US2363301A - Production of motor fuel - Google Patents

Description

Patented Nov; 21, 1944 arm Baa-1 mi; as; 1936' 15 chi "85.01

Thi application isga division ofiappllcation U; s. SerialNo, 155,918, filed July 27, 1937. r

This invention relates to the production ot 'f a" high class'niotor :fuel adapted for use-as avi ation or motor spiritconstituent1o! high an 1:;

knock rating and consisting essentially it not ehtirely of iso-paraflins.

According to, the invention an'oleiine' is subparamn containingatertiary carbon atom) i I the presence or a mineral acid, whereby onset e5 merit an upper hydrocarbon layer separates which is composed substantially of saturated I hydroirom which a fully saturated aviation or motor tion. The reaction may be carried'out without the necessary use of high pressure. paraiiins such asIisobutaneandisopentane' and oleflnes such as propylene, isobutene, diisobutene and triisobutene'or mixtures of such paraflin or of such oleiines maybe used, and the conditions" of operationare advantageously such that that liquid phase is maintained during the period of contact. Furthermore, the iso-parafllns maybe I I employed in admixture withnormal paraiiins carbons boiling, within the motor spirit 'rang'e'f spirit or constituentmaybe producedon di'st'iil'al v f ie a t which are incapable ofehterirrg into the r action; The olefine too may be admixed with inert mate rial: As a general rule, howevenit ispreferable ,7 v 4 to utilise bothreactants in as pure a state possible, since there is; tendency for theyield to be poorer and difllculties may possibly be en'- countered inseparating the non-reactive material from the product. 7 a

According to the invention moreover the 'isoparaflin or iso-paraihns may advantageously used in substantial or considerable excess of equi; molecuiar'proportions with; respect to the cleaneor oleflnes'used. I II I The invention comprises the process carried out under th conditions hereinafter described and the product's thereof. I I

It i jlrn'o'wn to treat with sulphuric acid at low temperatures hydrocarbon fractions coriii aflriing" oleflnes that also contain iso-paraflinsb'ut in such hydrocarbon fractions the content or the iso" paraflinsIis low, and this isthe case in hydro- 1 carbon fractions thatcontain lower oleflnes'such as is'o: and normal bfitenes suitable fIor use wcording to the invention for the production of saturated iso-paraflin-derivatives boiling in the motor spiritrangeQ I I Where however equimolecular proportionsoi iso-butane or iso-pentane and the selected ole-'- fines react qu va nt pr portions when'the renewing examples wherein mavens-erases en'i:

I reacted. som 01' 40 add d gradually to sh n I fist l prhceasg 'r e ne e1.mo r,1 n u molecular proportions ss'oft isip M a. meshes should added this while thestirrmg I ture employed manQifdinarily b'e a I the ease of ischutsh however of the reaction isde I I continued for a; short period after l me rec has been added, whereupon the mixtureis snowed to settle and the lower aci'dllayer withdrawn' o settlement, apparently little changed except in'respect 'of colour. The clear colourles upper hydroh, carbon layer srter settlementis soda-washed and distilled.- It is round almost entirely saturated, the olefine I I I I I H I I r ana swam covered and" can'bef reprocessed; when normal ermits are resent-1 the; feed hack they t o I willbefrecoverd unchanged; Theyshould prererab ly be separated; rrom the r covered u changed iso-mi raflm per re rte-processin the lat-' teri; The residual materialwhasa pleasant odour I and is almost entirely-iso-paramnic in composition;

In+carrying out the reaction advantageously, it is desirableto' employ ayolume' ratlo' of j hydrocarbonto' s'uHuric' acId initially oi betweenj about 15:1 and about 2.0:1 with ajcalcuiated.

ratio after all of the olefin has been 6Q between about 2.5:1 and about 4.4' :1;. These rathis will be apparent from" an msp ehohr the 8 wh ei com For practical purposes the ratios may be determined by computing upon the basis of volumes of isoparafiins, oleii'n's andisuliiuric acid actually employed, althoughit is realized that the final volumetric ratio when computed on the amount of hydrocarbon to sulfuric acid employed is not strictly accurate at the conclusion of the alkyla-; tion reaction since some olefinic reactant remains absorbed in the acid and the alkylateproduced together with the unreacted hydrocarbons may possess a slightly decreased volume with respect to the initial total volumes of th reacted reactants added to the sulfuric acid. However, the'ratios do provide an indication of the relative amounts f of both types of reactants asswell as sulfuric acid which are admixed in order to form the reaction mixture.

The following are a number of examples of the carrying out of the process or production of mo torfuelaccording to the invention under a variety 5'; colourless hydrocarbon layer withdrawn. The acid which .was a pale straw colour increased in 1 volume in the treatment by 5-15 cc., while the v EXAMPLE 3 Six hundred cc. of isopentane and 400 cc. of

.sulphuric acid (approximately 97 per cent) were placed in a vessel cooled in ice and the mixture vigorously stirred. When thoroughly cold 400 cc. of diisobutene were slowly added over a period of 2 hours, after which stirring was continued for a further half hour. The hydrocarbon to acid volume ratios were maintained within the ranges set forth in Example 2. The reaction product was then allowed to settle and the upper volume of the hydrocarbon layer after neutralisation was approximately 875 cc., its specific gravof conditions and in'theuse i-various olefines 1 Four hundred of concentratedcommercial sulphuric acid (approximately 97 per cent) are charged with-400 grams (about 867 cc.) of liquid isobutane"at' "12 C.' into avessel fitted with an eillc'ient stirrer and surrounded by a bath oi. coollug liquid maintained at -10 c. to -12 c.

400,.gra'ms (about 533 cc.) of diisobutene are slowly run into a mixture over a period of two hoursfand ,s'tirri'ngis continued for a further periodof minutes after thegaddit'ion oi. diisobutene. The'volume ratio of total hydrocarbon to acid'was about 1.67:1 initially and was aboutl3zl or somewhatlower after all of the diitywas .713 at 60 F., and its bromine number (Francis method) 4. The Francis method of determining bromine number is described in The Principles of Motor Fuel Preparation and Application" by Nash and Howes, vol. II, paragraph produced had. a high antiknock rating and was isobutane had been added. The mixture is al-" lowed to settle and. the lower acldlayer is run off; The aci'dlayer is straw colored and has increased in volume by about 15 cc. The upper hydrocarbon layer is soda-washed and distilled.

Itboils over acomparatively wide range, and contains a considerable quantity of unreacted isobutane, the iraction 50-150 C. representing 48 per cent of the" total hydrocarbon charge. The portion boiling between 90 and 110 C. has. an octane number 01955 (C. F. R. motor method). The C. F. R. motor methodof determining knockrating is described in The Principles of Motor' Fuel Preparation and. Application by Nash and Howes, vol. II, paragraph 759.

EXAMPLE 2* Four hundred cc. of concentrated commercial sulphuric acid (approximately 97'per cent) are thoroughly mixed with,.600 cc. isopentane in a vessel surrounded by iceandfitted' with a stirrer. Fourhundred' cc. diisobutene are added gradually overfafiperiod'iof two hours., The initial volumeratio of total hydrocarbon toacid wasabout 15:1. The final ratio was about 2.5:1 or actually slightlylower due to the condensation. Stirring is continued fora further'period of 30 minutes after the diisobut'ene has been added. At the end of this time the mixture is allowed to settle and the lower acid layer'is removed. The recovered acid is straw coloured and has a volume of 415 cc.'.approximately. The upper layer of treated'hydrocarbon is soda-washed and distilled. It

distills over a wide range and contains a proportion of isopentane which has not reacted. The fraction boiling from 50-175 C. represented 52% of the total hydrocarbon charge and is pracproduced without the application of heat and without pressure.

EXAMPIE 4 A polymer gasoline produced by the catalytic polymerisation of olefines and having a boiling range of -120 C. was used as the olefinic material, having a specific gravity of .727 at 60 F., and a bromine number v (Francis) of approximately 200. The treatment was carried out as in Example No. 3 using 400 cc. acid (97 per cent), ,440 grams (about 730 cc.) of isobutane and 440 grams (about 587 cc.) of the polymer gasoline. Th polymer gasoline was slowly added in a period of 1% hours, the stirring being continued fora further hour. The recovered acid was rather darker in colour than that recovered in Example No. 3, and had increased in volume to 450 cc. The amounts of reactants and acid cor respondto an initial hydrocarbon'to acid volume ratio of about 1.82:1 and a final ratio of about 3.29:1. The hydrocarbon layer after the removal of isobutane had a specific gravity of .728 at 60 F., and bromine number (Francis) 31. Fractionation yielded a product boiling over a wide range, 74 per cent boiling to 200 C., having a specific gravity of .715 at 60 F., bromine number (Francis) 21.5 and a residue having a specific gravity of .801 and bromine number (Francis) 57. The distillate boiling to 200 C. had a pleasant odour and an octane number 84.6 (C. F. R. motor method). With an addition of ethyl fluid equivalent to 2 cc. tetra ethyl lead per (Imp.) gal. the octane number was raised to 95.5. It may be noted that while the bromine number of the fractionated reaction product was high, the bromine number of the polymer gasoline was very high, and that modification of conditions would have resulted in an even lower bromine number of the fractionated product.

, treatment in.the use of diisobutene as olefiriic ma- I .terial and isobutane'as the paraflinare recorded 1 below in run No. 2 of Table No.1, together with e ,sca,ao1- e iected to -a cracking distillation may first be treated in known manner with sulphuric acid (60 per cent) followed by heating and polymerisation whereby thereis produced a mixture of di- Sixteen hundred cc; of sulphuric acid (97 percent) were placed in a pressure vessel provided with a stirrer and an external jacket through which cold or warm kerosene or the equivalent could be circulated, and 1800 'gramslabout 3210 cc.) of isobutane were added. 'Th 'acidand parafiln were then stirred, with warm kerosene cir-e culating through the jacket, until the. temperal cure the mixture F f 1 thg-prevssure x triisobutene'may be fractionated and the diisoreaching 45 lb. per sq; in h 8 18 111801300 'butene may be hydrogenated by known means to grams (about 2490 cc.) of diisobutene were slowly .prdduce an isomctane of 10 octanev number and added w v o stirrlna- Cooled kerosene L the triiso'butene may be subject to contact with portion of unchanged material. The diisobutene and triisobuten'e may be subjected to contact with anisoparafiln, in the presence of sulphuric acid as hereinbeforedescribed.

Alternatively the mixture, of diisobutene and was circulated through the jacket during this an 1s pa am in the presence of smphuric acid addition to remove the heat evolved; somainv v as hereinbefore described for the production of a w n n the mperature of the mixture at abou saturated spirit of high 'antl-knock'value having 20 C. The addition requi /2 hours. after --an octane number of about 89'to90. which stirring was continued for a further /2 From the product'of the reaction of isobutane h r- T p re h then l n t bout 20 and isobuteneor polyisobutenes. iso-octane, (2.2.4 -15 lb. per sq. inch (gauge). .The hydrocarbon tflmethylpentane) may be separated fragto. id. ratios ere initially about 2:1 and finally tionation. Among other hydrocarbons which may about 3.56:1. a a be isolated by fractionation are: 2-methylbutane To facilitate handling, the product was then (isopentane); 2.3 dimethyl-butane, 2,3- and 2A- cooled down to 0 C., the acid and hydrocarbon 25 dimethylpentane and 2.2.5 trimethylhexane.

Tut: No. 1

Tabulated examples of treatments carried out accord g to the invention in which the following oleflns, viz: (i) diisobutene. (ii) triisobutene and (iii) propylene were used with isobutane, in each case in the following proportion:

' Sulphuric acid (approximately 97% except in run No. b in which the acid strength was 100.6%) ..cc.. 1800 isobutane 1800 Olefine (i) or (ii) Oleilnc (iii) Boiling range of product: 27-185 C. Residue 185 Per cent Ru Tom product Engine teat No olefin 0? 51 2 95 l er cgn Bromine a o F i out Bromine V I 0110 a ne +114 cc. on oleflne S. G. 00 F.

take taken 50% in Neat tatraethyl taken I H. 0. S. lead per I e ,v (Imp.) gal.

(1) 52 10c 1 .700 12 0 02.1 I 105 as. 4 22 .786 (1) 133 1 710. 70 6 89. 3 99. 7 l3. 5 .781 n) -10 152 106 1 .710 11 2 tax 100.0 as. 1 as .792 (ii) +20 103 1'38 1 704 68 9 .88. 7 98. 9 2). 5 l3 782 (m) -30 150 122 1 ms 67 4 52.5 93. :1 2a. 0 2. 5 .110

1 Basic blending matcrial,-52.5 octane'nurnber. e layers separated, and the hydrocarbon layer com TABLE No. 2 I

pletely neutralisedwith soda. The results of, the

A. S. T. M. (American Standard Test Method) referred to in Table No. 1

the results of similar runs when using triisobutene under: the same conditionsiruns 3 and 4 Table mm 2 Rm 4 N0. 1) Similar results are obtained when operating e at +30 0. although there is a little more so: i ffflfiffiff" Q; 32 If 3;; formation than at the lower temperature. The i5? 0'0 5 69 acid however retains thesai'neappearance. 1 20%: 102 03.5 By operating at l0 C. a somewhat lower yield 50 110 10 00 of useful product, that is a fraction having a boil f 1' j ing range of 27-185 C. is obtained, but this 129 131 122 possesses a slightly higher octane rating (runs-1 11,, }g,g;g and 3Table No. 1). I The efilciency or the agita- 196 5 ms 200' tion is an important factor. the product improvr tiifii ii lit t i test 32 3% 32 ing with increasing efnciency of agitation. Residue 1 1 1 The acid in these runs is not spent and may be t 5 used repeatedly or" employed for other refining operations.

. Isobutene may be 'used instead of or together with diisobutene or triisobutene or other such olefines or mixtures of diisobutene andetriisobutene may be used. 1

Thus in carrying out the'process, gases from a tween isobutane andpropylene was conducted in the same way as with isobutane and diisobutene. Propylene was added as liquid under cracking plant in which apetroleum stock is subpre sure and sulphuric acid containing free isobutane and. .triisobutene in addition to a pro- I distinctions of the products of runs 2, 4 and 5 In run No. 5of Table No. 1 the reaction be- 4- 2,868,801 sulphur trioxide (equivalent to 100.6% sulphuric relatively little disadvantage since it can be easily acid) was used. At the end of the reaction the recovered by distillation and re-used.

pressure fell practically to that. of the atmos By substantial or considerable excess is phere on cooling the vesselto C. 1 meant a substantially greater excess of isobutane Inasmuch as when using propylene a. small than that small excess required to ensure against amount of dialkyl sulphate is present in the :the momentary presence in the vigorously stirred hydrocarbon layer, neutralisationshould .be reaction mixture of a local excess of the olefine thoroughly carried out (as for-example by stiras it is slowly added and admixed with isobutane ring with per cent soda for 5 hours) to preorisopentane and sulphuric acid during the pevent the formation of free acid and acid prod- 10 riod of contact, which substantially greater'exucts with consequent charring of the contents of cess may reach a considerable proportion with the the still during the subsequent distillation. practical advantages referred to;

' Tenn: N0. 3 Tabulated results of two experiments carried out according to the inventionin-which the isobutanerdiisobutene ratios by weight were respectively 1:1 and 2:1. I

Diisobuteneand isobutane at C. using 96.9 percent acid 1 Pressure used sufil cient tomaintaln the isobutane 1n the liquid phase I Time of addition: 90 min. Time of stirring: min. Ezpf. No. l.l:l 3000 cc. isobutane I 1800 g. diisobutene Erpt. No. 2.2:1 4500 cc. isobutane 1350 g. diisobutcne v (2490 cc.) (1875 cc.) Ratio hydrocarbon: acid Initial 1.38411 Ratio hydrocarbonzacid Initial 3.75:1

Final 3. Fmal 5.3:1

.Iroduct 27 v Product 27-185 0. Residue .2 p 1 E E p A. S. T. M. distillation 5 Engine test 5 g c s s Cl 0 g g s 5 0' a 5 0' a e -c".e.eg .%.e tie. cs2==3 gs c s 552225? 125 mi ss sstssssss fidsaasasssj ad-aldfisfiiidfi 1:1 1,000 105 as 45.5 53 66.5 04 10511151115125513751005 107 257 975 1 5 13a 1 .705 71290.5 08 22 14 .783 2:1 1,200 134 3s 3 49,64 80 101107 112 118.6128 143 101 230 90 5 15s 1 .700 71101.3 98.9 14.8 0.5 .7132 v The product from this reaction contains con- EXAMPLE 7 22 2: quantltles and 2'4'd1methy1pen To 3000 cc. isobutane and 1600 cc. of sulphuric EXAMPLE 6, 0 acid (97 per cent) were added while maintaining the temperature at 20 C., 2250 cc. of liquid bu- In the foregoing examplesthe proportion of t duri g a period of 1 /2 hours and sufficient the isoparaflin to olefine is approximately such pr ssure was applied to maintain the liquid p ase. that for each molecule of the former one mole- After a tati f r a ur r /2 u th product cule of the latter or its equivalent in the case of was separated f nd w ed p s in P o s 6X- polymerides is taken. Since the polymerides so imlples The initial volume of hydrocarbon to far examined behave as though depolymerised acid ratio was about 1.87:1 while the final ratio to the monomeric form before reaction, the quans ou 3. 811- T e overall yield of product tity of iso-paraflin required is determined by the ed upon the olefine taken was 16 Pe e monomeric equivalent of the polymer, e. g. two the speplfic avlty of the Product 3706 at molecular proportions of iso butane to one f and the-bromine number (Francis) 3. On distillaisobutene, three molecular, proportions of isothe q of the ,fraclfion having the boiling butane to one of triisobutene and so on. The range 27-185 was equivalent to 148 P cent proportion indicated in the foregoing examples of h olefine takenhi fraction 2 a Specific are not however essential. On the contrary subgravlty of at -l bromme number stantial or considerable excess of the iso-paraflln (Francis) less than and octane rating of or ismmmfims is generally advantageous in 90.2 octane number increasing to 100.3 octane point of overall yield of the product high number on additlon of ethyl fluid equivalent to portion of useful material in the product and the 2 tetra ethyl lead per gallon T lower boiling range of the Small residue obtained 60 d1st1llat1on range of the product was substantially These advantages were demonstrated in the rethe same PF when dilsobutene is sults recorded in the following Table No. 3 which under slmllar. condltwns- Fractlonation werev obtained with diisobutene and isobutane heated the presence of appreciable quantities of in the weight ratios of 1:1 and 1:2 The results iso-octane (2.2.4 trimethylpentane) in this prodrecorded in Table No. 3 indicate that a substan- 5 tial or considerable excess of iso-butane favours 1 EXAJWPLE 8 the formation of the octane fraction. The pro- The olefine employed consisted in a fraction portion of useful product is much higher than having a boiling range of 105-112 0. taken from when equimolecular proportions of isobutane and the product formed by the condensation of noleflne are used. The yield of 2.2.4 trimethylbutene and isobutene in the C4 cut from gas depentane recoverable by distillation is also inrived from an oil cracking plant, when using a creased considerably. Similar results were obphosphoric acid catalyst. The material in questained in the use of triisobutene in place of the tion consisted largely of the condensation proddimeride. On the other hand the use of isobunot from one molecule each of n-butene and isotane in substantial or considerableexcess offers butene, being essentiallya2.2.3,trimethylpentene,

i and is hereinafterreterre polymer To a mixture of 1600 cc.'sulphur1c acid (97 per:

cent)l.,and.3000 cc. isobutane were tadded1.800 g.

I (aboutg2430 cc.) of --butene-isobuteneipolymer; 1

'o'as-butene -isobiitene over a period of :90 minutes maintaining the temperature steady at 20 C. against-the heat of con; densation'," the pressure being sufficient to maine tain,=the liquidphase; Finally;.-after:a further 30. .5

minutes .agitation, the'p'rod uct was separated'frdmzthe. acid-yand 'jworked up as in-.preyiougiexamples. The .initial hydrocarbon toacid ratio. was-1 about. 1 l 1.81:1 with afinalratioiof;about23.4nl." The yield:

en-L. idistillatioir pthe yield of the:

of the crude productmfgspecific;gravity .713 ,at nd Jaromine: numberiitlirancis) v:2, was...

.5158; percent zyieldmased upon the.

alkylating-reaction conditions-and a volume rav tio oftotalquantities-of hydrocarbons .to sulfuric acid in thereactionzone of between about 1.5:1

the isobutane being present in at least 2 mols per moi-of diisobutylene, at a temperatur of between about ,-.-10 C. and about C. under suflicient superatmospheric pressure to maintain the reactants in the liquid phase, in the presence of concentrated sulfuric acid, maintaining vigorous fraction. having ;boil-ing.;r:ange 10f. 27%185" zC'. was

mine r glirancis) 16.55 than l and an octane rating Q 1f 8 7,-th6. fQGta-Ile number increasing to 919 with addition of ethyl fluid equivalent to 1.5

cc. tetra ethyl lead per gallon (Imp.).

The product obtained from a crude buteneisobutene polymer, a fraction of boiling range 95-120 C. which also contained a small amount of diisobutene' gave practicallythe same yield, but the octane rating of the product was 88.7 octane number, and 99.2 octane number with addition of 1.5 cc. tetra ethyl lead per gallon (Imp.)

' EXAMPLE '9 To 2000 cc. isobutane andl070 cc. of sulphuric acid (9'7 per cent) were added while maintaining the temperature at 20? C.and stirring vigorously, 2700 cc. of a crude C4 fraction cut from cracking gas and containing 94% of C4 unsaturated hydrocarbons, the pressure used being suflicient to maintainthe reactants in'the liquid phase. Addition was carried out over a period of 90 minutes followed by a further 30 minutes agitation. The initial :hydrocarbon to acid volume ratio was about 1.87 :1 with the'final ratio being roughly 4.421. The crude product after a thorough neutralisation with caustic soda was redistilled and yielded a fraction boiling 27-185" C. with a. gravity of 3706/60? F. and bromine number (Francis) of 1. Tested on the engine the neat product gave by the C. F. R. motor method 91.6 octane number rising to 99.5 octane number with the addition [least one isoparaflln with at least one olefin in the presence of concentrated sulfuric acid while correlating the reaction conditions to produce a normally liquid, substantially completely saturated product, the volumetric ratio of the total "hydrocarbon present inthe reaction zone to the amount of sulfuric acid present therein being maintained between about 15:1 and about 4.4:1.

2. A process which comprises reactinglow boiling olefins with low boiling isoparafl'ins, the isoparaiiins' being present in the reaction mixture throughout the entire reaction in substantial molar excess over the stoichiometrical equivalent monomeric contents of the olefins in the presence of concentrated sulfuric acid whil maintaining agitation of the reaction mixture, maintaining a r volumetricratio of total hydrocarbon to acid in the reaction zone of from about 1.5:1 toabout' 4.4:1, for a, length .0f time sufilcient toefiect a substantial alkylation reaction, and recovering the normally liquid saturated product from the reaction mixture.

5. A process as in claim 4 wherein the process is carried out continuously.

6. A process as in claim 4 wherein the diisobutylene is substituted by .a polymer gasoline prepared by condensing olefins having no more than 4 carbon atoms per molecule.

7. A process for the production of normally liquid, substantially completely saturated hydrocarbons boiling within the gasoline boiling range which comprises condensing isobutane with monoolefins having fewer than five carbon atoms per molecule, the isobutane being present in suband recovering the reaction products from thereacted mixture.

8. A process as in claim '7 wherein Ci monoolefins are employed and the reaction is carried out continuously. V

9. A process forthe production of normally liquid, saturated, branched chain hydrocarbons which comprises reacting isoparafiin with liquid monoolefin in'the presence of concentrated'sulfuricacid of alkylating strength with vigorous agitation under alkylation reaction conditions and under suflicient superatmospheric pressure to maintain liquid phase operation while maintaining a hydrocarbonzacid volume ratio between about 1.5:1 and about 4.4:1.

10. A process as in claim 9 wherein the olefin is added gradually with agitation to a pro-admixture of the isoparaflin and the sulfuric acid and wherein the isoparaflin is maintained in substantial molar excess over the olefin throughout the reaction. 7

11. A process for the production of motor fuel constituents comprising essentially branched chain, saturated hydrocarbons boiling within the motor fuel range which comprises reacting a liquid monoolefin with at least one isoparafiin in the presence of 97-100% sulfuric acid under alkylation reaction conditions wherein the total hydrocarbonzacid volume ratio is maintained between about 1.5:l and about 4.4:1.

12. A process which comprises maintaining a liquid admixture comprising essentially at leis'b one tertiary cErb'onat'om per molecule all! time acid having a cofienfirfltion between abeut" 97% and abdufi 100% in a volume ratio- 01' be tween about 1.521 about 2-21; maintaining tlons, alkylaflng' the contenttfiefeet by adding gradually to the mixture mondolefln while agitating the reaction mixture; the ml hydrocarbomblcld' ratio" Being lilalintialned durin 1 I the reaction between (them-265:1 a'nd= abdutfil :1 13. A process which eoihiirlses condmlfiift least one is'opa'l a mn wim an least oneuofi'uill y liquid olefinlc pol y'zixef m me presence'ot' cmieem alkylation remmn d'ndltlbh's While mmzm g i th'vblumetric ratio 0! will hy dldcarbon td sulfuric ald betweenabout 1.521 and about' 414211 14'. A pro'c'ess' claim I3 Whereln thevolu metrie ratio 1s maintaltied inltla'll'y' betweh ibdut 15:1 and about 2.0:11 and nnany from ab'out2k5'il and about 41411 and? wherein the 1mparamn is lnasulit'ant-lelly molarexcess over the Olefin;

15%. process tar like; production of mommyleast one with amv least one normally llguld' olefin at a: temperature between about --10' SfldIBOl It -FM C} lindr' Ma least i about 1.5 :1 'andE afiout 424 1 while maintaining the teact'ldfl lin'l xfilr'e' intensively asiiat'ed for a length-l at time sun'lclent lieeflect a substantial