US2773896A - Manufacture of alkyl aryl sulfonates - Google Patents

Description

Dec. 11, 195e J. W. PUTT VMANUFACTUREZ OF ALKYL ARYL SULFONATES Filed April 24. 1952 ATTORNEY United States Patent l MANUFACTURE F ALKYL ARYL SULFONATES James W. Putt, Los Angeles, Calif.

Application April 24, 1952, Serial No. 284,041

21 claims. (cl. 26o-sos) This disclosure is concerned vwith a .very economical method for the manufacture vof surface active agents and synthetic detergents, particularly with the active .ingre dient of such synthetic detergents. Generally speaking, there are three classes of surfaceactive agents: anionic, .cationic and nonionic. Furthermore, there are various types of organic .chemical compounds included in each class. For instance, the anionics may include salts of (l) alkyl sulfates, .(2) long chain fatty acids and (3) sulfonic acids of mononuclear .and polynuclear aromatic hydrocarbons, their alkylated derivatives and other derivatives of such hydrocarbons. The present invention is especially concerned with the sulfonic acid of alkylated aromatic hydrocarbons, vand salts of such acid. A salient object .of this invention is to devise a process whereby such salts can be prepared in a high degree of purity in a very economical manner.

Fhe greatest proportion of the alkyl aryl sulfonate In -the new method the olefin employed may be the same as the dodecene used in most of the alkyl aryl types of active sold heretofore. However, -the process is not limited lto dodecene. For instance, tripolylene (nonylene) diisobutylene and trsobutylene have 'been employed Vto yield la `very successful product.

' While benzene may be used Aas the aromatic hydrocarbon, it is by no means essential.V In `the newmethod it Vis displaced 'by Ia mixture of aromatic hydrocarbons particularly :those boiling between 390 -FL and 600 F. or preferably between 400 F. and l550 F. Essentially this mixture consists 'of -alkylfnaphthalens with or Awithout naphthalene itself. While lit -is preferable that this mixture -be substantally free from non-aromatic hydrocarbons, it is not essential because Vthey are ysubsequently eliminated in the process. The required hydrocarbons,

Y constituting the starting material, :may be obtained from type of surface active agent sold at .present consists ofV the sulfonate of dodecyl benzene. Its manufacture involves the following general steps:

l. 'Preparation of dodecene. 2. Alkylation of benzene by reaction with at least an equivalentquantity of dodecene to form dodecylbenzene followed by its separation and purication.

3. Sulfonation of the .dodecylbenzene with a large excess of fuming sulfuric acid. l

4. Neutralization of the sulfonationl mixture to yield the active, sodium dodecyl `benzene sulfonate, ,admixed with a large proportion of sodium sulfate.

5. Extraction of the sulfate-sulfonate mixture with ethyl alcohol to separate the sulfonate and separation of the alcohol therefrom.

6. Drying.

Builders such as polyphosphate, borax, carbonate may be added before or subsequent to step .6. To a large extent step 5 is .a Apresent omitted Vbecause .it is very expensive, and because the product :otherwise would Ybe hygroscopic. The omission, of course, leaves a product withavery large proportion of sodium sulfate, an undesirable 'feature because it limits the concentration of surface active agent Iin the nished detergent and causes 'a disagreeable reaction of the detergent .on the hands Y of petroleum naphtha required.

ln the new method of the invention for the production of alkyl aryl sulfonates, both the starting substance land the steps of the process are modified in a novel manner so that the product is obtained at a vastly reduced cost.

coal tar or the like. -l-n sharp lcontrast with fbenzene, the chemical ydemand for =the v390 F.-600 F. is not great. -lt Ais easily -procurable ata -steady'price -Fu'rthermore, yespecially of 'great importance this fraction forms a large proportion `of the product from'the subjection of certain petroleum fractions of wide boiling range in accordance with my VPatent lNo.2,207,-552, and may be derived from such product 'by simple fractionation.

As hereinabove stated, the prevalent Vmethod used for the production of alkyl aryl sulfonates -involves the interaction of benzene and ,at 'least an -equimolecular quantity of olefin, followed by Athe isolation and vpurification of alkylated vbenzene andthe sultonation of this product with :turning sulfuric acid ina distinctly separate step.

in striking contrast, -in the -new method, sulfonation takes place inthe same kettle in which the alkylation step is carried out Without yany -priorseparation 'whatsoever. Aromatic hydrocarbon, olen and sulfuric Vacid are .all mixed in a kettle to yield the desired sulfonic acid of the .alkylated aromatic hydrocarbon in one Vsimple process step. While due .to the possibility y.that alkylation proceeds at a faster .rate than .does sulfonation, alkylation may actually take placesrst', followed by sulfonation, to all intents Aand purposes from va practical standpoint, alkylationand sulfonationare .carried .out in one step with agreat saving in plant Ainstallation vcost and opertaing cost. Y

The new Ymethod has a .further important economic advantage in that it has been found that because .of peculiar properties .of ythe .mixture .of aromatic hydrocarbons, .an equimolecular :quantity of oleiin'is not required. quantity of oleiin gave a good product. This .is .quite an economicgadvantagein yiew .of the .fact that lthe olen is more costly than .the-aromatic hydrocarbon mixture especially .when the latter is prepared in .accordance with Patent No. 2,207,552. Furthermore,gin the..presence of so low a Vrelative quantitycf volefin .there is very Vlittle Vor no likelihood 4:for .polyalkylation and esteriiication of the sulfonic acid -to take place.

The aromatic mixture -used inthe .process is much more .easilysulfonated than is benzene. As a Yresult the.

sulfonation can be carried out .With98% sulfuricV acid although turning acid 4can/be used. acid would not be suitable. However, ithas ,been found that the required reaction can be carried out with greater facility by using stronger acid than 9,8%, preferably ,by starting out with '98% sulfuric Vacid to the extent of about 30%60% of the total acid required and thenv completing the reaction with Istronger acid such as 5% to 20% fuming 4sulfuric acid.

lt has been stated above that :the sulfonationofdodecyl benzene requires alarge excess of sulfuric acid. This is also true in the vcase of the lmixture of varomatic hydrocarbons `used in ,the :present process. However, in :the

In fact, Vas little as 30% of an -equimolecular With benzene 98% 'Y "fuging the sulfonic acid layer. Vthe ability to recover this excess acid results in three very modity.

A embodiment of the process.

case of 'dodecyl benzene, the dried sodiumsalt of the sulfomc acid is quite hygroscopic and is therefore sold in admixture with a high concentration of sodium sulfate in order to overcome this difficulty.` To provide this sodium sulfate, the excess sulfuric-acid is neutralized together with the sulfonic acid. YA product containing sodium sulfonate Vadmxed with a large proportion of sodium sulfate results. This operation'fnecessarilv requires a large expenditure of sodium hydroxide;VY This is dlsadvantageous because itdepreciates a large quantity of 'sulfuric acid, a fact of quite some yconcern in these days of short supply of sulfur. .It consumes large quantities of sodium hydroxide Yand Yresultsinra product with a lowv concentration ofacrtive.'V Furthermore, wheneven despite the hygroscopicity, a product with `ahigh concentration of surface active agent is desired, the expensive step of alco-` hol. extraction has to be resorted to because of the large quantity of sulfuric acid sulfonic acid. Y Y

`With the/aromaticrmixture usedl in thisV process, however, the resulting Vsodium sulfonate is non-hygroscopic and can thus be maintained exposed toVordinary-'atmo'sthat remains dissolved in the phere Without danger lof* caking or of vany other defect.

Because of the highv concentration in which the surface active agent can be prepared, the range of finished detergents has f beenV enhanced tremendously. Furthermore.l

this high concentration of surface active agent canibe procured quite simplyfbecause the greater part of the excess sulfuric acid separates by gravity from the Sulfonic acid and is therefore easily recovered therefrom. A further quantity of sulfurieacid is obtained upon centri- As will be appreciated.

important economic advantages: The recovered sulfuric :acid is made available for further use, a factor of extreme importance becauseY of the very short supply of this corn- Secondly, ja great-savingv in thecost of alkali is V"achieved because alkaliV does'nothave to be used to'neu- Vtralize this excess acid. Finally, the surface active agent is recovered in very high concentrations because it is notfaccoinpanied by very large quantities-ofY sodium sulfate asin the prior processen, I, Y 1 l Any residualy sulfuric acid remaining ,adr-mixed .withthe sulfonicj acid is removed *by conversion by addition Vof lime to calciumlsulfate andjseparated by filtration.V Thu's Vtheprocess -is capableY ofproducing surface 'activerv agent accompanied Yby'little or no sodium'sulfa'te although a small proportion yfisallowed to remain because 1t acts asY `abulder.l f 'H In orderto insure' a clear understandingof the new process and an evaluation 'of itsfnjeritsgreference is made to the accompanying drawing which illustrates but one vAsrshownin the drawing, a Ypetroleum oil,V prefer-ahh.'

Vone the major portion of which/boils between 400 and V600" VFisltaken'rfrom storage 1 and is continuously passed 'Y to Van` extraction unit 2. "Any" solvent such as sulfur dioxide, furfural or 'thelike which will eliciently separate the parajns from the other hydrocarbons, particularly the aromatics and ole'tinrs, may be employed. Treatment in the extraction unit leads to the formation of a raflinate which Vishwithdrawn throughline 3 and an extract withdrawnthroughlin'e 4; The solvent is removed: from both the rainate and V.extract by 'suit-able. means, not shown.V The Yraliinate is removed. from Ythe system as one of the 'Y ndproducts fof the process. f Y t The extract is then subjectedY to cracking at elevated rate through compressor 7 and heater Sbeore it comes in contact with the heated stream of extract in line 6.

The air reacts with some of the heatedroilresulting in Y an increase in temperature to the desired level of about Y 1050 F. to 1200o F., preferablyfbetween 1125u F. and

1175 F. As is well understood, the quantity of air in aromatization occurs, ldepending upon the gravity ;and

sidual ,oil is further processed to lyield pitch with a desired n il Aboiling range of the'raw chargeand reaction temperature.` 20

series of Vseparators 10, 11 and 12. VFromseparat'or `1t) Y The product from vreactor 9'is conductedthrough a heavy residual oil is removed through line;` 13.V Thisy re.

melt point. The vapors Vfrom separator 10are fractionated in Vessel 11 from which is discharged an overhead containingV light products and water` formed from the Y action 'of the air and extract. The light products `contain combustion products, hydrogen, methane, other paraftns and olens with V2 to 5 carbon atoms andaromaticslwith 6 t0 9 carbon atoms. This overhead is passed through condenser 14 and accumulator 15 wherein waterY is al- Y lowed to separate and is dischargedtherefrom through lineV 16. Some light oil is returned by means of pump 17 as reux to fractionator 11rr The remainderis discharged through line 18 to storage. This oil may be refined by treatment with sulfuric acidras is well understood and a pre-benzeneY cut removed by fractionation.VV 1

The'remainder containing toluene; yxylenesr, a mixture of C9V aromatic hydrocarbons together with' a small quantity of benzene may well be employed as aviationrich mX- *V i l i ture or separated into individualV components., Alterdischarged .from tower 12 Vthrough. line'v 20.toV storage.`

This oil may beV later treated toseparate carbazole-free i anthracene suitable for oxidation. to anthraquinonei j ',The detergent stock leaves Yas vaporlhfromthe upper portion of tower 112,1is passed through cooler 21, ,thenceVV nately the light oil may iirst beA fractionated, particularly` to separatealphamethyl styrene,.before being subjected Vto chemical treatment. Y 1

g vThe 'uncondensed portion of the products may be separated in accumulator 15, discharged through line19and" Y Y conducted to an absorption system toreover condensible Y y products therefrom and'maythen be employed as fueljor ared. Y

The portion is passed to fractionator 12.Y Herein detergent Vstock boilingbetween 390"V and 550 Ffis separated as ,an Aoverhead. from a heavier and higher .boiling oil which has the A' characteristics of Yanthracene oil. .The anthracene oilis to accumulator 22. Arportion is returned as redux by temperaturesparticularly in ,theV presence of an extraneousVY gas; In`the particular embodiment chosen, airYV is Vused as the extraneousgas whichserves to provide autogenous yheat. 'The extract is pumped to arheater 5 .where'it is heated to about 700 F. and thence conducted to line 6 where it meetsand is mixedwith aV stream of heated air. airhad'previouslybeen passed Tat Va predetermined Ythetype herein described; j Y

means of pump 23 toto'werlZ and 'the remainder con verted to detergent.V Dependent upon', factors extraneous to the'. matter or `detergents,'it maybe'gdesirable to separateA Y Y a part or all .ofthe naphthalene` fromV the detergent stock. This can be .done inany knownmannenisuch asby close fractionation. The naphthalenecanthen be marketed as such or converted to derivatives such as phthalic anhydride, beta-naphthol, naphth'ylramineor to adeterg'entpfV Before thek detergent stock Y has lto be chemically treated. g VThe art of treatingdeter- Vgenttstocl is the'same as that'practiced in the prepara tion of pure aromatic 'hydrocarbons such as benrzenerrand Y toluene,AV destinedV forthe manufacturero dyesand:medieV Y of the product tower llvaboiling.generi ally above 390 F., leaves the tower at Ythe bottom and Y is. converted, however, it 'f 5 cinals. Therefore, the treating process will notY be described in detail. However, it should be noted that the detergent stock should first be treated with alkali to remove phenolic compounds, then with acid recovered in a later step, to extract nitrogen bases. The phenolic compounds and nitrogen bases can be recovered by neutralizing their respective solutions. It is economically advantageous to do this. v

After the oilhas been freed from acidic and basic constituents, it is treated one or more times with a relatively small amount of sulfuric acid. Spent acid obtained in a later step can advantageously be employed for at least a part of the reiining treatment followed by commercial 66 B. sulfuric acid in an amount equal to a total of from to 20 lbs. per barrel, in two steps. With proper care known in thetreating of aromatic hydrocarbons and lubricating oil, the acid-treated oil is washed and then redistilled. It is then ready for conversion to active or detergent.

The description of the new process followed to convert the detergent stock into surface active agent and detergent may be more easily understood by study of the following' mol. equivalent of nonylene is employed. Thus both naphthalene and nonyl naphthalene derivatives arepresentv in the final product. The reactions may bel represented as follows:

(i) CH3 where R is the radical remaining upon removal of H from The compound designated by RSOsNa is, of course, the desired surface active'agent. s l

In' carrying out the process, the. treated detergent stock is. transferredto a jacketed kettlel 24 equippedwith. agritator; the valves 26 and 27 remain closed during the-whole sulfonation reaction. An olefin such as tripropylene, tetrapropylene or other olein or mixture of olenscontaining 8 to 18 carbon atoms is also charged to the kettle 24. Y The quantity of oleiin may vary between 10 and 100- mol percent depending upon the boiling range of the-.aromatic'hydr'ocargon mixture, the olen employedand the l quality of the surface active agent desired. A surface Vactive'agerrtofv high quality has been obtained from theV use of: 310 mol percent of tripropylene. The olefin and aromatic vhydrocarbon are thoroughly, mixed. by means ofthe stirren The-mixture is then subjected to an alkyl- Y ation-and sulfonation reaction in one step. Sulfuric acid-A is used'zin both reactions: tained .in operation, sulfuric acid of 98% concentration- While the stirreris ,mainor.v stronger is at first added? slowly at such rate that the temperature does not rise above about 105 F. to 110 F. A. streamv of cold water is passed through the jacket of the kettleA to control this temperature. Usually it takes 20'to 30 minutes to add the acid in a volume equal toV about 1/2 of the total volume of detergent stock and olefin. When such a volume of acid has been added, another like volume of acid is added to the reaction mixture. This can be done more quickly and without the aid of the cold stream of water. A period of about 10 minutes can be taken for such addition. Thus the total volume of acid employed is equal to the total volume of hydrocarbon undergoing reaction. Stirring is preferably continued but the reaction is aided by allowing a stream of hot water to pass through the jacket to raise the temperature of the reaction mass to about 145 F. and to maintain it at this point until the sulfonation is complete.

AsV the reaction proceeds, the mass which is reddish in color, becomes more and more viscous.` The end of the reaction is determined by noting the behavior of a drop of reaction mass on a glass wall. A shiny appearance alkali or sodium carbonate.

` completion a large volume of dense stable suds is obhas reached about 15% of the total original hydrocarbon volume. ably decreases.

The Viscosity of the mass then notice- The volume of' added water is noti critical. More than the noted volume may be employedr Without harm to the reaction. However, such increasedk volume increases the cost of drying the finished product. A periodV ofabout' l0 minutes is generally required for the addition of the water. Stirring is then stopped and'A the mass allowed to remain in a quiescent state; This permits excess sulfuric acid or'a part thereof, to separatel asa lower'layer from the sulfonic acid. Water, equal inA volume to about V5% of the original total volume of, hydrocarbons, is then very slowly and carefully poured down one' side of kettle 24. Upon intermingling with the' acid mass, the water causes the separation of a layer of oilthat had not been sulfonated, either due to actual incompleteness of the reaction or because some unsulfonatable oil was originally present, or both.

With this procedure a three-layer system is obtained, the sulfonic acid beingV established between an upper layer of' o'il, lgenerally about 10% of the volumeY of the original detergent stock, and a lower layer of sulfuric acid.4 About 20 minutes is allowedV for separation to take place. The vlower layer'of sulfuric acid isthen withdrawn through lines 33 and 28 by opening valve 27 and is passed through line 2S to storage for later concentration or conversion to useful products such as ammonium sulfate or copper sulfate. After complete removal of the sulfuric acid, valve 27 is closed and valver'26 is opened and the sulfonic acid is then separated from the unsulfonated oil and transferred to jacketed kettle 29v through lines 323 and 3S' for further purification. After such separation kettle 24 is vavailable for another sulfonation batch.' lf desired, the' sulfonic acid may iirst Y be subjected toa centrifugal action in centrifuge '30,

- whereby a further amount of free sulfuricV acid is separated and withdrawn'through line 28. Lines 33,734

and 35YA are. unusually large in diameter on account of Some free sulfuric acid amounting to about20 to 30% Y,

- detergent builders.

Y as hot air or hot combustion gases.

known in the art and therefore need not be describedi 60" Ytom either continuously through line 41 by VmeansY of a 'the detergent dried'in drier 40.V l

of that originally added still remains 'dissolved inthe sulfonic acid. This is neutralized by means of Vlime added in kettle 29 which isl equipped with'stirrer. The contents'of this kettle are agitated and Ycooled by meansV of a stream of cold water passing'throughf the jacket 5 31V;V From hopper 32, lime slightly in excess of the amount Vequivalent to the free vsulfuric acid in the sulfonic acid mass is added and caused to react with the acid mixture. Sufhcient time is allowed to insure 'substantially complete reaction with the sulfuric acid. At l least Asome, of the excess lime neutralizes an equivalent amount of sulfonic acid. VThe calcium sulfonate formed, however, remains dissolved in the sulfonic acid to by far'the largest extent. Y

'Afterfcompletion of Vthe neutralization,reaction, the 15 contents of the kettle are discharged from the bottom andare passed to thefilter. The calcium sulfate formed in kettle 29, together with any lime'that may have escaped A reaction, is thus separated from the'sulfo'nic acid by filtra? tion. The ltrate is then passed'toneutralization tank 20 38. The filter 36 may be of any. known type and may,

if desired, even be replaced by a centrifuge. f

Therdesired surface-active compound is the sodium salt of the sulfonic acid. The sulfonic acid is converted to its-sodiumvsalt by neutralizationwith an equivalent amount of sodium hydroxide solution. -The'quantity of alkali is-very critical becauserthe addition of too` much would leave free alkali associatedv with the finishedr detergent, an undesirable situation as Vis now very well known. On the otherhand, the use of an insufcient 30 amount would, of course, leave free sulfonic acid. This similarly is undesirable because it would interfere with the drying` of the finished detergent, would lgreatly decrease its quality asY a washing compound'and would Y produce a corrosive product. However, the addition of an Vinsufcient quantity of alkali` can be corrected -at a later step. A very good method Yto follow Vis to add alkali until the mass becomes-neutral as indicated Vby'a pH of 7. 'i

The nsolution at this point may contain a small amount 40' of calcium Vsulfonate as a result of theprior addition of more lime than was necessary'to neutralize the free sulfuric acid in the sulfonic acid. This calcium sulfonate is converted to the4 desired corresponding sodium salt by Y adding thereto sodium carbonate or its aqueous solution not decreasein anyV way the quality ofthe detergent because/sodium carbonate is recognizedas one of 'the' v The last step in the process involves the Vremoval ofy the water from the solutionof the Vsurface Aactive comipound. This is accomplished by transferring the filtratel from filter 39 to drier 4! wherein the water is evaporated by means of indirect yheat, exchange with hot gases such This step is well TheY dried surface active agent is withdrawn at theV botscrew or intermittently. Water vapor and other gases orf vaporsle'ave the drier at the top through line 42.

Surface-active Vcompounds .infa'"concentrat1on of 90% or overfare Yobtained inthis manner. Builders such as Y phosphates, polyphosphates, borax, carbonates ,orV siliagents such Vas lauryl sulfate f andrvmodiers such` asy y carboxy methyl cellulose may also be added. However, any or all oftheseY substances mayalso be addedrtoA the.

Vsolution of surface active agentvr in tank13`8,`jwherein they can Vbecome intimately mixed, Vandthe solutioniiof 7 t times itehas been kfound that hydrcxizarbon.r oil'inay remain dissolved in the solution of surface active agent.

This oil reduces the quality of the finished detergent; i ItV matic hydrocarbon mixture as described above, it appears that alkylation is virtually completerbeforethe sulfonation reaction sets in to any degree. case, some olefin would be in contact with sulfonic acid and Ysulphuric acid. Bothof these acids are esterication catalysts. and thereforesome esterication would befex-V pected. lf esters wereV formed, they would b e present in the oil obtained upon the careful addition of waiterV to the sulfonic acid.V This oil was analyzedandwwas Vfound to contain VlessV than 1% of sulfonic ester. YIn view of the fact that the volume of the oil constituted only about 10% ofk the volume of original aromatic hydrocarbons, ester formation took place to the extent of lessV than 0.1%, a negligible quantity.

The process as described involved the subjection of th -V Yraw feed .to anV extractionv step followed by a` thermal cracking reaction, to prepare the aromatic" hydrocarbon Vmixture for the alkylation-sulfonation step in kettle 24.

These steps may be modified in several ways without in l any way affecting the nature'nor the novelty of the pr`oc`V ess. For instancefthe raw feed may be made to undergo one of several catalytic cracking processes, such as Fluid,

TCC, Houdry, followed by separation of gasoline, lighter'V Y products and fuelV oil, and subjection of thecrackedY product boiling between gasoline andfuel oil to the cracking step in reactor 9. Furthermore, insteadjof. interact-v ing oil vapors'with air, they may be subjected to direct vheat Yexchange relationship with hot combustion gasesor any other gas heated in sucient'quantity and to a sufliciently high degree Vso asto heat the oil vapors in reactor 9 to a temperature of 10570" F..to 1200" F. y

The cracking step of the processas effected in reactor'. 9 has been described as being purely thermal. YHowever, y

natural or synthetic catalysts ofthe types used in ordinary petroleum catalytic cracking process -may `Vbe employed effectively. Y

, Furthermorea portion'of coal tar boiling'between V 390 F. and 600 F. 'before or Vafter removal of naphthalene may be chemicallyl treated*Y with alkaliV and sulfurie acid as described above in connectionuwith the purifcation Vof the detergentV cut frornaccumulator'ZZ, and then subjected to the Valkylation-'sulfonationYj.reaction,Y without undergoing Yanyextraction or'cracking steps whatsoever, to yield an acceptable detergent..

In an'example of one'embodiment of theprocess,"ex tract from diesel oil boiling between 407 F; and 600 F.V

was vcharged under a pressure of 60 p. sgi. g. toY heater f 5 at the rate of 9.3V G. P. H., and heatedV to a temperature ofj700fa At ljunction Y6 theroil vapors werebrou'ght in intimatecontact withn a stream ofV air flowing through heater 8 at the rate Vot 320 C. F. /hr. VAfter mixing, .the

temperature rose V-to 1170 Ff CrudeV aromatics were Y formedin afvolumetricY yield of 77.67% which, upondistillation, gave 38.01% detergent'cut, based on charge to heater 5,- 4.85 aviation richv mixture, 2.18%'fresinlcut (350 F. to 400'F.);and 32.56%v anthracene oil, pitch and distillation loss'. Y The .detergent cut was treated con--4 secutively with 35% NaOH to remove tarV acids, recovl ered ;H2SO4 toremove tar bases, twice with'J 66 Be. VVH2804 in aV quantity'of 8.6 lbs/bbl. to improvecolor and-j then redistilled. A-portion. of the treated detergentcut, f '230 cc., wasmixed Vwith 70 cc'. offt'riprop'ylene' inaaski equipped with a stirr'er. TotheY mixture in a cooll waterV bath was addeddu'r'inglminutes 150 cc. of 98%H2SO4.

aty such rate that the,temperatureldidA not rise above 1107"- F.iThe water-bath was thenremoved and camere If this were not the amasseof 98%, H2504 was added during 5.. minutes. Tri.: mixture was then heated on af hotV water bath; whereby the temperature was allowed toy rise to, 145 F. wl'iile-tllfev stirring Vof the mixture, now quite. viscous, was continued. In about l minutes, tests as above; explained, showed that the alkylationrsulfonation reaction was practically complete. 50 cc. of water was added slowly and the mixture transferred to a separatoryfunnel.` Sulfuric acid began to separateimmediately. About 20, cc. water was allowed to run down the wall whereby unsulfonated oil began to rise from the sulfonic acid. The excess acid layer was removed followed by thesulfonic acid leaving 22 cc. unsulfonatedoil. Io, the sulfonic acid was added 50 gms. of lime, thoroughly mixed and the CaSOi separatedVv by lti-ation. The filtrate was neutralized by addingY 30% NaOH until' the pH was raised to 7. The solution was then-heated and to itwas added a small quantity of NaCOa solution unt-il-t-hepllof the solution was raised to 8. Calcium carbonate" precipitated. This was separated byjiltratiorr;V ltrate was washed twice, with benzene and then heated to drive o t the water.

A lght'colored slurry was `obtained which analysis` showed to contain active in a concentration wel over 90% on a Water-free basis and in a yield of over 80% of the theoretical, based on the detergent stock charged.

The product formed a large amount of long lasting dense suds and upon a washing test after addition of sodium tripolyphosphate and carboxy methyl cellulose, was found to have a very high degree of detergency and whiteness retention.

lt is to be noted that in processes known heretofore, a surface active agent with a high degreeot" detergency can be obtained only by extraction of the active solution with a solvent such as alcohol. This is expensive. in the described process, a product with a higher concentration of surface active agent than any anion surface active agent generally on the market is-obtained without the necessity or" an alcohol extraction of the sulfonate solution.

The process has been especially described in connection with the sodium salt of the sulfonic acid. Similar sulfonate of other metals or of ammonium, alkyl ammonium, or hydroxy-ammonium compounds can be prepared in the same manner by employing the oxide or hydroxide of the desired metal or ammonium derivatives as the neutralizing agent. The sulfonates of the alkaline earth metals such as calcium deserve attention, for their preparation is quite easy since all that is needed is to add an excess of metal oxide to the mixture of sulfuric acid and sulfonic acid. The calcium sulfonate solution is easily separated by filtration from the precipitated calcium sulfate and the water evaporated by known means from the solution to obtain the dry sulfonate. This saves many steps that are necessary in the preparation of the corresponding sodium sulfonate.

The method of'producing anionic detergentsV herein described has been directed toward the fraction essentially aromatic hydrocarbons boiling between 390 F. and 600 F. as the feed to the detergent reaction. it has been found, however, that equally eiective detergents can be prepared by utilizing the lower boiling aromatic oil boiling between 180 F. and 390 F., and even the broader cut boiling between about 180 r. and 600 F. Y

as the feed. ln utilizing this fraction containing the lower boiling aromatic hydrocarbons, it was found desirable` but not absolutely necessary to separate the fraction boiling between about 360 F. and 390 F. from which proplyene benzene can be isolated. The use of 98% sulfuric acid followed by stronger acid, as has already been described above, is ofl especial bene't when detergentsV are made from oil containing the cut boiling between 180 F. and 300 F. to 400 F. Y

While preferred modifications of the inventionr have been described, it is to be understood that these are given didacticaily to illustrate the underlying principles in- 1:0 volved and not as limiting its useful scope to the particular'illustratedj embodiments.

Iclaim:

l. A'process of producing anionic surface-active com-` pounds which comprises simultaneously alkylating and sulfonating a mixture of aromaticy hydrocarbons having a boiling range within the limits from substantially 390 F. to substantially 600 F., with an olefin inthe presence of sulfuric acid in a'single'reaction zone; agitating the reaction mixture in said smgle reaction zone until alkylation andY sulfonation are substantially completely eected, adding water tothe reacted mixture in amounts-and under conditions'controlled to effect layer separation of free ysulfuric acid, unsulfonated oil and alkyl aryl` sulfonic acid, separating thelayers, recovering the alkyl aryl sulfonic acid and neutralizing the sulfonic acid with basic material4 to form the corresponding alkyl aryl sulfonates.

2.A-process in accorda-nce with claim 1 in which the quantity-of olefin en iployexi' isfless thang-an equimolar quantity of the aromatic hydrocarbons.

A3.Y A process in4 accordanceV with claimy l; in; whichj the sulfuric acid employed-in. thereaction comprises; substan- 4. A process in accordance with claim l in which the..

aromatic hydrocarbon mixture has a boiling range of from substantially within 430 F.5 00 F.

- 5. A process in accordance with claim 1 in which the aromatic hydrocarbon mixture is comprised preponderantly of alkyl naphthalenes.

6. A process in accordance wtih claim 1 in which the aromatic hydrocarbon mixture is comprised preponderantly of alkyl naphtha'lene and is substantially free from basic and acidic constituents.

7. A process in accordance with claim l in which the aromatic hydrocarbon mixture is derived from cracked petroleum oil.

8. VA process in accordance with claim l in which the aromatic hydrocarbon mixture is derived from coal tar distillates.

9. A-process in accordance with claim 1 in which the separated alkyl aryl sulfonic. acid is treated with an alkaline earth reagent in amounts su'icient to react with and oil.

ll. A process in accordance with claim 1 in which the olen is chosen from the group consisting of dodecene, tripropylene, diisobutylene and triisobutylene. Y

12. A process in accordance with claim l in which the aromatic hydrocarbon mixture has a boiling range of from substantially 180 F. to 600 F.

13. A process in accordance with claim l in which the olen is added to the extent of 30 to 70 mol percent in relationship to the hydrocarbon. y

14. A method of producing an alkyl aryl sulfonate from petroleum oil which comprises ysubjecting a petroleum fraction boiling within about 250 F. and 600 F. to the solvent action of SO2 to extract the non-parainic hydrocarbons, separating the solvent from such non-paranic hydrocarbons, subjecting such hydrocarbons to cracking conditions of temperature and pressure controlled to prol ing between about 390 F. and 600 F. treating the separated fraction to remove therefrom the phenolic cornpounds and nitrogen bases; simultaneously alkylating and sulfonating the purified separated fraction with an olen in the presence of strong sulfuric acidy in a singleireaction zoneV while agitating thev reaction mixturel for a period of time suliicient to substantially complete Vthe @gasses alkylation and sulfonation reactions; adding vvater to' the t reaction product in an amount and under conditions concipitate -an alkaline earth sulfate, VYneutralizing the thusV treated sulfonicV acid with a basic material, separating the liquid from V'the precipitate, treating the neutralized product'with an alkaline carbonate to yield substantially a pH of 8, andseparating the precipitate byliltrationrV from the Valkyl'aryl sulfonate. f

-16.,A^ process in accordance with claim 14 in which the f sulfuric acid employed inthev "reaction comprises 98% sulfuric acid. f f 1 17.7A process in accordance with claim 1,5 in which prior to drying the alkyl-aryl sulfonate is extracted Vwith a selective solvent to remove any contained unsulfonated oil.

;1'21 u 18. vprocess in accordance with' claim 14 in which the relationship'to the aromaticv hydrocarbon.

' 19. A process in accordance with claim 14V in which the sulfonic acid is converted to an alkali metal salt. t

' 20. Aprocess in accordance with claimV 14 in which. the sulfonic acid is converted to Van alkaline earth salt. Y V21. A process in accordance with claim 14 in vwhich the quantity of olefin employed is less Vthan an equimolar 'Y 1'0 quantity of the aromatic hydrocarbon.V

'References Citedrin thefle of this patent Y f STATES PATENTS Y 15 2,072,153 Brusoneta1., 1 25 1 fMar.72, 1937 2,227,999 v Y Brandt etal. 1 Jan.V 7, 1941 2,652,427 Y Shultz sr sept.,15,-1953 2,655,530 V`Nevisoli ,Oct. v13, 1953 20 f Y Y OTHER REFERENCES Y 4Schwartz-Perry: Surface Active IAg'entS, Interscience r Pub1ishers,1949,pp.116,124.. Y

olefin is added tothe extent of 30% to 70- mol percent `in

Claims (1)

1. A PROCESS OF PRODUCING ANIONIC SURFACE-ACTIVE COMPOUNDS WHICH COMPRISES SIMULTANEOUSLY ALKYLATING AND SULFONATING A MIXTURE OF AROMATIC HYDROCARBONS HAVING A BOILING RANGE WITHIN THE LIMITS FROM SUBSTANTIALLY 390* F. TO SUBSTANTIALLY 600* F., WITH AN OLEFIN IN THE PRESENCE OF SULFURIC ACID IN A SINGLE REACTION ZONE; AGITATING THE REACTION MIXTURE IN SAID SINGLE REACTION ZONE UNTIL ALKYLATION AND SULFONATION ARE SUBSTANTIALLY COMPLETELY EFFECTED, ADDING WATER TO THE REACTED MIXTURE IN AMOUNTS AND UNDER CONDITIONS CONTROLLED TO EFFECT LAYER SEPARATION OF FREE SULFURIC ACID, UNSULFONATED OIL AND ALKYL ARYL SULFONIC ACID, SEPARATING THE LAYERS, RECOVERING THE ALKYL ARYL SULFONIC ACID AND NEUTRALIZING THE SULFONIC ACID WITH BASIC MATERIAL TO FORM THE CORRESPONDING ALKYL ARYL SULFONATES.

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