 2001, which ishereby incoxporated by reference. A summary of the prior ar, in terms of production, ‘modification and charocterization of molecular sieves, is {scribed in the book "Molecular Sieves Principles of Syn- thesis and Identification”: (R. Szostak, Blackie Academic & Professional, London, 1998, Second Fon) In addition to ‘molecular sieves, amorphous materials, chiefly silica, alum ‘num silicate and aluminum oxide, have boen used as adsor- ‘bens and catalyst supports. A number of long-known tech- niques, lke spray dying, prilling, pelletizing and extewsion, have been andl are being used to produce macrostectures ia the form of, for example, spherical particles extrudates, pe! Jets and tablets of both mieropores and other types of porous ‘materials for use in eatalysis, adsorption and ion exchange. A summary ofthese techniques i described in “Catalyst Man- facture” A.B. Stiles and T- A. Koch, Marcel Dekker, New York, 19:US 7,652,184 B2 13 The stability ofthe eatalyt(s) used inthe present process may be increased by steaming. U.S. Pat. Nos. 4,663,492; 4,594,146; 4,522,929; and 4,429,176, desribe conditions for the steam stabilization of zeolite catalysts which may be utilized to steam-stailize the catalyst Reference is made to these patents fora detailed description ofthe steam stabiliza- tion technigue for use with the present catalysts. The steam Sabilzation conditions typically incInde contacting the cata- Iyst with, 5-10026 steam ata temperature ofa least about 300" C. (24, 300°-650" C. fora least one hour (eg. 1-200 hours) ta pressure of 101-2.500 kPa-a. Ina more particular ‘embodiment. the catalyst may be made to undergo steaming ‘vith 75-1008 steam at 315°-S00" C. and atmospierie pres Sure for 2-25 hours. The steaming of the catalyst may take place under conditions sufficient fo inital increase the AAipha Value of the catalyst, the significance of which is ‘discussed below, and produce a steamed catalyst having an ‘enhanced Alpha Value If desired, steaming may becoatinued to subsequently rece the pha Value from the higher Alpha ‘Value to Apa Value whic i substantially the seas the Alpha Vale ofthe uasteumed catalyst. ‘The alpha valne test isa measnre of theeracking activity of ‘a catalyst and is deseribed in U.S. Pat. No. 3,384,078 and ia the Journal of Catalysis, Vol. 4, p. 527 (1965); Val. 6p. 278 (1966); and Vol. 61, p. 395 (1980), each incomporated herein by reference as to that deseription. The experimental condi- > tions of the test used herein include constant temperature of S538" C, and variable Now rate as described in det in the Journal of Catalysis, Val. 61, p. 395. Apparat ‘In one embodiment, this invention relates to an apparatus forthe production of a monoalkylated aromatic compound, ‘comprising: (a) a rector having at least one inlet, atleast one reaction zone, and at least one outlet, the inlet adapted to inteoduce ‘eed strea(s) into the reaction zone, the Feed stream(s) com- prising t least one an alkylating agent and at least one lky= Iatable aromatic compound, the reaction zone having a water ‘content aid adapted to contsia at least one alkylation oF transalkylstion catalyst, wherein atleast one efllent may be produced when the alkylating agent and the alkylatable aro- ‘matic compound are eontacted inthe presence ofthe alkyla- tion or transalkyltion eatalyst unde suitable alkylation or transalkylaton conditions, the effluent which compeses the ‘monoalkylated aromatic compound and polyalkylated aro- ‘matic compound), the outlet adapted to removethe eluent: (b) ameans for monitoring the amount ofthe monoalkyated sromatie compound or the amount of the polyalkylated aro- ‘tie compound(s) in the ellluat (6) 8 means for adjusting the water content from about 1 ‘wpm to about 900 wppin in the reaction zone, and whereby a desired combination of the moaoalkylated aro- matic compound andthe polyalkylated aromatic ‘compounl(s) may be produced inthe reaction zone. Inone aspect of this invention, the means for adjusting the water content ofthe reaction one includes introducing Water to the esetion zone in the form of steam, liuid Water, or & mixture thereof, Other such means inclide removing water from the alkylatable aromatic compound andr the alkyat- ‘ng agent by drying with a molecular sieve ar dehydration by disillation, or other suitable means knowa o those skill the art or by combinations of these techniques suchas isi Jatin followed by drying over a molecular sieve or clay. ts well know to person skilled inthe art that the mans {or monitoring the amount of the monoalkylated aromatic ‘compovnd or the amount of the polyalkylated aromatic com- poutidineludeany conventional techniques, suchas, online oF s 14 olline Gas Chroaatograph (GC), online or ofline Gas Chro- ‘matograph Mass Spectrometer (GC-MS), material balance analysis, FTIR, UY, elementary analysis, density analy ‘tavity analysis, other suitable techniques 19 meastre aro ‘matic compound known toa skilled artisan, and any comb sation there. In an alternative embodiment of this inveation includes a smthod for retafiting an existing alkylation nit having a reactor asdeseribed above. Thismethod comprises the step of ‘adaping said reactor with a means for mositoring The amount of said monoalkylated aromatic compound or the amount of said polyalkyated aromatie compound(s) in suid effluent ‘means foradjustng said water content from about I wppm to bout 90 wppm in said reaction zone, and whereby a desired ‘combination of said monoalkylated aromatic compound and sid polyalkylted aromatic compound(s) may be produced fn said reaction zone. This method x stitable for retoiting ‘anexisting ethylbenrene or eumene plat with wpor phase ‘atleast partial liquid phase, or mixed pase alkylation reactor In particular, the process of this inveation may be used to retrofit an existing ethy benzene or eumene plant using poly- ‘mer gnide or chemical grade ethylene or propylene with ‘minimum amount of new equipment, such as, extra compres” sors for the alkylating agent, extr-separation column [or Tight gas and aromatics, and other equipment The invention will be more particularly deseribed with reference tothe following Examples. ‘Testing Procedures Peed Pretreatment ‘Benzene (99.96 wt. %6) was obtained from the Fxxon¥Mobil ‘Baytown Chemieal plant. The benzene was passed throvgh a pretrcatment vessel (2 | Hoke vessel) contining absorbent ‘materials fom inlet (0 out, Al absorbent feed pretreatment ‘materials were dried in a 260° C. oven for 12 hours belore sing Polymer grade propylene was oblained from Seott Spe- cialty Gases (Pasadena, Tex., USA). Propylene was passed through # 300 ml vessel containing absorbents which were ried in 260° C. oven for 12 hours before using Ulta high purity grade Nitrogen was obtained from Scott Specialty Gases. Nitrogen was passed through 2 300ml ves- ‘sel containing absorbents which were dried at 260° C. Tor 12 hours before using. Catalyst Preparation and Loading ‘MCM-22 catalyst was prepared according to U.S. Pat No 4.954325, the whole content of which i incorporated herein as reference. MCM-49 catalyst was prepared secording 10 US. Pat, No, 5,236,575, the whole caste of whieh i incor porated herein as reference. Catalyst activity was calculated using the second order rate ‘constant under the reation conditions (lemperature 130°C. and pressure 2170 kPa-a). Reaction rate-constants were cal tated using methods knowin to those skilled inthe art. See “Principles and Practice of Heterogencous Catalyst" J. ML ‘Thomas, W. J. Thomas, VCH, 1st Edition, 1997, the dselo- sure of which is incorporated herein by reference. Catalyst selectivity was calculated using the weight ratio of eumene produced over d-isopropy] benzene unde the reaction con- Sitons (temperature 130° C, and pressure 2170 KPa), “Two grams of catalyst was dried in air at 260° C. Tor 2 hours. The catalyst was removed immediately after drying, The bottom of a eatalyst basket was packod with quartz chips followed by loading ofone gramof catalyst into basket on top of the quartz chips. The catalyst was then covered by add ‘ional quart chips. The catalyst basket containing thecatalyst ‘nd quartzchips was dried at 260" C. ina for about 16 hous. Before each experiment the reactor and all lines were leaned with a suitable solvent (such as toluene) followed byUS 7,652,184 B2 15, Slowing of air after cleaning to remove all cleaning solve The eatalyst basket containing the eatalyst and quartz chips ‘as placa in reactor immediatly after drying. “A'300 ml Pagr® batch reaction vessel (Series 4563 mani Bench top reactor with a stati catalyst basket, Parr Iasrd- ment Company, Moline Il USA) equipped with a stir od and static catalyst hasket was used forthe activity and selec- tivity messtrements. The reaction vessel was ited with 60 removable vessels forthe introction of benzene and propy lene respectively. ‘The reactor was purged with 100 ml/min ofthe treated ultra high purity nitrogen, Na, for 2 hours at 170° C. Then, the reactor temperature was redaced to 130° C. under nitrogen How. All inlets and outlets of the reactor were closed of afterward. Pretwated benzene (156.1 gram) was transferred Jno the reactor under 791 KPa-aultes high pully niteogen blanket. The reactor was sted st $00 pm for I hour. Pre- tested liquid propylene (28.1 pram) under 2170 kPaa ultra high purity nitrogen is then wansferred 40 the reactor. The reactorwas maintained st 2170 kPa-a hy the 2170 kPa- ultra high purity nitrogen. Liguid samples were taken at 30, 60, 120, 150, 180 and 240 min after alition of the propylene. ‘Water was added tothe reaction mixture by either of 160 smethods. First, the Water wos ade tothe pretreated benzene supply to obtain the desired water level inthe reation mix- ture, Second, the pre-dried catalyst was humidified until dhe proper amount of waler adsorbed corresponding to he ‘sired amount of waerin the reaction mixture was obiained. ‘The amount of water in the reaction product at end of test was measured hy Karl Fischer ittaor (Mettler ‘Toledo, Inc. ‘Columbus, Ohio, USA) which is typically accurate to within 50 wp Examples (One grat MCM.22 catalyst (65 wt. %MCM-22 and ‘% alumina), one gram MCM89 catalyst (80 wt. %% MCM-22 snd 20.1. 9% alumina), andl one gram zeolite bet catalyst (80 ‘wt. % Beta, SVAI, of 24, and 20 wt % alumina) were tested lander the conditions and method described shove, ‘The activity ofthe zeolitebeta catalyst increased by 88% at ‘Owppm 11,0 as compating to the activity ofthe zeolite beta catalyst at same conditions except at a water content af 872 ‘ppm. The activity ofthe zeolite MCM-22 catalyst increased by $44% at O wppm HO and 22% at 448 wppm H.0 as ‘comparing tothe activity of the zeolite MCM-22 catalyst at same conditions except water content of 922 wppm. The ‘aetvity ofthe zeolite MCM-49 catalyst increased by 497% at Owppm HO and 33% at 474 ppm 11-Oas compared tothe activity ofthe zeolite MCM-49 catalyst at same conditions ‘except weler content of 85 wpa. “The selctvity ofthe zeolite beta catalyst inerease from 4.76.1 Owppia 1,0 w 14.49 91872 wpa 1,0 as compared Wo the selectivity of the zsolite beta catalyst at the sume ‘conditions except ata Water content of O wpa. The selec tivity of the zeolite MCM.22 catalyst increasetby 43% at 922 ‘ppm HO and 412% at 211 wppm H,O as compared to the selectivity ofthe zeolite MCM.-22 catalystat same conditions ‘except water content of Opp. The selectivity ofthe zeolite MCM-A9 catalyst increased by 78% at 885 wpm [1,0 and 36% at 474 wppm ITO as compared othe selectivity ofthe ‘zeolite MCM-49 caalystat same conditions except ata water ‘content of O wpm, All patents, patent applications, test procedures, priority ‘documents aticles, publications, manuals, and] other docu mens cited herein are filly incorporated by reference 0 the ‘exten such diselosure isnot inconsistent with this invention | fn for al jurisdiction mite. 0 o 16 ‘When numerical lower limits and anmerial upper limits are listed herein, ranges from any’ lower limit any upper Timit are contemplated. ‘While the illsrative embodiments ofthe invention have been described with particularity. it will be understood that various other maxificaions will be apparent to and may be readily made by those skilled in the art without departing ‘rom the spirit and scope ofthe invention. Accordingly, it is ‘ot intended thatthe scope ofthe claims appended hereto be Jimitad w the examples and descriptions set forth herein but ‘ther tht the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, inchading all features which would be tested as ‘euivalenis thereof by those skilled in the art to which the invention pertains ‘What is claimed is: 1. A process Jor alkylation of benzene with atleast one alkylating agent to produce a monoalkylated benzene, com- prising the steps of (@) providing at Teast one reaction zone having a water ‘content with ot Teast one alkylation catalyst having an ‘cliviy and a selectivity for said monoalkylated ben- Zone, said alkylation catalyst comprising a porous ery talline molecular sieve of MCM.56: (b) supplying suid reaction zone with said benzene and suid at least one alkylating age (6) operating said reaetion zone under suitable alkylation ‘conditions, to produce at Teast one effluent which com prises a monoalkylated benzene and polyalkylated ben- Zonet) (é) monitoring sid amount of sid monoalkylated benzene ‘or said amount of said polyalkylted benzene(s) in sid ‘effluent and (e) adjusting said water content in range from shout 1 ‘wppm to about 900 wppan in said eaetion zone tosecure ‘8 dosirod combination of sad activity and said solctiv= ity of said alkylation catalyst based on said amount of said monoalkylated benzene or sad polyalkylated ben- zene() of). 2. The process ofelaima 1, wherein sad a least one alky Jating agents selected from the group consisting of ethylene, sropylene, batenes and pentenes 3. The process of claim 1, wherein sad at least one alky~ Jating agent i selected from the group consisting of metha- ‘ol, ethanol, propanols, bulanols and pentanols. 4. The process of claim 1, wherein said monoalkylaced benzene comprises ethylbenzene and said alkylating agent comprises ethylene or ethanol, '3. The process of claim 1, wherein said monoslkylated ‘benzene comprises cumene and said alkylating agent com prises propylene or propanol, 6. The process of claim 1, wherein said monoalkylated benzene comprises sce-buty-henzene and said alkylating ‘agent compeses butylene or butanol. 7. The process of claim 1, wherein said water content of said reaction zone is selected from the group consisting of Tess than about $00 wpm, Jess than about 200 wppm, less than About 100 wppm and fess than about $0 wpm. '8. The process of claim 1, further comprising a finishing reactor downstream of said reaction zane 9. The process of claim 1, wherei said suitable alkylation conditions include a temperature from about 100°C. to about 400°C, pressure from about 203 to 4500 kPa-a, a WHSV from about 0.1 to about 10h, and a molar ratio of said over sid alkylating agent from about 0.11 10, The processor claim 6, wherein aid suitable ally concltons maintain said reaction zonein atleast prt phase conditions