US 3766290 A
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oct. 1s, 1973 C. D. CARLSON PROCESS FOR THE PREPARATION OF ETHYLBENZENE Filed Aug. 1o, 1972 Imi " United States Patent O 3,766,290 PROCESS FOR THE PREPARATION F ETHYLBENZENE Cleo Dale Carlson, Lake Jackson, Tex., assignor to The Dow Chemical Company, Midland, Mich. Filed Aug. 10, 1972, Ser. No. 279,652 Int. Cl. C074: 3/62 U.S. Cl. 260-672 T 7 Claims ABSTRACT 0F THE DISCLOSURE An improved process for the alkylation of aromatic compounds in the presence of an aluminum chloride-based catalyst wherein the catalyst is formed in situ in the alkylation reactor and is used single pass with no recycle. The reactor is operated at temperatures of between about 130 C. and about 250 C. and at a pressure suicient to maintain the aromatic reactants in the liquid phase and for a time of about 2 to about 15 minutes residence time. Simultaneous dealkylation of higher polys is possible while maintaining good production of mono-alkylated product.
This invention relates to a process for producing alkylated aromatic hydrocarbons wherein an aromatic hydrocarbon such as benzene is alkylated with an unsaturated aliphatic hydrocarbon and recycled higher alkylated aromatics are simultaneously dealkylated or transalkylated in the presence of an aluminum chloride-hydrocarbon complex catalyst. More particularly, this invention relates to an improved process for the production of ethylbenzene and other alkylated aromatic hydrocarbons which permits the use of smaller equipment, higher throughput rates, higher conversions of polyalkyl benzenes without loss of alkylation efficiency, no catalyst recycle and generally improved industrial efciency not heretofore achieved.
For many years, alkylated aromatic hydrocarbons have been produced on a large commercial scale by the alkylation of benzene with ethylene in the presence of an aluminum chloride-hydrocarbon complex catalyst. As shown by the ACS Monograph entitled Styrene, much of the early day ethylbenzene was produced by feeding ethylene, benzene, particulate aluminum chloride and recycled polyalkylbenzenes to an alkylator together with ethyl chloride of HCl as promoter. The alkylator was operated at a temperature of about 95 C. and at a pressure of about 5 p.s.i.g. A crude alkylate, along with the entrained complex catalyst passed from the reactor, was cooled and settled. The catalyst complex which settled out was then pumped back to the alkylator and the crude ethylbenzene was treated with caustic to remove any remaining catalyst and subsequently fractionated. All of the recovered benzene was dried and returned to the alkylator. Likewise, the light polyalkylated benzenes (mostly diand tri-ethylbenzenes) were returned to the alkylator and the heavier polyalkylated benzenes (residue) were sent to a special dealkylator operated at more severe conditions.
In more recent times, it has been taught to produce the aluminum chloride-hydrocarbon complex catalyst from aluminum metal, HC1 and a hydrocarbon rather than using particulate aluminum chloride, e.g. U.S. 2,948,763. The catalyst complex prepared from aluminum metal has also been prepared in situ by feeding a slurry of `line aluminum particles and HCl to the alkylator but it has been generally preferred to prepare the catalyst complex in a separate vessel and then feed it to the reactor rather than form it in the presence of the reactants.
Beyond the preparation of the aluminum chloridehydrocarbon complex catalyst from aluminum metal and HC1 in hydrocarbon solution to avoid the handling problems associated with aluminum chloride, very little change has taken place in the basic ethylbenzene process in the last 20 years. In practice and as shown by the recent literature, alkylators are usually operated at between and C., at or near atmospheric pressure and benzene, catalyst complex and polyalkylated benzenes are all recycled to the reactor.
It is an object of this invention to provide a more efficient process for the production of ethylbenzene. It is a further object to provide a process for the production of ethylbenzene which requires less residence time in the reactor than present commercial processes and which is capable of dealkylating a higher proportion of polyalkyl benzenes during the alkylation reaction. A still further object is to provide an ethylbenzene process which does not require the recycle of the highly corrosive and hazardous catalyst complex to the alkylator. Yet another object is to provide a process in which the reactor and other equipment are many times smaller than the conventional process equipment for equivalent production, thus providing a sizeable capital savings. These and other objects and advantages of the present process will become apparent from the following detailed specification and claims.
It has now been discovered that numerous significant and unexpected advantages are achieved by employing the process steps and conditions of this invention as hereinafter described. In its general terms, the process of this invention comprises the steps of (1) thoroughly admixing, in a reaction vessel, particulate metallic aluminum, an aromatic hydrocarbon, an olen, polyalkyl aromatic hydrocarbons and anhydrous HC1, (2) simultaneously alkylating the aromatic hydrocarbon and dealkylating or transalkylating the polyalkyl aromatic hydrocarbons in said reaction vessel in the liquid phase at a temperature of between about and 250 C. and a pressure suicient to maintain the aromatic reactants substantially in the liquid phase, (3) separating the crude product from the catalyst complex, (4) separating the alkylated aromatic hydrocarbons from the unconverted aromatic hydrocarbon, (5) separating the monoalkylated aromatic hydrocarbon from the polyalkylated aromatic hydrocarbons, (6) recycling the aromatic hydrocarbon and polyalkylated aromatic hydrocarbons to the reaction vessel, and (7) recovering the monoalkylated aromatic hydrocarbon.
The catalyst in the present process is preferably formed in sit-u in the alkylator by feeding a slurry of particulate aluminum metal and gaseous anhydrous HC1 directly to the alkylator. Substantially any form of particulate commercially available grades of aluminum metal may be employed but those forms exhibiting a fairly large Surface area, such as metal turnings, granulated metal, etc., are highly preferred. Granulated or powdered aluminum having a mesh size of from about -10 to about |40 mesh is particularly desirable. A preferred method of feeding the aluminum to the reactor is in the form of a slurry of the metal in a liquid component such as benzene. It is desirable that the aluminum contact HC1 soon after entering the reactor. It has been found that under the reaction conditions of this process, the aluminum chloride complex catalyst formed in situ has suicient activity to produce the desired alkylation of the benzene without making excessive amounts of undesirable reaction products. The amount of aluminum metal used to form the catalyst in situ is an amount sucient to make the reaction go at an acceptable rate. Generally, the amount employed is such that the weight ratio of total hydrocarbon fed, i.e. aromatic, olefin and polyalkyl aromatics, to total aluminum metal fed is not less than about 1000 to 1, nor more than about 10,000 to 1. The preferred range of operation is from about 2500 to 1 to about 5000 to 1.
In this manner of operation no separation and recycle of catalyst is required. It was unexpected to discover that in this process, the recycle of catalyst complex is not necessary either to enhance or sustain the reaction and quired. `to'keep .thek reactants Vin v'the liquid phase.
that the alkylator can be started with Vin si'tuifeniied' i catalyst in the absenceY of anyrecyclecatalyst complex andwithoutany preheating of the aromaticV raw 'maf terials. The start-up timel is actuallyreducedover: the processV which uses particulatesv AlCla. lAlthoughfvthere 1s no needto recyclethe catalyst, there is nothing to prevent Y of` reactorsV so long as the ow yis rsiuiciently:,turbulentt. l tofprovide thorough mbtiugY off the reactantsand'` the .j l,
residence time is maintained Within Ythe desiredfl'imits, .Y
The figure shows a rschematic ilow diagramv of onel preferred embodimentV of the process of this?V invention..As
shown inthe ligure, aluminum lines are admixed infvessel this as 'longV as theresidence Ytime is short enoughftoj prevent loss of activity in the catalylst.
In order @achieve uwY objected this nvenuemf-itis necessary that the alkylator beoperated at a temperature of between'about 130V and 250 C. at a pres'suresuicientto maintain the aromatics in the liquid phaseAtl temperatuers below about` 130, C. in the instant system Y. the dealkylation reaction is too .slow and a lorlgerre-Hr action time is necessary to eifect transallylation.l Attemperatures above 250 C. the amount' of pressure needed to l keep the` aromatic liquid becomes morey costly.
yA pressure of at least 115 p.s.i.g. is usually re 'anda pressureV of between Y'about 1'9'0--300Y ,pis preferred.y YHigher pressuresY may rbe employedy bu ere is no'V advantage lin usingpressure higherv than hat The processV of the* present: invention, e lthugh described primarily in terms of ther ethylation of benzene, e
has been employed to make cumene fromr propylene and quired Y benzene and to make' ethyltolueneY fromA lethyleneandA` toluene'under,substantially the saine conditions'as'hereinVY set forth; Likewise, with only slight alterations! in temi y peratures and pressures,Y keeping in `mind .,thenecessity of maintaining the aromaticsingtheliquid phasee-fother lower olefins and aromatic hydrocarbons can be employed in the alkylation reaction. a
The operation of the presentprocess permits the/use; Y
of a feed to the alkylator containing up to by weight polyalkyl benzenes. It is usually/desirable, however,Y `to employ polyalkyl benzenes in the feed of fromY 10 'to V2.0% based onsthe benzene fed. WhileV all of the polyallfrylA benzenes produced in this process may be recycled tothe a'lkylator, it is preferredV to recycle the diV andrtriethylV benzenes (commonly referred to as light polys).- f y.
Under Vthe conditions 0f this process,4 the required residence timeiinV the reactor varies with reaction conditions but in general a residencetime of from about, 4
to aboutV 8 minutes in preferred. At residence `times signi:y licantly shorterthan'Z minutes,` the' conversion wouldbe] so low that` considerable recycle'oi unreacted materials f Y .would'be required. At reactionptimes greater thanf30 minutesanffundesirable amount of side reactionsbegin 10- with dry benzene and polyalkylbenzenes to formv a slurry. The slurryY passes: through linell'and just before enteringthe alkylator 12,'the slurry of aluminummetal ina mixture of benzeneand poly allrylb.enzenes-V is furtherv f mixed with the ethylene feed stream. Anhydrous hy` Y drogen chloride is added'to the alkylator `12,.through a pipey 13 near the bottom thereofA throughvakspa'rger so n that rapid vcontact takes 'place between the mixed feedV stream from line 11 and the HC1S from-:line 13. They alkylatorY product passes from alkylatork Il!` through line 14 to a quench spool 15 where direct, Contact is made VVbet tween the hot allrylatlur` product anda kstreamof, Water f containing dif-17.0% *causticforcoolingV ndxwashinei Y.
from linesV 16.v 4The small amount of; caustic'is added.' o, prevent corrosion withinr the wash, system,Y Alteru'atively,V
the het product Y from" Vthev alikylatienf-. reactor]y maybe j cooled by cross heatexchange to more eliicientl'y utilize" the B.t.u. contenterr thehotveilluent prioritorwashing with; aqueous caustic.. i The kwater-qtneuched products passes Y through line 1'7 to a settling tank 128. In settling tank` 18' theV 'aqueous4 and r'n'ganic@layersV separate with the aqueous layer being passed through line.V 2L to a waste-diposal system in accordanceV with approved ecologiealz praetieeand the yorganic alkylfate product passing 'fromettlingtank 18 through vline 19V where itfisadmixe'd and Vsweetened with diluteaqueous caustic (640%) and. passed to settling tankr20. The aqueous causticflayer may be, recycled through line 22 'for optimum utilization.beforeV it is drawn Y Y oilV and passed to theV waste disposal system mentioned abovetand the crude ethyl. benzene issentfto a'Y standardU separation and purification section Wherefbenzene andr polyethylbenzenes are recycledto the alkylator 12.
to occur. Also,`V it has been found thaty aluminumchloride@ complex becomes less catalytically'active at the'V temperatures employed'when exposed forthis length ottime.`r` Y Ethylene of y 99% purity; is most preferred.
, es Minna1.-@las?noireR,rannonuancey Although the ligureV illustrates coolingv and washing the productl with aqueous caustic, it may be preferrrcdto sepaV arate the catalyst complex, eg. by gravity, utilizing the heatr of the crudeY in vits distillation without any cooling or Washing'. The catalyst complex may then be washed prior to its disposal. Any Vresidual.V useable polys obtainedKY i5YV .Y with known technology. The followingY examples 'are provided to.; illustrate the from the catalyst complex may beutilizedln accordanceL practiceV of theV invention but are not to beL construed as lmitingfto the scope thereof., i
j EXAMPLE y1 j f Y A series of experimentsfwas conductedA toillustratethe Voperation of the present'processpunder various. conditions.
Each of the experiments was conducted in equipment and' Vin" a process substantially 'as shown iin the-ligure. The results are shownin Table I.
Abbreviations used are: Bzfinanziarie` Et=ethyleue, EBmetlztylbenzene;k Polys=pollyalkyl benzenesy 32H4 Reactor' Residence"yY percent E :Mole
teeth, temp., ltime," .er t/hr. C. j minutes :noie Ezel* 380 198 Y j 5.4 .57v Y'360' 199 '5.4Y k.55
`312 199 f 8.3 Y l 61 640# 199 a2 so fr the alkylator and pressure is reduced as it passes through a control valve. The products .crude ethylebenzene may, be utilized in any proven preferred manner by Vthe user.
Although the figure illustrates a conventional reactor vessel, there is nothing to prohibit the'use of other types 75 f ir-This ratio is actually the mole ratio of al1 ethyl groups to all benzene As the liquid reaction product isrformed, it passes Yfrom 70 Y Runs l and 2 were made under substantially the sameV Vconditions to illustrate; reproduceability of the data.V The slightly lower yield to ethylbenzene in Run 2 reflects the Y slightly lower e (ratio of ethylV groups to benzene rings) employed in Run, 2.
Runy 3 illustrates the ability Yof the processrto/ simula Y*Product analysisywn taneously convert high levels of polyalkylbenzenes to ethylbenzene.
Run 4 is presented to show the use of lower proportions of polyethylbenzenes.
Runs 3 and 5 illustrate the effect of increasing the e ratio on the yield to polyethylbenzenes.
Run 6 illustrates the effect of reduced residence time on the distribution of products in the reactor eilluent.
While light polys are used in the feed of the above examples, similar results are achieved if the polyalkylbenzenes are recycled to the alkylator as produced. All of the above runs were conducted at a pressure of about 190 p.s.i.g.
EXAMPLE 2 Experiments were run under different conditions of temperature, time and' epsilon values, using both high purity and low purity ethylene. Table II below is provided to show the specific reaction conditions and the results. Note that epsilon values of about 0.3 (Runs 3A and 3B) and 0.5 (Runs lA and 1B) at identical times of approximately 5 minutes and at temperatures ranging from 130 to 148 C. provided good dealkylation or transalkylation of polyalkylbenzenes while maintaining good ethylbenzene production. Note also in Runs 5A and 5B that higher temperatures, shorter times, and an intermediate epsilon value (approximately 0.4) still provide good dealkylation of polyalkylbenzenes and production of ethylbenzene. However, shorter times and lower temperatures in Runs 6A and 6B give low ethylbenzene production and much less dealkylation of polyalkylbenzenes.
Table II also shows that, using the instant process of in situ catalyst preparation, the low purity ethylene gives substantially the same results as the high purity reactant. As mentioned previously, however, the amount of inerts in the ethylene has an effect on the sizing of equipment and the pressure required for the reaction.
The A runs employed 93.5% pure ethylene while B runs employed 99.9% pure ethylene.
TABLE III Weight percent composition Com- Feed conditions ponent Feed Product Run No. 1:
Benzene, 4,0001bs./hr Bz 81.6 57. 7 Ethylene, 310 lbs/hrz-.. El; 6.3 Polys, 600 lbs/hr E Y 30. 8 Temp., 197 C 0.6 6. 7 Pi-sssure, approx 200 p 1. 2 1. 2 E= 10.3 Run No. 2: 3 6 Benzene, 4,000 lbs./hr Bz 73.5 57.3 Ethylene, 380 lbs/hr.w Et 5. 8 Polys, 1,200 lbs./hr EB 21.8 Temp., 19 DEB 2. 6 7. 8 Pressure approx. 200 p.s.i.g TEB 1. 9 3. 1 e=0.53 Res.l 16. 2 10. 0
1 Res.=residue, largely higher polyalkylated benzenes I claim:
1. An improved process for the production of alkylated aromatic hydrocarbons in the presence of an aluminum chloride complex catalyst which comprises (a) admixing, in a reaction vessel, aluminum, an olefin, aromatic hydrocarbons, polyalkylated aromatic hydrocarbons, and anhydrous HC1,
(b) simultaneously alkylating the aromatic hydrocarbons and dealkylating the polyalkyl aromatic hydrocarbons in said reactor in the liquid phase at a. temperature of between about 130 C. and about 250 C.,
(c) separating the crude product from the catalyst complex,
(d) separating the alkylated aromatic hydrocarbons from the unconverted aromatic hydrocarbon,
(e) separating the monoalkylated aromatic hydrocarbon from the polyalkylated aromatic hydrocarbons,
(f) recycling the aromatic hydrocarbon and polyal- TABLE II Dealkylated Feed (mol. percent) Product (mol. percent) Ethylene polys Temp Time Total purity (mol. Run number Bz Polys Et e C.) (min.) Bz Polys EtBz moles (percent) percent)* 73. 5 16. 9 9. 6 0. 48 136 5. 2 59.8 5. 2 35. 0 108. 0 93. 5 11. 7 73.0 16. 8 10. 2 0. 50 148 5.2 59. 3 5. 4 35. 3 105. 6 99.9 11. 4 77. 7 14. 2 8. l 0. 27 130 5. 1 73. 3 2. 4 24.8 144. 5 93. 5 11. 8 77.3 14. 1 8. 6 0. 29 140 5. 2 72. 3 2. 3 25. 4 113.0 99. 9 11. 8 68. 6 16. 8 14. 6 0. 41 180 1. 96 62. 2 6. 5 31. 3 108.7 93. 5 10.3 68. 4 16. 8 14. 8 0. 43 175 1. 96 66. 0 6. 1 27. 9 108. 3 99. 9 10. 7 75. 9 15. 8 8. 3 0. 29 126 2. 1 79. 5 9. 3 11. 2 115. 1 93. 5 6.3 75. 7 15. 7 8. 7 0. 30 128 2. 1 80. 3 9. 6 10. 111. 0 99. 9 6. l *This figure is the dierence between the mole percent oi po lys in the feed and in the product, or the net amount of polys dealkylated.
EXAMPLE 3 In the preceding experiments, the polyalkylbenzenes fed to the reactor were primarily diand triethylbenzenes with approximately 10% of them being heavier than triethylbenzene. The following two runs show feeding approximately 20-25% by weight polyalkylbenzenes, of which approximately 78% are those having molecular weights above triethylbenzene. This product which is largely higher polyalkylbenzenes, and ordinarily a waste product, is referred to as residue in Table III. The results indicate good dealkylation of these higher polyalkylbenzene waste products While maintaining good ethylbenzene production. Thus, the first run, which shows a somewhat lesser total amount of polys in the product than in the feed, indicates that the deallrylation results in the production of some ethylbenzene as well as large amounts of higher polys, i.e. diand triethylbenzenes. The second run shows no decrease of total polys in the product, but nearly 1/3 less of higher polys in the product (30.4% less) than in the feed. The conditions of reaction and amounts of feed and products are shown in Table III. The ethylene used had a purity of 99.9%.
6. The process of claim 2 wherein the aluminum is employed in an amount such that the weight ratio of total hydrocarbons admixed to aluminum metal is not less than 1000 to 1, nor more than 10,000 to 1.
go UNITED STATES PATENT @what I CERTIFICATEFOF Q'HN Patent: No. 3 766,296 f l, .Rated october 16, 12973 Invientor(s) Cleo Dale Carlson It is certified that error appears in the aboveidentifed patent and that said Letters Patent are hereby corrected as shown below:
Col. 3, line 5, "particulates" should be changed to -parti ':ulate.
Col. 3, line 13"temperatuers''should 'be'. changed to -temperatures.
Col. 3, -line 44, change "in" to -is.
Col. 3, line 73, change "products" to -jproduot-n Col. 4, line 24, change "B.t.u." to -f-B`.T.U..
co1. 6, Tabl-e 11 change "144.5" to -114.5-*.
Col. 5, lie 70, change "higher" to -lighter.
Signed and sealed this 5th dayv of November 1974.
MCCOY M. GIBSON JR.v C. MARSHALL DANN Attesting Officer Commissioner of Patents