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. Patented Jan. 25, 1938 Q j ‘ 1,106,521, - - UNlTED'STA'l'lIS PATENT oFFicaF ‘ 2,106,521 ' ' p - _ "commons mn'rnon or REAGTING ‘mourn REAGENTS .— Richard lid. Deaneoly, Berkeley. Calif” assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware .'No Drawing.. Application September 9, 1935, Serial No. 39,809 ‘ 1s ouma. (c1. zoo-99.12) This invention deals with a novel procedure for conducting chemical reactions between liquid re actants, particularly liquid reactants, each of which has a low physical solubility in the other, .5 in a continuous manner whereby greater e?lciency, ‘ in the consumption of reagents and economies of the reaction substantially takes place ‘whereby eiiicient use may be made of all reactants and highreaction rates attained. ~ . . - ‘Y My invention may be practicedtwith any suit- I able reactants in the liquid state which form re action mixtures made up‘o two liquid phases, operation may be e?ected. regardless of the nature of t e chemical reaction - The process of my invention essentially com or reactions involved. As examples of the diverse prises continuously adding the liquid reactants to _10 a reaction mixture of a composition with .respect reactions to which my invention may be applied, the nitration of toluene, the sulfonation of ben 10 to elements in the feed which differs from the zene, the hydrolysis of amyl chloride, the saponi?- , composition of the total feed with respect to those cation of esters, particularly fats and fatty oils, elements. To this end I ?nd it advantageous to and the esteri?cation, etheri?cation and ~hydra- "' continuously return to the reaction zone a sub ‘ tion of oleiines may; be mentioned as typical. 15 stantial part of one constituent of the reaction, While my invention is thus broadly applicable whether a reactant or a reaction product thereof, ' wherever liquid reagents of low physical solubility ' ‘ preferably after separation therefrom of any with respect to each other are reacted to give re . diluent materials which may be present-therein, action ‘mixtures made up of two liquid, phases, it . 'while withdrawing a reaction product from the has particular advantage in the treatmentv of hy 20 system substantially ‘at the rate at which'it is drocarbons with aqueous reagents since the solu-. formed. By this procedure I have found it pos bility relationships are especially adverse in such sible to adjust the conditions of reaction to the reactions. For this’reason my invention will be properties, both chemical and physical,’ of the re ‘ _ described with more particular reference to re actants so that each of the components may be - actions of this class, especially the typical case 25 provided with a time of residence in the reaction ' of the production of ole?ne derivatives by absorp zone best suited to its properties independently tion of the corresponding ,ole?ne in acid acting of the other component or components. media, but it will be understood that this is merely My process is thus radically different from prior in the interest of‘ conciseness and clarityiand‘ ~ Procedures for reacting together reagents one of ' impliesnov limitation since by obvious modi?ca '30 which has a low physical solubility ‘in the other, ‘since such prior methods have been largely re stricted to batch operations with their obvious at . tendant disadvantages prominent among which are usually an undesirably long. induction period which materially reduces theaverage production rate of the apparatus and high labor costs, etc. tion my invention may be applied with equal .ad 30 vantage not only to the other types of reaction’ listed above but also to many other reactions “between still different liquid reactants. As applied to the manufacture‘ of ‘alcohols, . Proposals have" been madeJor carrying out such ethers, esters and'li'ke derivatives which maybe producedby absorption of the corresponding ole ?nes in acid acting-media, my invention may be reactions continuously-whereby some of. the de? practiced wtih any suitable ole?n'e or ole?nic mixture regardless oithe source or character of 4_0 The continuous methods proposed heretofore‘ suf its olefine content. As suitable starting material, fer from the disadvantage of not providing for hydrocarbons derived from mineral oils aspetro "prompt removal from the reaction. mixture of leum, shale oil, and the-like, or from mineral oil components thereof which are undissolved in .the - products, orIfrom-natural' gas, or from c'oaL-peat \ phase in which reaction takes place. This loads and like carboniferous natural material, 'may be 45 to undesirable dilution of the reaction mixture used,’ as well as those derived vfrom animal-and ‘ .' and greatly reduced capacity of apparatus. ' My vegetable oils. fats and waxes. The ole?nes pres method. on the other hand not only provideafor ent in such starting_mat'erial may. be‘ of natural _'__"“the continuous‘ removal. of such components of occurrence,’ the result ot- dehydrogenation, distil the reaction’mixture butalso permits selective lation, vapor or liquid phase cracking, or other - ciencies of the batch methods maybe overcome.‘ 59 return to the reaction zone of the phase in which 1 pyrogenetic treatment._ The oleiines may be used 50 21 2, 106,581 in a pure state, either as individual ole?nes or pure ole?nic mixtures, or in admixture with . para?ins .or other compounds which may. be, considered as inert in the process. Furthermore; such ole?nes may comprise hydrocarbon fractions 1 ‘ If'we consider the case of the reaction between two liquids. or components oifv them of limited physical solubility, it is clear that the complete ‘ reaction .requires two steps which may be con sidered separately, viz. ‘ I-the transfer by agi- ‘ consisting of, or predominating in, hydrocarbons‘; tation of the reactant in one‘ phase to a state of containing the same number of carbon atoms to 1 solution in other phase-the- latter being the the molecule, or of mixtures of non-isomeric hy- - phase in which predominantly, if not wholly, re drocarbons. Ethylene and/or secondary‘base ole action takes place, and II.—the homogeneous Ii) ?nes (i. e. ole?nes, both iso and normal, which yield secondary derivatives, as propylene,>1-bu tene, 2-butene, l-pentene, Z-pentene, 3-methyl l-butene, and the like) and/or tertiary-base ole?nes (i. e. iso-ole?nes which yield tertiary dc‘ 15 rivatives, as 2-methyl propene, 2-methyl-2-bu tene, 2-methyl-1-butene, and higher homologues chemical reaction in the latter phase. For most 10 e?lcient utilization of the reaction zone, 1. e.' greatest overall reaction rate, it is desirable that ' there shall be present in the‘ reaction zone the greatest possible ‘amount of the latter phase, sub ject to the provision that there shall be as much of the former phase as is required to permit a rate of transfer of. reactant by agitation from the former phase to solution in the latter equal-to the in this application of my process include: ins ' rate of reaction of the transferred reactant in the 20 organic acids, of which sulfuric, phosphoric, pyro latter (or reaction) phase. Now while the condi phosphoric and hydrochloric are typical; or or-' ' tions conducive to. the physical process of rapid 20 ganic acids, as‘ benzene sulfonic, naphthalene phase transfer are those of degree of turbulence, sulfonic, toluene sulfonic,'and homologues and interfacial tension and the like, the conditions analogues thereof; or "acid liquors” such as are conducive to the chemical process of homogeneous and analogues) may thus be used. Suitable acid acting media which may be used obtained _by the absorption of ole?nes in mineral acid acting acids such as the above; or aqueous solutions or suspensions of acid-acting salts, such, for example, as sodium bisulf-ate, and the like. The concentrations in which such acid acting '30 media may be used'in any particular case will de pend upon the nature of the acid acting compound and ole?ne or ole?nes employed, the concentra tion of the plefine or ole?nes used and the tem perature at which the absorption is carried out. 36 When the acid acting agent is sulfuric acid, for exampl‘e, I have found'that concentrations with; in the range of about 40% to about l00.% may be satisfactorily used. For the absorption of ter tiary-base ole?ne concentrations of about 40%. 40 to about 80% are preferable, while for secondary .base ole?ne concentrations of about 80% to about 100% are more suitable. Irrespective of the tem perature conditions or acid concentrations used Iprefer to ‘carry out the process with the ole?ne 45 or ole?nes undergoing. treatment in the liquid phase, that is, at ‘pressures greater than the vapor _ reaction are temperature and concentration of 25 reactants and catalysts. It is the purpose of this ' invention to achieve an arrangement of operat ing conditions which satisfy these independent requirements and is not limited by the stoichio metric relationships of the reaction which govern so, the composition of the feed. Whereas in the prior art in continuously react- ' _ ing together liquid reagents in a mixing zone and continuously withdrawing reaction products in equivalent amount, proportions of the chemical 35 elements present inrthe reaction zone were in variably those proportions present in the feed, . with the novel arrangement here described the proportions in the reaction zone can be varied entirely ‘independently of the proportions in the 40. feed with , resultant considerable advantages. Whereas formerly if it was desirable to carry out a reaction continuously‘in thepresence of a large excess of one of the components of the reaction whether reactant or product, it was necessary to add that excess of component to the .feed and pressure of the ole?ne at the operating tem'pera- V remove it from the product in a separate opera; tures. By operating with the ole?ne in_ the liquid tion process, with the presentarrangement-that '‘ phase, more accurate control of the proportions desirable excess of one component in the reaction 50 of acid phase to hydrocarbon in the reactor may be had in a very simple manner irrespective of the proportions of the feed or products. a mixture can be achieved while introducing the 60 reactants as feed in the stoichiometric propor tions; _ - In general reactions between liquidsreagcnts of‘ low physical solubility with respect to each other In‘ .the absorption of ole?nes in acid acting media, the rate of transfer of ole?ne from hydro 55 appear to take place predominantly in one of the ‘carbon phase to acid phase depends not only on phases -only,~thus I have found that the reaction the degree of agitation,‘ altho this is highly im of ole?nes with acid acting media takes place in the acid phase, so that, provided enough agitation is created to maintain the acid phase saturated vwith ole?ne, the output of a reactor, other things beingequal, depends upon .the volume of acid portant, but also upon the inter-facial tension and, diifusioh and solubility characteristics of . the ole?ne'wlth respect to the acid phase, which vary m‘arkedly with the composition of the acid phase. The velocity of the homogeneous reaction ' phase present. The volume of acid phase which in the acid phase is in?uenced to an even greater _' ' ,; may be present is only limited’by the size of the extent by~thesolubility of the ole?ne in the com ‘ mixing unit-which in any given case will be deter phase, the rate of reaction increasing as the con mined by economic considerations of pump and centration of adsorbed but lmreacted ole?ne in 65 . creases. Depending upon the ole?ne or ole?nes . ' separator size. ' The latter in particular, is pref erably limited to such a size as will make excessive being treated, the composition of the acid layer recycled in accordance with my invention will residence times whether in the separator or‘re vary. In the case of the tertiary base-ole?nes actor,“ which might lead to decomposition, un 70 necessary. .The minimum size reactor, on the where‘ to the corresponding absorption in aqueous tertiary acid alcohol andare, for all 70 other hand, is that which when maintained prac ,practical purposes, synonymous. the acid layer tically full at all times permits the transfer under will have an alcohol content practically eqmw agitation of as much ole?ne per imit- time as-will lent to the reacted ole?ne content, while for . ' 16 react with the acid phase. abmrption products of and similar 2,100,521 . _ . - 3 ole?nes which form less easily hydrolizable ad about two minutes. The following'results were dition products with the mineral acid acting acid present, the acidic layer will have a com‘; obtained: > 1 ’ '~ "‘ ' isobutylene content of the‘; dis position characterized by'ratios of esters to free I Unreacted charged hydrocarbon layer ' _ alcohol determined by the hydrolysis equilibrium per cent by volume__ 10.5 of those esters under the reaction conditions} ' Due to the low free water content eof the re-l Absorbed isobutylene in the absorption prod uct as % of the isobutylene fed to the cycled acid, the decline in activity of the acid reactor _.._'_____'_ _____ __ ____ _‘_per cent... ‘72.7’ owing to dilution with reaction products‘ is more Mols of isobutylene absorbed per‘ mol. of 10 than offset, up to a certain point, by the in sulfuric acid used.‘ _______ __'___-_mols__ 1.64 creased solubility of unreacted ole?ne .in the acid phase. Thus the overall rate of reaction - Gallons of tertiary'butyl alcohol produced‘ per 24 hours per gallon of reaction ,is not by any means lowered as a result of re gallons“ 38.2. cycling acid layer, and so, in effect, reacting the l5 ole?ne with nearly fully reacted acid. Further, In larger scale operations it has been found 15' ' the use of nearly fully reacted acid of low total ' more advantageous to replace the ‘above de acidity as the absorption medium permits. the scribed mixer by an'ei’?cient centrifugal pump 10; Spa" ’ . ' employment of temperatures very much higher and a series of tubes having a volume equivalent - than would be safe with fresh acid to that of a mixer of the required increased ca The actual conditions of operation adopted in pacity.. In this system it is particularly desir 20 v any given case will depend upon the eillciency of ' able to ‘provide a .by-pass whereby the emulsi conversion desired. It has been found for ex ?ed reactants may be recirculated and unneces ample, that isobutylene present in a concentra- . sary load on the separator thereby avoided.' ' tion of 20%v in 80% of inert diluents may be con In Example I there was available a hydro verted to tertiary butyl alcohol-by my method at a'rate of about 25 to 30 gallons of anhydrous carbon mixture'which it was desired. in order to 25 comply with the stoichiometric requirements of alcohol per dayper gallon of reaction space with ' the reaction,-to react continuously with one a conversion of over 85% of the isobutylene in the feed. Much higher rates of thruput are 30 possiblewhen the conversion is allowed to fall. fifth of its volume of sulphuric acid of a cer tain strength. By the methods previously used the passing of this feed at a rate of ?ve gallons The following examples which show applica so of hydrocarbon per-hour continuously through a tions of my invention to the selective absorption mixing and reaction zone of 1 gallon volume of tertiary and secondary base butylenes in would have resulted in there being present in aqueous sulfuric acid, illustrate 'the advantages they reaction zone at all times ?ve-sixths of a of my'novel process.‘ It will be understood, how gallon of hydrocarbon to one-sixth of a gallon 35 ever, that as has already been pointed out, many‘ of acid (ignoring volume changes due to reac other applications and modi?cations are possible > tion) so that both materials would have a resi- . ' dence time in the reaction zone of one-sixth of an hour. Now thisv residence time of'one-sixth of an hour is more than su?icient for the physi 40' without. departing from‘the spirit of my inven tion. ‘ ~ Example I cal processor phase transfer of the'whole of the As starting material for theproduction of ter reagent from the hydrocarbon phase into the tiary butyl alcohol in one typical instance, a' acid phase, but is less than su?lcient to permit butane-butylene fraction ‘having the following the chemical reaction of this quantity of reagent approximate composition was used. ' 1 Per cent by volume Paraffin hydrocarbons___*_ ______________ __ 30.8 . Butene 1 and butane‘ 2 _____________ _>____ 29.6 Isobutylene ‘ 39.6 '50 ‘This hydrocarbon mixture was fed, in the liquid state, at a rate of about 3.13 gallons per hour per gallon‘ of reaction space to a' continuous re actor comprising a mixer of about 800 cc. vol ume ?tted with a high speed stirrer so as to act as an ine?lcient centrifugal pump and discharge from the circumference to a separator. At the in the volume of acid phase present. - - 45 Accordingly by the methods of my invention I reduce the residence time of the hydrocarbon phase and increase that of the acid phase by withdrawing from‘ the reaction zone at a. rate of ‘thirty gallons per hour to a separator and return 50 from the separator to the reaction zone twenty- . four gallons per hour of the acid phase. Thus altogether Ihave entering and leaving the re action 5 gallons per hour of hydrocarbon and 25’. gallons per hour of, acid made up of one gallon 'of fresh acid and twenty-four gallons of recycled _ acid phase, 1. e. acid'which contains absorbed ' same 5time a 63.2% solution of sulfuric acid ole?ne, so’ thatthe reaction zone now contains ma'tely 49° C. and the‘ rate of ‘discharge there from was kept substantially constant at about 30 gallons per hour per gallon of reaction space. .*"The reactor and separator were maintained under ‘sufficient pressure (e; g. about 100 to 150 acid phase'of all they-reactant hydrocarbomwhile " the’ acid phase is inemulsi?ed contact with the . one-sixth of a_ gallon of :hydrocarbon- and ?ve was added at the rate of about one gallon to sixths of a gallon of acid phase. Thus the hydro GO each 5 gallons of hydrocarbon feed. The tem carbon now has a residence time of one-thirtieth ‘perature of the‘ reactor was kept at approxi- ‘ ‘of an hour, which suf?ces for the physical, process lbs./_sq. in.) to ensure both being kept full at alltimes and the unabsorbed hydrocarbons were withdrawn as fast as separated whilea part of " the absorption product was. recycled‘ to give a ratio of about -11 volumes of acid phase to one volume of hydrocarbon phase 'in-the reactor and 75 an average time of contact of the two phases ofv of transfer from the hydrocarbon phase to the hydrocarbon phase for ?ve-sixths’ of an hour.»' The acid‘ phase now has a ?ve times greater volume inthe reaction-zone than in the former‘ case and the amount of reaction which can there 70 fore take place in it is vincreased proportionately. The extra‘degree of freedom'in choice'of operat- - ing conditions and consequentrarivvantage ?ll/11S obtained enabling the" adjustment cf conditions .to the requirements of thexprocess‘is thus clearly. 4 ‘2,108,521 seen whether from the standpoint of adjusted possible. For example, results practically identi residence time or adjusted reaction phase volume. Example H cal to those described in the above examples may be obtained by substituting phosphoric acid solu— tions of the same concentrations for the sulfuric acid solutions described. Another modi?cation 5 which may sometimes be desirable, a'ltho involv ing more equipment, comprises carrying out the ' In order to compare the e?ect of recycling hydrocarbon layer instead of acid layer the fol lowing tests were made using the same apparatus. In each case the isobutylene content of the absorption in more than one step. 10 the sulfuric acid was 64%. Recycling hydro ' layer 15 on the same oieiine containing material may be 10 , Recycling acid carbon layer M015 0! a??? _Mols oi ‘Lea-cs?‘ isobuty‘ butylene lsobuty' butylene leue -. led lsobutylene input- _-_. -- 79. 8 100. 0 Isobutylene in acid layer. 20 Isobutylene in hydro- ' 65. 0 82. 5 butyl alcohol ________ -- lene. _ fed . 54. 3 100. 0 an “acid liquor?’ as absorption medium for one 61. 5 stage of the operations and approaches in eifect v I . 2.4 3. 0 2. 2 7. 75 9. 5 12. 8 ' ed for ________________ .- Duration of experiment_Average tertiary butyl 4.0 5 0 alcohol content of acid layer__ ___________ _>.____ 7.7 hours 6.0 the mineral acid acting acid agent. The use of alkyl acid esters of mineral acid acting acids as 11.1 absorption agents is especially useful where both 3. 9 6.0 hours A " 45.1% i 25.2% A 4 Average production rate (gram mols of total al cohol per hour) ______ __ .30 8.8 the use of an alkyl acid sulfate, for example, as 23. 3 ' lsobutylene unaccount 25 used, a major portion of the resulting-absorption product being recycled to the same mixer in each case and'the separated portions of the absorption products being combined for working up into the desired end product, or the minor part of the absorption product from one stage may be used in lieu of fresh acid in -a preceding stage. The‘ latter procedure is the equivalent of the use of 33. 4 ' carbon layeras tertiary As free .isobutylene- _ _._. Thus two or more independent mixers operating successively hydrocarbon feed was 40.2% and the strength of 5.9 secondary and tertiary-base ole?nes, particularly‘ 25 _ isomeric secondary and tertiary-base ole?nes, are to be absorbed. In such cases the secondary-base cle?ne or ole?nes may be absorbed in a polybasic mineral acid acting acid of appropriate strength and that partof the resulting absorption product 30 These results show the advantages both in in- creased rate of production and emciency of op-_ which is separated from the recycled portion may eration obtainable by having a large volume of be used, advantageously after dilution, to absorb desired tertiary-base ole?ne using my novel recycled acid layer present during absorption. the recycling step as before. In this way substantial In the above case about 95 to 97% of the contents acid economies may be effected since the total of the reactor was acid phase when acid layer was‘ ole?ne content of the ?nal absorption product 35 recycled and only about ‘10 to 15% when the acid - may be much higher than is commercially feasible , passed thru only once. . in prior art procedures. Whatever modi?cation " v ‘ Example‘ III e of my process is used,git'is desirable to separate 40 For the preparation of an absorption product unabsorbed hydrocarbons from the recycled acid 40 > of secondary-base butylenes in sulfuric acid, a liquid hydrocarbon mixture obtained as a hydro liquor as needless dilution of the-reaction mixture is thereby avoided. Altho the above examples have been described carbon layerv from a butane-butylene fraction ‘which had been treated according to the pro 45 cedure described in Example I, was used. This of alcohols it will be apparent that the absorp had the following approximate'composition: be converted, by known methods, into a wide va with more particular relation to the preparation 45 tion products ob ained by my novel process may riety of other end products. Distillation of the absorption product under more acid conditions than those used for the recovery of alcohols favors 50 l-butene and 2-butene ________________ _ Iso and normal butanes ________________ __ the formation of ethers, while reaction with fatty This hydrocarbon mixture was fed, together with acids, for example,‘acetic acid, may be used to 84.4% sulfuric acid in the proportion of 1.3 to‘ 1.4 produce the corresponding esters. Alternative mols of acid per mol. secondary-base ole?ne, to ' ly the alkyl acid sulfates present in the absorp the above described reactor. The hydrocarbon tion products may be converted by treatment with feed was at the rate of 6.5 gram molsof second-' alkaline agents such as sodium hydroxide and the like into salts which are valuable wetting agents ary-base butylenes per hour and the reactor con and detergents. Or the absorbed ole?nes may be " tents were maintained at about 30° C. About. polymerized by rapid heating, preferably underv ~ 95% of the acid layer was recycled to the reactor pressure; to give higher boiling hydrocarbons of 60 60 - Percent Isobutylene as before- The average ole?ne content of- the exit hydrocarbon layer was 6.6%. Only a; very small amount of polymer about equivalent to the , isobutylene content of the feed could be detected. _ high anti-knock value. Alkyl substituted phenols may be produced by reacting the absorption prod ucts obtained in my process’ with an excess of The average composition of the separated acid ‘ phenol. My invention is also useful in the prepa ration _of pure ole?nes from 'ole?nic mixtures 05 layer wasI ' ' - _ I I _ Percent by weight Secondary butylenes ( 'as alcohol) _______ __ 31.0 Total acid (as H2804) ____ .._' ____ _;__; ____ _._ 59.6 Free titratable acid (as H2804) __________ -_ 49.0 - This represents a 93.4% conversion of .l-butene since by means of. my novel absorption process the more reactive of such ole?nes may be selectively removed and the resulting absorption product used to regenerate, in a substantially pure form, , the absorbed ole?ne by controlled heating. or - The foregoing examples illustrate applications’ and 2-butene at a rate equivalent to 16.9 gallons ' of my'invention in which the presence of a reac ' of anhydrous secondary butyl alcohol per day per gallon of reaction space. 75 ’ Many ‘variations in myprocess are obviously tion product in the recycled phase increases the solubility of the other reactant therein'and con sequently promotes-the homogeneous reaction in 75 s 2,100,591 the recycled phase in accordance with the Mass action law. The following example which is typif cal of applications of my invention where an ex cess of a reactant in the recycled phase accom-. - plishes the same result, shows the wide applica-' ’ bility of my process wherever the reaction mix ture forms two liquid phases. ' zene sulphonic acid and 9.6% unreacted H2894 ’ and the balance water equivalent to that formed by the reaction.v The reaction mixture when under‘ steady operating conditions showed" one part of upper layer to 12 of lower layer, in contrast to the (approximately) 2 volumes of upper layer to 1. volume of lower layer in the feed. .' It will be obvious that this continuous sulfona-~ Eicample I V tion procedure may be applied not only to a wide Alcohols may be reacted with ole?nes by my . variety of other aromatic compounds including process to give particularly good yields of. ethers at for example toluene, xylene, nitro benzene and , 10 ‘ high‘ rates. In one such application of my inven tion a continuous reactor similar to that described in Example I, was charged with a mixture of 15 methyl alcohol and sulfuric acid in the propor tion of 3 volumes of alcohol to 1 volume of ‘acid. A, mixture of 'pentanes and amylenes analyzing about 25% tertiary base ole?nes was then fed in together with methyl alcohol in the ratio of 1 other suitable benzene substitution products as " well as naphthalenes, naphthols, anthraquinone and the like, but also ole?nes such as ethylene and its homologues and, by the use of oleum, par amn hydrocarbons such for example as hexane, the octanes, etc. is ,From these typical examples it will be evident _ > not only that my invention may be used in the volume of alcohol to 20 volumes of hydrocarbon; production of a wide variety of valuable products The reactor was maintained at about 50° C. and but also that in all'its many applications it of 20, - under 50 pounds pressure to ‘prevent volatiliza fers important advantages over prior methods‘ tion of hydrocarbons. The addition of reactants _of operation. It furnishes a particularly desir- ' was at a rate of about 1 volume per minute per able method for carrying out continuous reac-. 47.4 volumes of reactor contents and the with tions in which all components of the reaction 25 drawal of emulsi?ed mixture was exactly equiva mixture including the reaction product are ad lent. The withdrawn'mixture was conducted to vantageously maintained in the liquid phase in‘ a separator where it was allowed to stratify. All order to avoid undesirable side reactions orv for the acid layer was continuously returned to the other reasons. It will be evident that while‘ my reactor while the upper hydrocarbon layer was invention has been illustrated by examples in' 80 removed. After equilibrium conditions had been ' which the operations of mixing and reacting were reached the upper layer was found to contain on carried out in different apparatus from that used the average about 18% by weight of methyl for stratifying and separating the phases of the‘ tertiary amyl ether which could be recovered by resulting reaction mixture, such operations may washing to remove traces of acid and amyl al readily be .carried out in the same unit by suit. as, cohol and then distilling. ' \ably providing reaction and separation zones This method of continuous etheri?cation may therein. ~By my process the. usual induction pe not only be successfully applied to the higher riod accompanying reactions ‘in‘which ‘the ve homologues of methyl alcohol, such for example, locity of solution of one reactant in the other’ is as ethyl, propyl, isopropyl, normal, iso-, second greater than the velocity of reaction between said 40 ary and/or tertiary butyl alcohols and their suit reactants, .is substantially avoided and the. re able substitution products but also to polyhydric suiting‘ average rate of reaction is thereby not alcohols, such as ethylene, propylene, butylene only increased but also made more uniform, and like glycols, polyglycols as diethylene glycol, Furthermore my invention has unique advan dipropylene glycol, propylene-ethylene glycol, etc.', tages in carrying out reactions in the presence of 45 glycerol, sorbitol, etc. In all cases other ole?nes inert diluent materials, particularly where such besides the tertiary amylenes above illustrated diluent material is immiscible with‘ the reactant may be used. phase in which the reaction takes place, since by This reaction_exempli?es, particularly well, the recycling that phase only from a separator as advantages of my process using a high proportion described in Examples'I, II and III, not only is of acid phase to hydrocarbon phase. In this case, undesirable dilution of the incoming reactants 50' ' where the usual batch methods, in which the ratio of hydrocarbonto acid is reversed, are applied, about two hours are required to reach chemical equilibrium despite the‘ best of mixing; .while in my proceduredless than two minutes are neces sary under otherwise similar conditions. " Example V For the preparation of benzene sulphonic acid it is required toreact together benzene and 100% sulphuric acid in the proportions~ 78 gms.-(89 cc. _ I approx.) to 98 gms. (53 cc. approx.) . The react \ants in these proportions were fed into a reactor avoided, but also alreaction mixture is provided which is richer in that phase than can-be ob tained by. mixing the required amounts of the two reagents without such selective recycling. ' _ 56 While I have in the foregoing described in some detail the preferred embodiments of my inven tion and have particularly emphasized its appli-' cations to reactions of acid acting media with liquid hydrocarbons'it will be obvious‘ to those 60 skilled in the art that alkaline reagents, as in the hydrolysis of halogenated hydrocarbons with NaQH, NazCOa, and the like solutions, for ex; ample, may also be used. and therefore my in- ‘ \ of 400 cc. volume continuously. Reaction mixture , 'vention is to' be regarded as limited ‘only byv the, was withdrawn to-a separator at rate of 10,000 terms of the accompanying claims. cc./hr. or 25 volumes per volume of reactor per hour. 8000 cc. of the lower layerv from the separa tor was returned continuously to the reactor and 7‘ the reni'ainder withdrawn as product. The level in the reactor was maintained by feed of reagents in the ‘stoichiometric proportions above. The ‘ - produce was found to consist of 9.0% mol. unre- . acted benzene which separated as upper layer and '75 could be returned to the process, 89.4% incl, beny' I claim as my invention: ‘ I 1. .A pro ess for continuously reacting an ‘or ganic liqui “reagent reactive with another liquid reagent in which it’ha‘sa low physical solubility which comprises continuously adding said re agents to a reaction mixture of a composition with respect tothe elements in the_.feed which is'Ydifferent from the composition of the total iced, continuously removing ‘reaction mixture 75 6 2,100,021 pounds of din‘erent reactivity toward a liquid re from the‘ reaction zone without substantially changing its composition, separating at least a part‘ of the reaction product corresponding to ‘agent in which said component has a limited , physical solubility which comprises continuously contacting saidhmixture in the liquid state with that formed in the reaction and continuously re said liquid reagent at a temperature and at a pressure at which reaction between the more re-‘ turning sumcient of a remaining component of the reaction mixture to said reaction zone .to active component and the liquid reagent takes place in the presence of substantially reacted liquid reagent without substantial conversion of at least one component ofv said organic mixture, 10 ‘continuously withdrawing reaction mixture from the reaction zone, separating the liquid phases present, removing the phase containing the un maintain said composition difference between the total feed and the reaction mixture. 2. A process for continuously reacting an or 10 ganic liquid reagent with a second liquid re agent in which its solution velocity is greater than the velocity of the reaction between said reagents under the existing conditions which comprises continuously contacting said liquids reacted organic compound and continuously re turning such a part of the other phase as does 15 15 in a reaction zone containing a preponderance of the liquid phase in which the reaction sub ,not contain reaction product equivalent to that stantially takes place, ‘continuously withdrawing formed in the reaction to said reaction zone. 7. A process for continuously reacting an or reaction mixture from said reaction zone with out substantially changing its composition, sep 20 arating reaction product therefrom equivalent to that formed in the reaction and continuously ganic liquid reagent with a second liquid re-/ agent with which it forms a reaction product of 20 low physical solubility ‘in said ‘second reagent returning to said reaction zone at‘least a part of the withdrawn phase in which the reaction which comprises continuously adding said re substantially takes place. of said second reagent, continuously withdrawing ' , 3. A process for'continuously reacting an or agents to a reaction. mixture containing an excess reaction mixture from the reaction zone without 25 ganic liquid reagent reactive with another liq substantially changing its composition, stratify uid reagent in which its solution velocity is great -- ing the withdrawn mixture into a phase contain-‘ ‘ er than its characteristic reaction velocity under ing reaction product and a phase containing said ' the existing conditions which comprises contin second liquid reagent, continuously removing the uously adding said reagents to a reactor main ~ phase containing the reaction product from the' 30 tained at a temperature at which reaction be system and continuously returning the phase tween the two reagents takes place,’ continuously containing said second liquid to contact with withdrawing reaction mixture from said reac ' fresh reactants; tor at a rate substantially greater than the total 8. A process for continuously reacting an or rate of feed of said reagents without substan ganic liquid reagent'with a second liquid reagent tially changing the composition of said mixture, in which it has a low ‘physical solubility and with separating material immiscible with the phase in which it forms a reaction product which is.sol-‘ which the reaction takes place, removing at least uble in said second liquid which comprises’ con - a part of the reaction product equivalent to that tinuously-contacting said reagents in the pres ence of an excess of a phase containing said 40 40 formed ‘in said reaction and continuously return ing the remaining components of the withdrawn ‘second liquid reagent, continuously withdrawing reaction mixture to the reactor. ‘ -_ g . reaction mixture therefrom without substantially 4. A process for continuously reacting an or changing its composition, separating material im ganic liquid reagent with another liquid reagent . miscible with said second liquidqreagent, remov 45 in which it has a limited physical solubility which ing from the system a part of the phase con-. - comprises continuously contacting said reagents taining said' second reagent containing reaction in the presence of a reaction product thereof at a .product equivalent» to that formed in the re temperature and at a pressure at which reaction . between said reagents takes place with the for 50 mation, of a reacted mixture ‘made up of two liquid phases, continuously stratifying and sep ’ . aratin'g said phases and retumingat least a part of one of said phases containing said reaction _ . product to contact with fresh reagents in the re - 55 action zone. I v 5. A process for continuously reacting an or ganic liquid reagent with another liquid reagent in which it has a limited physical solubility which comprises continuously adding said reagents to 60 a reactor containing a substantial excess of one reagent above the stoichiometric proportion in which said reagents react while maintaining said reactor at a temperature and at a pressure’ at ~which reaction between said reagents takes place 65 in the liquid state with the formation .of a re acted mixture made up of two liquid phases, con tinuously withdrawing reacted mixture from said reactor, stratifying and separating said two‘liq uid phases, removing one phase from the system, 70 recovering reaction product substantially equiva lent to that formed in'the reaction and contin uously returning the other of said phases con taining said excess reagent to the reactor. ' 6. A process for continuously reacting at least 75 one component of» a mixture of organic com action and returning the remainder of ‘said phase to. contact with fresh reactants. “ > “a .9. A process for continuously reacting an or- . " ganic reagent with another reagent in which said organic reagent has a solution velocity greater than the velocity of_ the reaction between‘said . reagents under the existing conditions which comprises continuously adding said- reagents to: a reaction zone maintained at a temperature at which reaction between said reagents takes place vand under a pressure at least ‘equal to the vapor. ' pressure of the most volatile component of the 60 reaction mixture, continuously/withdrawing re action mlxture from said zone without substan tially changing its composition at the ‘rate at: which solution of said'organic reagent in the » phase containing saidi‘other reagent is complete, . ' continuously separating material present in said withdrawn mixture which is immiscible with said liquid phase, continuously withdrawing’ from the system reaction product at substantially the rate at which it is formed, and continuously returning such- a part of said liquid phase that, the average time 'of residence thereof insaid reaction zone . substantially corresponds to complete reaction. 10. A process for continuously producing a hy drocarbon derivative which comprises continu 1.6 7] . aioacar ously feeding a hydrocarbon and a liquid reagent cess of said reactive liquid reagent maintained reactive therewith in which said hydrocarbon has ' at a temperature at which reaction takes place, a low physical solubility to a reactor maintained continuously withdrawing reaction mixture substantially liquid-full and at a temperature at‘ from said reaction zone withoutasubstantially changing its compositiomremoving undissolved said reagent takes place, continuously withdrawe hydrocarbon from the reactive liquid reagent, re- ing reaction mixture therefrom ,without substan-'-, . moving a part of said reactive liquid reagent tially changing its composition at a rate sub-' ‘containing reaction, product equivalent to that stantially greater than the rate of feed of hydro- “ formed and continuously returning the remain der of said liquid reagent to said reaction zone. 10 10 carbon and reagent, separating material immis which reaction between said. hydrocarbon and cible with the phase in which the reaction takes 15. A continuous process of absorbing an ole place, ‘continuously vremoving reaction product ?ne in an acid-acting medium which comprises - substantially at the rate at which-it is formed - adding said ole?ne in the liquid phase and said and continuously returning ‘at least -a part of acid-acting medium to an absorption product of 15 said phase in which the reaction takes place to said ole?ne in saidvmedium, withdrawing the re said reactor. ' ' ‘ > > ' - suiting mixture at a higher volumetric rate than that of said ole?ne and acid-acting medium ad 11'. A continuous process for producing hydro carbon derivatives which comprises continuously ‘ ditions, separating an amount of the resulting ' feeding a- hydrocarbon and an aqueous reagent ole?ne absorption product equivalent to the acid acting-medium- addition and returning the re 20 reactive therewith to a reactor containing pre ' ponderantly substantially reacted aqueous phase mainder of said absorption product to the ab ' » ‘ maintained at a temperature at which, reaction sorption unit. between said hydrocarbon and said aqueous re agent takes place and at a pressure at'which all components of the reaction mixture are in the liquid state, continuously withdrawing reaction 16. A continuous process of absorbing aniole- . ?ne in a mineral acid-acting acid which com 25 prises continuously feeding said ole?ne in the liquid phase and said acid to a mixer maintained substantially liquid-full and under strong agita» ' mixture. from said reactor without substantially changing the composition thereof, separating any . tion, continuously withdrawing the resulting mix- hydrocarbon material which may be present un ture to a separator .also maintained substan tially liquid-full, ‘separating unabsorbed hydro- I v30 dissolved in the aqueous phase, continuously re moving reaction product substantially at the rate carbons which may- be present from the result at which it is formed and continuously returning ing oleflne absorption product, separating an- . amount of‘ absorption productl substantially aqueous’ phase to said reactor. " 12. A continuous process for producing a hy-' equivalent to the acid feed and returning the re- ‘ 3 drocarbon derivative which comprises continu- ‘ maining absorption product to the mixer. ' ously feeding a hydrocarbon and a liquid vacid acting'medium to a reaction zone containing an excess of said acid-acting medium maintained at a temperature at which reaction between said 1'7. A continuous ‘process of absorbing the tcr- , ' tiary-base ole?ne content of an ole?nic mixture containing less reactive olefines which comprises continuously adding said mixture in the liquid ' '40 hydrocarbon and said aqueous reagent takes place state ‘and an aqueous acid-acting medium to an and at a pressure at which all components of the reaction- mixture are ’in they liquid state, con in said acid-acting medium at a temperature at v tinuously withdrawing reaction mixture from said - reactor without substantially changing the com absorption product‘ of said tertiary-base ole?ne which substantial absorption of the‘tertiary-base position thereof, separating any hydrocarbon ma ole?n'e takes place without substantial conversion of the less reactive ole?nes present, continuously 40. . terial which ‘maybe present undiss'olved in the withdrawing the resulting absorption mixture, ~ . acid-acting medium, continuously removing re separating unabsorbed material present, remov action product substantially at the ‘rate at‘which, ing a part of the absorption product from thev ' it is formed and continuously returning aqueous ‘ system and continuously returning the remain50 phase to said reaction zone. _ . " _ h 13. A continuous-process for producing a hy drocarbon-sulfuric acid reaction product which comprises’ continuously feeding‘ a hydrocarbon ‘der to contact with fresh tertiary-base ole?ne' containing ole?nic mixture. and aqueous acid acting ~medium.~ w " ~ I , . > _18. A continuous process of absorbing iso-' butylene containing hydrocarbon in the vliquid .and- a sulfuric acid containing phase’to a reac tion ,zone'containing a preponderance of sub stantially reacted sulfuric acid phase, while main taining in said zone a temperature at which-re‘ action between said hydrocarbonan'd' sulfuric acid takes place ‘and, at a pressure at which all ; components of the reaction mixture-are in the ~ liquid state, continuously withdrawing reaction. about 40% to about 80% strength at a tempera ture at whichsubstantial absorptionof iso butylene is effected without substantial poiymer-' ization in the presence of a substantiallylarger from the reaction zone, separating hy drocarbon undissolved in the sulfuric acid, con? tinuously removing a part of the sulfuric acid phase containing reaction product equivalent to that‘formed and continuously returning the re suiting reaction mixture at a substantially higher rate than that "at which the isobutylene and acid solution are fed, continuously separating'un- ‘ absorbed hydrocarbons from the withdrawn mix 'mainder of the ‘sulfuric acid ”actionzone. ' - " said ref - phase with an aqueous sulfuric acid solution of volume of an absorption product of isobutylene .60 in said acid, continuouslylwithdrawing the-re ture, removing a part of ‘the resulting lsobutylene absorption product equivalent to the feed and ' continu usly .returningthe remainder. to con-' 14. A continuous process for producing an oieé Y tact with resh isobutylene and sulfuric acid solu 70 fine "derivative which comprises continuously tion at a rate atv which-the ‘composition of feeding oleflne containing hydrocarbon material absorption product isn'ma'intained in the liquid state and a liquid reagent reactive ‘therewith to a reaction zone‘ containing an’ extv 1 i constant. .' l] _ _ I_ MeLDEANELY; '