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United States Patent
Abichandani et al.
Patent Number: Date of Patent:
1211992 611994 9/1994 9/1994 1111994 1111994 111995 411995 411995 1011995 1211995 1211995 111996 211996 3/1996 5/1996 5/1996 1011996
*Nov. 18, 1997
 ETHYLBENZENE PRODUCTION PROCESS WITH EX SITU SELECTIVATED ZEOLITE CATALYST
Jeevan S. Abichandani, Voorhees; Jeffrey S. Beck, Princeton, both of N.J.; Sharon B. McCullen, Newtown, Pa.; David H. Olson, Pennington, N.J. Mobil Oil Corporation, Fairfax, Va.
The term of this patent shall not extend beyond the expiration date of Pat. No.
  Appl. No.: 382,103 Filed:
5,173,461 5,321,183 5,349,113 5,349,114 5,365,003 5,367,099 5,382,737 5,403,800 5,406,015 5,455,213 5,475,179 5,476,823 5,488,194 5,495,059 5,498,814 5,516,736 5,516,956 5,565,004
Absil et aI .. Chang et al Chang et al Lago et aI Chang et al Beck et al Beck et aI Beck et aI Beck et aI Chang et al Chang et aI Beck et aI Beck et aI Beck et aI Chang et al Chang et al. .. Abicbandani et al Beck et aI
5851475 5851475 5851475 585/470 585/475 585/475
585/475 502160 585/475 585/470 585/475 585/475 585/481 585/475
Feb. 1, 1995 Related U.S. Application Data
FOREIGN PATENT DOCUMENTS
European Pat. Off ..
    
Continuation-in-part No. 5,476,823.
of Ser. No. 69,251, May 28, 1993, Pat.
OTHER PUBliCATIONS Nakajima et al., "p-Xylene-Selective Disproportionation of Toluene over a Modified Pentasil Type Zeolite", Sekiyu Gakkaishi; 35(2), 185-189 (1992). (no month). Hibino et al., "Shape-Selectivity over HZSM-5 Modified by Chemical Vapor Deposition of Silicon Alkoxide" , J ournal of Catalysis, 128, 551-558 (1991). Chen et al., Shape Selective Catalysis in Industrial Applications, Marcel Dekker, Inc., New York, pp. 214-217 (1989). (no month). Lewis et al., "Ethylbenzene Unit Operates Well on Dilute Ethylene," Oil Gas J., 75, 55-58 (1977). Dwyer et al., "Efficient, Nonpolluting Ethylbenzene Pr0cess," Chern. Eng., 83, W-91 (1976). (no month). Dwyer, "Mobi1/Badger Ethylbenzene Process-Chemistry and Catalytic Implications," in Moser, W.R., ed., Catalysis of Organic Reactions, Marcel Dekker, Inc., New York, pp. 39-50 (1981). (no month). Primary Examiner-Steven Bos Assistant Examiner-Thomas G. Dunn, Jr. Attome» Agent, or Finn-PeterW. Roberts; Santini 
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3,257,310 3,437,587 3,682,996 3,698,157 4,016,218 4,060,568 4,086,287 4,090,981 4,100,215 4,107,224 4,117,024 4,127,616 4,145,315 4,169,111 4,224,141 4,283,306 4,326,994 4,402,867 4,443,554 4,465,886 4,477,583 4,487,843 4,522,929 4,548,914 4,559,314 4,843,057 4,851,604 4,927,979 4,950,835 5,157,185 611966 4/1969 8/1972 10/1972 4/1977 11/1977 411978 5/1978 7/1978 8/1978 9/1978 1111978 3/1979 9/1979 9/1980 8/1981 4/1982 9/1983 4/1984 8/1984 10/1984 1211984 6/1985 10/1985 1211985 6/1989 7/1989 5/1990 8/1990 10/1992
Plank et aI.. Elbert et aI.. Kerr . Allen et al .. Haag et al .. RodewaId. Kaeding et al.. RodewaId. Chen . Dwyer. Kaeding . RodewaId. RodewaId. Wight. Morrison et al.. Herkes .................................... Haag et aI.. RodewaId. Dessau. RodewaId. RodewaId. Telford et aI. . Chester et aI.. Chu. Shihabi. D' Amore et aI.. Absil et al .. Yamagishi et al .. Wang et al .. Chu et aI..
A process for ethylbenzene production that involves contacting a hydrocarbon feedstream including benzene and ethylene, under alkylation conditions, with a catalytic molecular sieve which has been modified by being ex situ selectivated with a silicon compound. The ex situ selectivation involves exposing the molecular sieve to at least two selectivation sequences, each selectivation sequence comprising contacting the catalyst with a silicon compound followed by calcination. The modified catalyst used in the process may also be steamed. Optionally, the modified catalyst may be trim-selectivated. 21 Claims, No Drawings
Pat.090.S. large to form within the zeolite pores or cages. The Herkes sition and under specific operating conditions. Pat.605 (Kresge).5.50 4. typically 2 to 5. for example.. to 900° 30 zeolite-catalyzed when a fraction of the feedstock is too large to enter the F. principally diethylbenzene (DIEB). 4. however. Pat No.689.283. By recycling the by-products to the alkylation reaction. No. olefin skeletal or double bond isomerization. (1981). Nos.755. which also are produced in increasing amounts as reaction 45 benzene. No. 4.145. edited by treatment.215.761. (1989). in distinction to the The present invention is directed to an improved process intermediate pore size zeolites used in the processes of alkylation of benzene with ethylene over a modified 15 described in the Keown.S. It may be reaction reduces formation of these species through equilinoted. New York catalyst. ex situ selectivation of zeolites has involved addition. but are usually maintained above zeolite pores to react. e. Marcel Dekker. Reactant selectivity occurs for the benzene/ethylene reaction vary from 600° F.823.169.g.477.4. Pat.379. 4. that a suggestion of multiple treatments was bration of the components because. No.476. U. Inc.173. treated catalyst is less active and less selective than the .426 BACKGROUND OF THE INVENTION (Inwood). increased conversion is obtained as the polyethy. U. Other types of selectivating agents are takes place.306 to Herkes. including both polymethylated and polydisclose specific methods for contacting a catalyst with a ethylated benzenes are recycled to the alkylation reactor in selectivating agent containing silicon ("silicon-containing which the reaction between the benzene and the ethylene selectivating agent"). agent". oligomerization and aromatic which vary between the critical temperature of benzene up disproportionation. Pat. %) may be obtained at the start of the the catalyst by treatment with a chemical "selectivating cycle.).616. 4. In the production of ethylbenzene by this process.547. A small change in the dimensions of the molecule or the zeolite pore can result in tion to the ratio of the reactants.) Several principal shape selectivity constraints operate in above the reactor inlet temperature and typical temperatures reactions. Shape Selective Catalysis in ethylene in the presence of a solid.504 (Keown).461. The process described in U. 36. 3. the principles behind shape selective catalysis have been reviewed success is the vapor phase alkylation of benzene with extensively.) at the reactor inlet The reactor are governed by constraints imposed by the channel size. in both of which a preference for large pore size zeolites such as zeolite Y is expressed. with the benzene space velocity varying accordingly. Under favorable operating conditions Various methods are known in the art for increasing the on the industrial scale.504 APPUCATIONS is of particular note since it includes a separate transalkylation step in the recycle loop which is effective for conThis is continuation-in-part of application Ser. 5. 4. Pat. catalyst treated once with an ethylorthosilicate solution entitled "Mobil/Badger Ethylbenzene Process-Chemistry followed by calcination against the performance of catalyst and Catalytic Implications". U. (315° C.060. The products of the reaction large diffusion changes leading to different product distriinclude ethylbenzene. The Herkes patent contrasts the performance of is described in more detail in an article by Francis G. Pat. Product selectivity. The entire disclosure of the above-cited applicaW cesses for the production of ethylbenzene are disclosed in tion is expressly incorporated herein by reference. In the commercial operation of this process. products to the desired ethylbenzene product Other pro5. 4.751. For example. 4.886. Inc.4.568 and 3.S.S.127. U. bed temperature may be as much as 150° F.) in order to keep the content of occurs when some of the products of the reaction cannot the more highly alkylated benzenes such as diethylbenzene leave the zeolite channels. No.981. in propor. No. In Traditionally.698. which is obtained in increasing probutions. Pat. No. the presence of the PEB during the alkylation single applications of the selectivating agent.S. Product distributions can also be at an acceptably low level. usually in the range di1fusion where the dimensions of the molecule approach of 1 to 6. reference is made to these patents for a detailed description of such CROSS-REFERENCE TO RELATED 5 processes.S. and U. Pressures typically vary from atmospheric to 3000 psig (about 20785 kPa abs) with a 35 altered by transition state selectivity in which certain reactions cannot occur because the reaction transition state is too molar ratio of benzene to ethylene of from about 1:1 to 25:1. 1993 now U. acidic ZSM-5 zeolite Industrial Applications. hydrocarbon conversion reacethylene is used as the alkylating agent and is reacted with benzene in the presence of the catalyst at temperatures 25 tions such as paraffin isomerization. Marcel Dekker.483 (Burress) describes a process for the producEthylbenzene is a valuable commodity chemical which is tion of ethylbenzene using zeolite ZSM-12 as the alkylation currently used industrially for the large scale production of catalyst.218 (Haag). No. the polyalky.465. 4. based on the ethylene flow. temperature increases.111 (Wight) and U. Dwyer. the PEB 60 patent discloses the promotion of crystalline silica catalyst recycle will reach equilibrium at a certain level. No. Ethylbenzene may be produced by a The term "shape-selective catalysis" describes unexnumber of different chemical processes.835. appearing on pages 39-50 of a 65 treated twice with ethylorthosilicate and calcined after each book entitled Catalysis of Organic Reactions. verting a significant proportion of the more highly alkylated 08/069. Another type usually about 5: 1 (benzene:ethylene).751. 3.157 lated benzenes.100.S. 3. catalytic molecular sieve. styrene monomer.016. in shape selective alkylations of polyethylbenzenes. but one process which has achieved a significant degree of commercial 20 pected catalytic selectivities in zeolites.S.55 known. 4. One such method is to modify 90 weight percent (wt. at a given feed compomade in U.950. (about 85° C.979.251 filed on May 28. No. Kresge and Haag patents.S. about 700° F.4. Pat. 4. (about 371 ° C.927. alkylation or transalkylation reactions to 900° F.S. lated benzenes (PEB) are converted to ethylbenzene (EB).583. This type of shape selective catalysis is portions as temperature increases. by Chen et al. Moser.315. This comby application of an amorphous silica such as ethylorthomercial process is known as the Mobil/Badger process and silicate... Weight hourly space of selectivity results from configurational constraints on velocity (WHSV) in the reaction is high. The Herkes disclosure shows that the twiceWilliam R.40 that of the zeolite pore system. Within a zeolite pore. on the other hand. together with various demonstrated. Pat. an ethylene conversion in excess of selectivity of zeolite catalysts. to 480° C.459.025 1 ETHYLBENZENE PRODUCTION PROCESS WITH EX SITU SELECTIVATED ZEOLITE CATALYST 2 Ethylbenzene production processes are described in U. (about 480° C. 4.
benzene and ethylene. form prior to SUMMARY OF THE INVENTION 65 modification.5. preferably paraffins having 3 or more carbons.. to which reference is will be more fully apparent from the following detailed made for the details of these zeolites.827.069 and Re.308. plmlo:112l1). i. ZSM-12.. ZSM-48. Oil Gas J. Lewis. disadvantages and deficiencies associated with conventional benzene alkylation processes in a manner that would enable use of modified catalytic sieves produced by methods which are both more efficient and safer and that would also increase product yields and reduce the proportion of undesirable impurities in the product of such alkylation processes. 29.832. reference is made to the following detailed description. the benzene alkylation process of the invention exhibits increased selectivity for ethylbenzene as well as 35 against certain of the by-products of the alkylation process. The catalytic molecular sieves useful for the invention are preferably in the hydrogen. The catalytic molecular sieve found to be useful for the process 5 of the invention has been modified by exposing the catalytic molecular sieve to at least two ex situ selectivation sequences. 3. The xylenes are undesirable because they cannot be easily separated from the product EB. F. 4.447.979. e. it would be a significant advance in the art to overcome the above-described difficulties.046.849. Zeolites which conform to the specified values of Constraint Index for intermediate pore zeolites include 55 ZSM-5. Accordingly. for example. ZSM-ll. Inc.. Advantageously.S. Y. followed by calcination of 10 the contacted catalytic molecular sieve.076. Marcel Dekker.107.025 3 once-treated catalyst as measured by methylation of toluene by methanol. with a modified catalytic molecular sieve. the process of the invention results in substantially lower production of residue. G. the trim25 posing the organic compound. 4.859. An especially preferred zeolite is ZSM-5. vided a process of vapor phase alkylation of benzene over a 45 processes . under alkylation conditions. in U. and greater product purity than do conventional processes.702. which. Shape Selective Catalysis in Industrial Applications. page 214. The in situ trim-selectivating may be performed by coke trim-selectivating wherein an organic compound is decomposed in the presence of the modified catalytic molecular sieve. The present invention solves the difficulties.. disadvantages. Nos. G. indicating that multiple ex situ selectivation confers no benefit and in fact reduces a catalyst's efficacy in shape-selective reactions. In another embodiment. The method for determining Constraint Index is described fully in U. In addition. disadvantages. Selectivating agents useful in the present invention include a large variety of silicon-containing compounds. No. Pat. Pat.689.e.245.. a substantial portion of the ethylene is consumed in the formation of polyalkylated compounds some of which result in the formation of heavy components (residue) which are rejected. 60 4. G.709. Other descriptions of benzene alkylation reactions are given in Dwyer. and Dwyer.218. results in substantially greater economy and efficiency of the benzene alkylation process. preferably silicon compounds which are substantially soluble in organic media. and Dwyer.. and combinations thereof. which is the feed to a styrene unit. For a better understanding of the present invention. 3.e. The catalytic molecular sieves useful according to the invention preferably include intermediate pore zeolites.949. 4. 3. and deficiencies of the prior art practice of these processes.046. in turn.224. 4. disclosure and appended claims. Oth er purposes and advantages of the present invention 4. F. Eng. because it is almost impossible to separate it from the styrene.341. at conditions suitable for decomAlternatively.556.397. 30 at reaction conditions. This residue formation is associated with loss of valuable feedstocks. 4.016. Such zeolites are described. 28. ZSM-22. E. but may be used in the ammonium or sodium form.S.g. J. "as-synthesized". ZSM-50. and its scope will be 40 pointed out in the appended claims. P. Garwood. It is well known to alkylate benzene with ethylene by means of zeolite catalysts.449. New York (1989). In addition. 75:55 (1977). the invention also includes a process of shape selective alkylation of benzene over a modified catalytic molecular sieve that has been further the modified catalytic 20 modified by in situ trim-selectivating molecular sieve. and Chen N. it is a purpose of the invention to provide an improved process for the vapor phase alkylation of benzene over a catalytic molecular sieve.e..016. P. In the vapor phase ethylbenzene (EB) process. selectivating may be performed by exposing the modified catalytic molecular sieve to a reaction stream that includes an organic compound and a trim-selectivating agent. the alkylation of benzene with ethylene invariably leads to the formation of a small amount of xylenes (ca. and Lewis. Each ex situ selectivation sequence includes contacting the catalytic molecular sieve with a siliconcontaining selectivating agent. including hydroIn accordance with the present invention. incorporated by reference herein. It is a further purpose of the invention to provide an improved process for alkylating benzene which overcomes the above-described difficulties.. The process of the invention also provides substantially reduced levels of undesired by-products.424. 4.S. It is preferred that the catalytic molecular sieves of the invention 50 exhibit a Constraint Index of between about 1 and about 12.842. "carriers" for the selectivating 15 agent) include alkanes. ZSM-5/zsM-ll intermediate.. Other materials may also be present. 1000 ppm in the EB product). Such a process is described in U. J. Pat No. there is progen precursor. the described modified catalysts have enhanced shape selectivity for the alkylation of benzene.. 4 modified catalytic molecular sieve by contacting a reaction stream comprising ethylene and benzene. 83:90 (1976). ortho-xylene and diethylbenzene. and ZSM57. DErAILED DESCRIPTION INVENTION OF THE The present invention relates to enhanced shape selective for the vapor phase alkylation of benzene with ethylene over modified catalytic molecular sieves. Accordingly.. The catalyst disclosed in this patent for producing aromatic compounds in high yield is a ZSM-5 type zeolite having 50-75% of the cationic sites occupied by hydrogen ions. and ends up as an impurity in the finished product Therefore. from amongst the xylene isomers the ortho-xylene is the most undesirable component..229. organic cations. together with other and further objects. including any of a large variety of silicon-containing compounds.640. 4. The process of the invention produces greater product selectivity.. W. ZSM-35.685. ZSM-23.886 and Re. F. 4. Furthermore.3. and deficiencies inherent in the prior art by providing an improved process for vapor phase alkylation of benzene. Such organic media (i. The xylene isomers exist in thermodynamic equilibrium quantities (i. Chern.
. such as SEM and TEM.16 sec "). 60 silicone. 185-189 (1992). preferably between about cation of the catalytic cracking activity of the catalyst two and about six times. The alpha test is organic solvent at a catalyst/selectivating agent weight ratio of from about 100/1 to about 1110.835.3' of 7.5.616.S. or Mathematics of Diffusion. these measurements have been made on 30 583. the disclosure of which is incorporated by reference 5 combination with a support or binder material such as. Such catalysts generally have an alpha value greater 55 indicate substances which will increase the shape-selectivity than 1. most preferably a solution including a silicondimethylbutane under these conditions is taken to be 1. 278 (1966).0704>% . 0 o . The relation between crystal size measured in microns. upon heating. The selectivating agent comprises a compared to a standard catalyst. and it gives the relative rate constant (rate of normal hexane conversion per volume of compound or polymer containing a main group or transition catalyst per unit time). The catalyst the rate of sorption of 2. herein. a "solution" is intended to mean sis. Pat. and for each crystal measured. In general. The crystal size is computed by In conventional applications.S.S. is: depositing silicon on the surface of the zeolite are found in d=D. 4. are exposed to at least two Catalysis. 61. present invention generally requires a catalyst having acidic As used herein. Pat. both ideal and colloidal. as closely as possible. 4. a porous inorganic oxide support or a clay binder. The organic carrier is preferably removed. Examples of methods of hydrocarbon. thermogravimetric electrobalance. 6. which are incorporated by reference herein. Microscopy methods. Sekiyu Gakkaishi. No. for the rate of sorbate uptake by a solid whose 20 a gas under the conditions of contact with a zeolite. about 100 C. Other examples of the deposition of a silicon compound on zeolite a computer controlled. 395 (1980). U.090. 395 (1980). The skilled artisan will appreciate and to exclude aluminum in the binder or in cationic or other that solutions.S. support may be from about 5% to about 98% by weight and values may be required in up to three dimensions. 61. the suitable molecular sieve may be employed in yield protons. the external the time required for the uptake of 30% of capacity of surface of the molecular sieve. Crank.1 hr to about 24 hours.886 and 4. such as quaternary nitrogen ions. U. 522-529 (1965). differ from emulform within the channels. The crystal material preferred for the For the modification method of the present invention. to about 1500 C.. No.20 micron. but these methods require measurements on lar sieve to the total composition of catalyst and binder or a large number of crystals. preferably of a catalytic molecular sieve to the-desired levels while maintaining commercially acceptable levels of hydrocarbon from about 10 to about 500. No. other non-acidic binder The crystal size of zeolites used for the invention is materials may be employed. and in U. 3. 3. such organosilicon compounds must be 994. Although zeolites with a silica to sions. Pat. a invention has a sorption time. The relative proportion of suitable crystalline molecuare often used. The composition may be in the form of an extrudate. 4. and 10.8 minutes. The catalyst is contacted with a amorphous silica-alumina cracking catalyst taken as an solution of the silicon-containing selectivating agent in an alpha of 1 (Rate Constant=O. at a temperature of from described in U. for example. The alkylation process of the of these selectivation sequences. with a selectivating agent dissolved in an organic solvent. the silicon compound applying the diffusion equation given by J.S.465. by distillation or evaporation. which For the improved benzene alkylation processes of this contain hydrogen substituents and which. it is preferred to "Hydrogen precursor" compounds include compounds well use zeolites having ratios of at least about 20 to about 1000. The deposited silicon compound preferably extensively covers. d. at a pressure of from about each incorporated herein by reference as to that description. for example. either incorporated with a binder or in unbound The "alpha value" of a catalyst is an approximate indiform. In addition. For the modification of catalysts according to the invention. 309. a uniformly dispersed mixture of one or mores substances at the ratio in the rigid atomic framework of the zeolite crystal 65 a molecular or ionic level. It is noted that intrinsic rate constants for many acide.. The silica to alumina ratio (SiOiAl203) of the catalysts soluble in organic solvents such as those described elseof the invention may be determined by conventional analywhere herein. In addition. 589-591 (14 Jun. Oxford at the Clarendon Press. with or without vacuum. and resides substantially exclusively on. For is preferably from about 25 % to about 80% by weight of the ZSM -5 materials described in the examples below. 4. bentonite and kieselguhr. an emulsion. preferably silicon. for example. for example. known in the art. by way of example. 35 zeolite. See.078 and in Journal of Catalysis. It is based on the activity of the 40 metal. silicon compounds such as phenylmethyl silicone. generally in the form of dried preferably greater than about 0. estimates were made of the effective average crystal size by measuring 15 composition. This methodological sequence comprising the step of contacting of the catalyst with the of Acidic Aluminosilicate Catalysts". Nos. dimethyl This type of steaming is discussed in U. then. The employed may be in the form of a solution. 10 materials include. 35. Such substances include. and a calculated crystal size of 0.127. the diffusion time measured in minutes. 45 psig to about 200 psig. and 60 may also be used in self-bound form. and a contacted catalyst is termed a "selectivation sequence. is contacted at least twice.755. organic increased by initially treating the catalyst by mild steaming. 4.2a liquid.950. beads or fluidizable rnicrospheres. torr hydrocarbon pressure. Pat.5x containing selectivating agent dissolved in an organic car10-14 cm2/sec. 4. In the present case.'12. the diffusion properties can be approximated by a plane sheet silicon compound is preferably contacted with the catalyst as model.g." The variable flow rate as described in detail in the Journal of catalysts of the invention. the term "selectivating agent" is used to activity. for a time of from about 0. catalyzed reactions are proportional to the alpha value for a particular crystalline silicate catalyst (see 'The Active Site The catalyst is then calcined. The accurate inorganic oxide gels or gelatinous precipitates. The alpha value of the catalyst may be conversion. 52-56 (1957). The experimental conditions of the test used 50 selectivating agent solution and the step of calcining the herein include a constant temperature of 5380 C. from about 1 to about 2000. 10.981.326. could obtain such data.483 to Burress.3' 25 rier. While the preferred binder is silica. 1984). invention. and blends thereof which have been found to be suitable.354. more preferably from about 10 to about 100.025 5 6 alumina ratio of up to about 200 are useful.2-dimethylbutane at 90 C.477.. Pat. but there are numerous ways by which one skilled in the art surfaces are described in Nakajima et al. Suitable clay measurement of crystal size of zeolite materials is frequently very difficult. Nature. No. the diffusion constant (D) of 2.1 micron.689. This ratio is meant to represent.
halogenated aryl. range of 150 to 10. may also be utilized.!minute to about 5° C. preferably single contacting of the catalyst with the selectivating agent methyl or ethyl groups. until reaching a silicone. polydimethyl silicone. including silanes and alkoxy sphere of N2. the zeolite is dependent include temperature of contact with halogenated alkyl. such as hydrocracker recycle oil. This co-feeding of selecorganosilicon selectivating agent include linear. Calcination should be performed in an atmosphere formula: substantially free of water vapor. tends to be greater when the deposition is alkyl. Preferably. Reaction conditions point greater than about 70° C. an atmosphere of N2 followed by an oxygen-containing These useful silicon-containing selectivating agents include atmosphere. This increased efficiency allows for the use of relatively small quantities of the silicon compound as well as relatively small quantities of the solvent carrier.689. methylhydrogen silicone. mixtures of low volatility perature of from about 3500 C. halogenated agent solution. phenylmethyl 20 compound. hexamethyl cyclotrisiloxane. to avoid undesirable uncontrolled steaming of the catalyst. R2. phenylhydrogen silicone. Optionally. Dow-550 and performed. or cyclic alkane having a boiling selectivation" or "in situ selectivation".e. and n is an integer of at least 2 and 15 In addition. as may silicones with other for between 2 and 6 hours. branched. It has been found that a scheme comprising at least two 5 selectivation sequences provides increased efficiency of deposition of the silicon compound on the surface of the catalyst. The calcination process may be performed in an atmoOther silicon compounds. Prefermay be cyclic. in the reactor Mich. and preferably containing 7 65 for this in situ selectivation step generally include a temor more carbons. alkoxy. and a organic compounds. where R1. order to avoid entry of the selectivating agent into the pore The feed of benzene and ethylene may be co-fed simuland any concomitant reduction in the internal activity of the taneously with a second selectivating agent and hydrogen at reaction conditions until the desired ethylbenzene catalyst. the selectivating agent. functional groups. for example.. methyltrifiuoropropyl silicone. may pressure of from about atmospheric to about 5000 psig.g. polymeric species to a solid state species. phenylethyl contacted catalyst is calcined to decompose the molecular or silicone.. ethylhydrogen silicone. is hydrogen.. hexaphenyl cyclotrisiloxane 30 range of 3500 C. the catalyst may be further modified in situ. than when the deposition is made entirely by a generally contain from 1 to 10 carbon atoms. Representative silicone compounds Following each contacting of the catalyst with a silicon include dimethyl silicone. In the tivating agent is discontinued. Subsequent to the ex situ selectivation of the catalyst. but Generally. 10 Accordingly.. the amount of silica deposited on the catalyst. The silicone compound need not be linear. the kinetic diameter of the high efficiency. alkyl. such temperature will be below 6000 C. hydroxyl. performed stepwise in a sequential fashion according to the alkaryl or halogenated alkaryl.. 35 air. 90%. aralkyl. diethyl silicone. alkyl. The various calcinations in any selectivation sequence need not be identical. m.. in formed. halogen. but may vary with respect to the temperature. alkaryl. The catalyst may be 40 calcined once or more than once after each contacting with a selectivating agent. Dow-550) and tacted zeolite. The product is maintained at the and octaphenyl cyclotetrasiloxane. aryl. and the number of selectivation sequences phenylmethyl polysilocane (e. the conditions of calcination of the condimethylphenylmethyl polysiloxane (e. wherein the silicon compound is deposited. the degree to groups. to 5500 C. as a fraction of the silicon compound in the selectivating where R. ably the temperature of calcination is within the approximate octamethyl cyclotetrasiloxane. branched. Especially preferred low volatility hydrocarbon carriers of selectivating agents include decane and dodecane. halogen. tetrachlorophenylethyl 25 about 0. hydroxyl. or an atmosphere containing a mixture of N2 silanes and alkoxysilanes characterizable by the general and air.!minute. whereupon the co-feed of selectivating agent is discontinued.. The -H~-+ c. R3 and R4 are independently selected from the 45 Factors upon which the amount of silica incorporated with group consisting of hydrogen. aralkyl. Midland. The molecular weight of sequences tend to be substantially higher than the activity the silicone compound employed is generally between about and selectivity of a catalyst modified by the deposition of a 80 and about 20. ~ is independently selected from the same group as R1.g. methylvinyl silicone and ethylviwhich the crystallinity of the zeolite is adversely affected. which the zeolite has been dried prior to contact with the Preferred silicon-containing selectivating agents include 50 silicon compound. i. nyl silicone.5. the silicone. and cyclic alkanes having three or more carbons.g. halogenated aralkyl. to about 5400 C. Mixtures of these comcalcination temperature usually for 1 to 24 hours. diphenyl silicone. the atmosphere and the duration of calcination.000 and preferably within the approximate comparable amount of silica in a single step.025 7 Useful selectivating agents include silicones and silicone polymers which can be characterized by the general formula: 8 be employed as carriers. tetrabe calcined by increasing the temperature at a rate of from chlorophenylmethyl silicone.. is attained. preferably silanes. it has been observed that the activity and selectivity of the catalysts modified by multiple selectivation generally in the range of 3 to 1000. aryl. This co-feeding of selectivatmethods of the present invention it is preferred that the ing agent with the hydrocarbon feed is a type of "trimcarrier is a linear. 55 in which the process of hydrocarbon conversion is perselectivating agent is larger than the zeolite pore diameter. The hydrocarbon substituents invention. halogenated aryl. Examples of suitable organic media (carriers) for the 60 selectivity.ethylethyl silicone.20 C. tetrachlotemperature greater than 2000 but below a temperature at rophenylphenyl silicone. e. Mixtures of these compounds may also be used. an oxygen-containing atmosphere. . the rate of temperature rise. such as tetramethoxy silane. Dow-710 are available from Dow Chemical Co.000. The catalyst may ethyltrifiuoropropyl silicone. and halogenated alkaryl silicon compound in the contacting medium. the type and concentration of the halogenated aralkyl. tetrachlorophenylhydrogen silicone. Dow-710). preferably pounds may also be used..
(about 4800 C. a temperature of at least 5000 F. various undesirable reactions occur. will normally be satisfactory. (about 4800 C. while the other components.g. pyrroles and pyridines. with the pressure from about 50 psig to about 500 psig. (about 850 C. This process involves exposing the modified catalyst to a thermally decomposable organic compound at an elevated temperature in excess of the decomposition temperature of said compound but below the temperature at which crystallinity of the zeolite is adversely affected. with a reactor inlet temperature which is above the temperature required to maintain the benzene in the vapor phase at the selected pressure. 65 The alkylation reaction is carried out at elevated temperatures in the vapor phase. In a typical low pressure vapor phase operation. this temperature will be less than about 6500 C. especially at high pressures or with other reactants. No. The weight ratio of ethylbenzene to diethylbenzene produced in the vapor phase alkylation step may be from about 2 to about 30. e. thiophenes. for example. based on the ethylene feed. The selectivating agent is co-fed in an amount of from about 0. The use of temperatures significantly above about 950 F. for the gas phase reaction. higher temperatures toward 9000 F. such as paraffinic. cycloparaffinic. These resinous compounds together with the degradation products may lead to the formation of coke-like deposits on the active surfaces of the catalyst which will rapidly inhibit the high activity necessary in the catalyst for acceptable conversion rates. more preferably less than 24 hours. will be the source of coke. are fed in the amounts set forth above. Alkylation of Benzene The modified zeolite catalysts useful in the present inven. to 427 C. oxygen-containing organic compounds such as alcohols. is undesirable because. typically between about 1 and about 6 WHSV. 4. During the in situ selectivation procedure the selectivity of the catalyst will be observed to increase further. the prevailing pressures are usually those of the reactant species.60 tion are advantageously used in the alkylation of benzene with ethylene to provide ethylbenzene (EB). Alternatively. for example. with a greatly reduced coking rate. In most cases. although a disadvantage of these higher temperatures is that the yield of xylenes would be increased.). e. The space velocity may be from about 0. fluidized or moving bed catalyst system. The alkylation process can be carried out as a batch-type.689. with a preferred maximum of about 9000 F. dimethyl silicone. encompass a wide variety of compounds including by way of example. The use of temperatures below about 9000 F. Pressures during the vapor phase alkylation step typically are between atmospheric and about 3000 psig (about 20785 kPa abs) and generally will not exceed 1000 psig (about 7000 kPa abs). Organic materials.) will normally enable these problems to be maintained within acceptable bounds. thermally decomposable under the above temperature conditions to provide coke trimming. Typically. for example. (about 4800 C. most preferably the ethylene itself being subjected to benzene alkylation. based on the ethylene.) to about 8500 F. According to one embodiment of the present invention. The ethylene which functions as the alkylating agent will tend to polymerize with itself.224. in U.).) would be preferred. but generally it is preferred to control the exotherm to a maximum of about 1000 F.1 to about 10 WHSV. forming resinous compounds within the reaction zone.1 WHSV to about 20 WHSV. (about 2600 C. The process is. typically about 5: 1 to about 30: 1. coke trimming is conducted at conditions outside the operating parameters used during the main time span of the catalytic cycle. the conditions are selected to maintain the benzene in the vapor phase. a silicone containing phenylmethylsilicone and dimethylsilicone groups in a ratio of about 1:1 is co-fed to the system. it is contemplated that a thermally decomposable hydrocarbon. the reactor bed temperature will be higher than the reactor inlet temperatures.). In the latter case. from about 1 to about 10 WHSV. but is usually maintained at a relatively high value. Depending upon the percentage of selectivating agent used. prior to contacting with hydrocarbon under alkylation conditions. cycloolefinic and aromatic.. the trimselectivation will last for at least one hour. 0 0 0 0 0 0 5 10 15 20 25 30 35 40 45 50 55 . about 50 or 100 psig (about 445 or 790 kPa abs). such as an olefin or paraffin. with ratios above 20: 1 being possible. to about 800 F. olefinic. accordingly. organic silicon compounds such as phenylmethyl silicone. The selectivating agent for trim-selectivation may be selected from among the exemplary silicon compounds discussed in greater detail above with respect to ex situ selectivation.). the hydrocarbon feed is continued in contact with the coke-containing catalyst under conditions of temperature and hydrogen concentration conducive to benzene alkylation. Because the yield of PEB and certain other by-products usually decreases with increasing temperature. Pat. % of the hydrocarbon according to this preferred embodiment. The reaction is preferably carried out in the absence of hydrogen and.. the temperature will be from about 600 F. sufficient to maintain the desired flow rates through the reaction bed. Suitable conditions can be selected 10 by reference to the phase diagram for benzene.g. (315 C. (about 550 C.107..001 wt % to about 10 wt. Normally. Usually.5.S. When the desired coke deposition has been effected. may be subjected to a trim-selectivation process known as "coke trimming". the disclosure of which is incorporated herein by reference. The ratio of the benzene to the ethylene in the alkylation reactor is typically about 1: 1 on a molar basis (benzene:ethylene. The reactants and the alkylated products undergo degradation resulting in the loss of the desired products as well as the reactants. the reaction temperature will be from about 3000 F.1 to about 20. and mixtures thereof are suitable. Alkylations of benzene in which the catalysts of the invention can be used are described. hydrocarbon and hydrogen.) will be used. undesirable residues may be formed from other side reactions. Relatively low temperature atmospheric pressures. hydrocarbons. the catalyst. In the vapor phase reaction. (about 1500 C. at these high temperatures. (about 4550 C. The silicon-containing polymer or molecular species may be dissolved in toluene or other appropriate aromatic or hydrocarbon carrier. the hydrocarbon is initially brought into contact with the catalyst under conditions of temperature and hydrogen concentration amenable to rapid coke formation.) with a yield of ethylbenzene increasing with increasing temperatures. usually from about 200 psig to about 500 psig. heterocyclics such as furans. In this scheme the silicon compound will decompose to deposit additional silica to on the catalyst. ethers. Because the reaction is exothermic.025 9 reaction stream is fed to the system at a rate of from about 0. preferably about 1 to about 48 hours. Hydrogen may be fed at a hydrogen to hydrocarbon molar ratio of from about 0. For example. semi-continuous or continuous operation utilizing a fixed. In addition. aldehydes. typically by as much as about 150 F. Generally. fresh feed). ketones and phenols. The ratio in the reactors may be higher as a result of the benzene recycle.
5. The feed stream may also include various impurities such toluene.025 11 12 The properties of the catalyst of the invention also greatly however. Diluents The present invention is described in detail below in relation to the alkylation of benzene over a multiply. which may be present in the feed in aggregate selectivated catalyst. . of polyalkylated compounds some of which result in the formation of heavy components (residue) which are Operating conditions employed in the process of the rejected. indicated as a percentage. with an ethylbenzene selectivity of greater than about the proportion of ethylbenzene. in turn.S. Furthermore. provided that the purity of the product is not product stream produced by conventional benzene alkylagreatly compromised. in a manner which will minimize moisture entering the In the vapor phase ethylbenzene (EB) process. almost pure para-DEB when diethylbenzenes are removed from the ethylbenzene may be taken as a by-product. This characteristic of the modified catalyst allows for substantially up as an impurity in the finished product. the term "ethylbenzene selectivity" means 98%. results in a product stream which includes ethylbenzene along with various C6-CS aromatics such as benzene. are conditions. it does not require any compromise in catalyst selection on operating that other polyethylbenzenes. mixed xylenes and other Cs aromatics as well as a as water. These hydrocarbons include byproducts from the vapor phase alkylation 10 the production of diethylbenzene isomers. However. Numerous methods known in the art are lation of benzene with ethylene invariably leads to the suitable for drying the hydrocarbon charge for the process of formation of a small amount of xylenes (ca. In contrast. transalkylation step may comprise other hydrocarbons in the constraints of the catalyst useful for the invention affect addition to benzene and diethylbenzenes. hydrogen sulfide and other organic compounds in variety of 4. In addition. Therefore. thereby lator. Pat. such as triethylbenzenes. in reality the transalkylator is also a dealkylator. Therefore. preferably operated in the general manner reduce ortho-xylene make. leaving all other polyalkylated product from the vapor phase alkylation step. preferably at least about As used herein. a sub.. The use of a separate vapor phase equilibrium.S. benzene and ethylene. it has been observed that an increase in temperasalkylator is to transalkylate DEB with benzene to produce ture can increase the activity of the modified catalyst more EB. it has been observed that the alkylaeither recycled back to the reactor or to a separate transalkytion process may be performed using 112 as a diluent. comprising benzene and ethylene.504 (Keown).55 dramatically increasing the cycle length of the catalyst For example. carbon dioxide and mixtures thereof. This reduces the residue make. or stantial portion of the ethylene is consumed in the formation the use of liquid charge dryers.504 for a description of the tions of the xylenes substantially away from thermodynamic process configuration. 100 grams of dry further with polyalkylated compounds to form more residue. The following Examples further illustrate the various such as n-propyl benzene and n-butyl benzene can only be features of the invention. pressure. The primary function of the tran. which. a catalyst treated in the manner described herein 65 silica-bound HZSM-5 having a crystal size of 0. molecular sieves or other suitable substances. improved throughput when compared to current commercial Typically. These methods include percolation through EB product). The major component in the polyalkylated benzenes is diethylbenzene (DEB). polyalkylbenzenes can contribute to the yield of ethylbenAs explained in greater detail elsewhere herein. 3. This residue formation is associated with loss of present invention will affect the ethylbenzene selectivity and valuable feedstocks. Since this hydrocarbons may include cumene.40 any suitable desiccant. space velocity. alkylated molecules. Pat No. the alkyreaction zone. and the hydrogen to hydrocarbon mole ratio separated from the product EB. preferably at least about 95%. Reference is made to U. activated alumina.2 micron was contacted with 102 grams of a 7.751. such as triethylbenzenes. enhancing the utility of the process by further included in the feed to the transalkylation step. molar ratio of the The xylenes are undesirable because they cannot be easily reactants. 30 carbon monoxide. Normally a single pass conversion of a amounts greater than the quantity of ethylene of benzene. No. which is the feed to a styrene (H/IIC). 1000 ppm in the the invention. hydrocarbon stream. Due to this EXAMPLE 1 compromise some of the products of dea1kylation react In a first ex situ selectivation sequence. In addition. It has also been observed that an increased space unit. silica gel.aromatics and polyalkylated aromatics.689. tion processes generally carries an unacceptably high 4. To the extent 15 secondary reactor is then a true dealkylation unit. Such conditions include the temperature. among all of the products of the alkylation reaction. which is defined in the appended claims. shifting the isomer concentradescribed in U.3% solution of dimyields a significantly ethylbenzene-enriched product from ethylphenylmethyl polysilicone (Dow-550) in dodecane at benzene alkylation with ethylene. from amongst the xylene isomers the velocity (WIISV) can enhance the selectivity of the modiortho-xylene is the most undesirable component.25 may include other hydrocarbons such as methane and ethane. plmlo: 1/211). for example. generally allowing the escape from the catalyst of only the parastep which are carried over along with diethylbenzenes diethylbenzene isomer. and are not intended in any way to removed by dea1kylation. and hence its catalyst selection 60 limit the scope of the invention. The hydrocarbon feed may also contain diluents. The xylene isomers exist in thermodynamic equilibrium quantities (i. These other materials to be diverted to a dealkylation unit. Additionally. conversions of at least about 95%. butylbenzenes and other polyethylbenzenes. 35 The hydrocarbon feedstock may also be dried. because it is almost impossible to separate from the styrene. The small amounts. 45 hydrocarbon conversion. nitrogen.751. the zene products obtained via transalkylation reactions of the 20 present invention provides a process for obtaining ethylene polyethylbenzenes with benzene.e. if desired. these other limiting residue formation. 3. 90%.polyalkylated aromatics content. and operating conditions are a compromise between the optimum for trans alkylation and dealkylation. the polyalkylated compounds are isolated and practices. The shape selective properties of the catalyst transalkylation reactor in the recycle loop for the higher 5 described herein also inhibit the formation of larger polyalkylated products is described in the Keown patent. the other polyalkylated compounds. increases the utilization of ethylene and benzene It will be understood that the hydrocarbon feed to the towards formation of more desirable products. Other diluents include gases such as hydrogen. and ends 50 fied catalyst in benzene alkylation reactions.
5. halogenated aryl. aralkyl. The sample was filtered and then C. the 45 para-xylene selectivity was at least 92. a pressure of from about 0. 98 grams of the 1. with a catalytic molecular sieve weight uptake was 2. and halogenated alkaryl. Rs and ~ are independently selected from The five-times selectivated catalyst of Example 1 is the group consisting of hydrogen.!min to 540 C. and alternative embodiments are calcined as described above for the first selectivation to be regarded as being within the spirit and scope of the sequence. The 20 duce ethylbenzene.65 % Si02. aryl. A process for improved shape selective alkylation of twice-treated catalyst was contacted with 98 grams of 7. because of the diffi55 is between 2 and 1000.45% Si02• selectivating agent dissolved in an organic carrier and In a fifth ex situ selectivation sequence.1%. The weight uptake a high price. Para-DEB. with mixing for two hours. alkaryl. and a temperature of 750 F.3% benzene comprising: Dow 550/dodecane solution at room temperature with mixcontacting a reaction stream comprising ethylene and ing for two hours. it will be apparent that numerous once-treated catalyst was contacted with 105 grams of a variations. the sample was heated at 20 CJrnin to 5400 C. aralkyl. employed for the alkylation of benzene with ethylene under alkoxy. and alternative embodiments of 7. halogenated alkyl. alkyl. Moreover. the purity of the product of an ethylbenzene production process using this catalyst would be expected to be substantially higher than the product of ethylbenzene production processes using conventional catalysts.4% to 87. The sample was filtered and then wherein each ex-situ selectivation sequence includes the calcined as described above for the first selectivation steps of contacting the catalytic molecular sieve with a sequence. hydroxyl. The sample was filtered and then calcined benzene.8%. After two hours at 1400 C. no more than 1% of meta-xylene was produced. weight uptake for the 5-step ex situ selectivation process 35 3. and n conventional processes. What is claimed is: In a third ex situ selectivation sequence. halogenated alkyl. a pressure of 300 psig. halogenated aryl. and halogenated alkaryl. The process of claim 1. the expected 50 xylene distribution would be 24% para-. hr ". 0 0 0 Data obtained from this reaction are illustrated in FIG. hydroxyl. alkyl. to 8000 F. and a weight hourly space velocity of from sequence. The process of claim 1. halogen. ortho-xylene would be substantially reduced as compared to halogenated aralkyl. along in 400 cdmin N2 at a heating rate of 10 CJmin to 1400 C. 40 grams of the from about 1 to about 12 and which has been modified three-times treated catalyst was contacted with 40 grams of by being exposed to at least two ex-situ selectivation a 7. modifications. tions further comprise a hydrogen/hydrocarbon mole ratio of from greater than 0 to about 100. The sample The ethylene conversion is greater than 95% in a single pass. (For a non-shape selective catalyst.2% Dow 550/dodecane solution at room temperature comprise a temperature of from about 1500 C. all of the specific embodiments. wherein the alkylation conditions a 5. No more was filtered and then calcined.7% to 36. The weight uptake was 2. no more and held for two hours. and culty of removing ortho-xylene from ethylbenzene.025 13 14 room temperature with mixing for two hours. wherein the selectivating agent 250 psig. a H:/HC comprises a silicon compound selected from the group molar ratio of 1. indicates that in the ethylation of benzene. under alkylation conditions sufficient to proas described above for the first selectivation sequence. four-times treated catalyst was contacted with 42 grams of 30 2. 10 While the invention has been described with reference to In a second ex situ selectivation sequence. The moist sample was heated than 5% of ~ is produced (reduced residue make).. and accordingly all such mixing for two hours.1 atmosphere to about 200 calcined as described above for the first selectivation atmospheres.65% Si02. alkaryl.. The weight uptake was 2. and a temperature consisting of of 7600 F. in nitrogen at tion by-product. aryl. Moreover.3% Dow 550/dodecane solution at room temperature 25 sequences. uncontaminated with meta and which time air was introduced followed by heating in air at ortho isomers. with no more than 500 ppm of p-xylene.0% Si02.3% Dow 550/dodecane solution at room temperature with the invention are possible. A process of claim 1.40 selectivation sequences. comprises dimetbylphenylmetbyl polysiloxane. Almost pure (>75%) para-diethylbenzene (para-DEB) is taken as a transalkylahours. halogen. and held for two 5 than 20 ppm of o-xylene is produced. 15 present invention as claimed. The process of claim 5. and R2 are independently selected from the 26% ortho-xylene) This extremely low ortho-xylene make group consisting of hydrogen. At toluene conversion rates of from 28. Within the xylenes fraction. no more than 500 ppm of o-xylene was produced. Accordingly. to about 4800 with mixing for two hours. EXAMPLE 2 4. The weight uptake was 1. was 3. 1. 60 -tt-+ wherein R3. The total silica about 0. the generation of alkoxy. wherein the alkylation condiwas about 10%. 5. which comprises a zeolite having a constraint index of In a fourth ex situ selectivation sequence. modifications. R4. 50% meta-. and held for 6 hours. conditions comprising an ethylene WHSV of from 2 to 4 65 halogenated aralkyl. a pressure of 6. 42 grams of the subsequently calcining the catalytic molecular sieve. wherein the catalytic molecular sieve has been modified by between two and six ex situ The five-times selectivated catalyst of Example 1 was employed for the disproportionation of toluene under con. and wherein R. The sample was filtered and then variations. 0 EXAMPLE 3 . is a very valuable commodity and commands 2 C. wherein the selectivating agent ditions comprising a toluene WHSV of 3 hr". The sample was then cooled to 300 C. The process of claim 2.689.1 to about 10. a benzene to ethylene weight ratio of 20.3% Si02. The ethylbenzene purity is greater than 95%.
The process of claim 18. The process of claim 20. wherein the organic carrier comprises dodecane. wherein said transalkylating step comprises recycling said polyethylbenzenes into said reaction stream. and mix- 16 tures thereof. 19. The process of claim 15. 16. 14. further comprising the step of combining said ethylbenzene produced during said transalkylating step with said ethylbenzene produced in said contacting step.025 15 7. wherein the organic carrier component comprises hydrocracker recycle oil. ethers. cycloparaflins. wherein the in situ trimselectivating step comprises contacting the modified catalytic molecular sieve with a reaction stream comprising hydrocarbon and a trim-seleetivating agent. branched. and combinations thereof.689. wherein the catalytic molecular sieve is modified in an as-synthesized condition. wherein the organic carrier is a paraffin containing at least 7 carbon atoms. 9. 5 10 15 20 25 ***** .5. 8. wherein the in situ trimselectivating step comprises contacting the modified catalytic molecular sieve with a thermally decomposable organic compound selected from the group consisting of paraffins. The process of claim 15. 20. wherein the catalytic molecular sieve contains an ion selected from the group consisting of hydrogen. The process of claim 1. The process of claim 1. The process of claim 8. hydrogen precursor. wherein the modified catalytic molecular sieve has been further modified by the step of in situ trim-selectivating the modified catalytic molecular sieve. 17. 18. 12. 21. The process of claim 7. The process of claim 7. 11. at a temperature in excess of the decomposition temperature of the thermally decomposable organic compound. or cyclic hydrocarbon. The process of claim 1. The process of claim 1. wherein the modified catalytic molecular sieve has been further modified by the step of steaming the modified catalytic molecular sieve. aromatics. wherein said transalkylating step comprises introducing said polyethylbenzenes into a separate transalkylation reactor and reacting said polyethylbenzenes with benzene under sufficient vapor phase or liquid phase conditions to produce ethylbenzene. 10. olefins. The process of claim 14. further comprising the step of transalkylating polyethylbenzenes produced during said contacting step. wherein the organic carrier comprises a linear. The process of claim 11. 13. phenols. cycloolefins. aldehydes. ketones. 15. wherein the thermally decomposable organic compound is ethylene. The process of claim 18. heterocyclics. The process of claim 1. organic cations. alcohols.
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