Патент USA US2412229код для вставки
Patente Dec. 1%, '. I _ era 2,412,229 smmon or snom'rrc ,- soc 1 hr ns _Raymond E. Scaad, Chicago, 111., Universal Oil :,- or to nets ilompany, Chicago, a corporation of ., were Application May 31, 1941, erlal No. scale: 20 Claims. (6i. zoos-s11) 2 ,butadiene and isoprene, also non-conjugated This invention relates to the treatment of ,diole?ns, and other poly-ole?ns. Oleilnic hydro aromatic hydrocarbons to produce alkylated are? carbons utilizable as alkylating agents are obtain able from any source and are present in products of thermal and catalytic cracking of oils, in those matic hydrocarbons. More‘ speci?cally it is con cerned with the production of mono-alkylated and poly-alkylated aromatic hydrocarbons in the presence of a catalyst. obtained by dehydrogenating paramnic and It is recognized that in general the catalytic alkylation- of aromatic hydrocarbons has been ole?nic hydrocarbons or in the products resulting from dehydrating alcohols. Alkylation of aromatic compounds may also be known for some time. However, the present in vention di?erentiates from the prior art on this subject in the use of a particular catalytic mate rial comprising as its active ingredients. pyro= phosphate of a metal selected from members of the right-hand column of group I of the periodic e?ected in the presence of catalysts hereinafter described by charging with'the aromatic hydro~ carbon a substance capable of producing ole?nic hydrocarbons under the operating conditions chosen for the reaction. Such ole?n-producing 15 substances, include alcohols, ethers, esters, and table. alkyl halides which are capable of undergoing ole In one speci?c embodiment the present inven hydration or splitting to olefinic hydrocarbons, tion comprises a process for producing alkylated containing at least 2 carbon atoms per molecule, aromatic hydrocarbons which comprises subject which may be considered as present in the re~ ing an aromatic hydrocarbon and an ole?nic hydrocarbon to contact under alkylating condi 20 action mixture even though possibly only as ‘transient intermediate compounds which react tions in the presence of a catalyst comprising as its active ingredient a pyrophosphate oi‘ a metal . further with aromatic hydrocarbons to produce desired reaction products. selected from members of the right-hand column of group I of the periodic table, and preferably of Aromatic hydrocarbons, Catalysts suitable for use in effecting the proc 25 ess of the present invention comprise preferably ' copper-and silver. such as benzene, toluene, other almzlated benzenes, napththalene, alkylated naphthalenes, other poly=nuclear aro- - matics, etc., which are alkylated ‘by olefl'nic hydro carbons as hereinafter set forth, may be obtained copper and silverv salts of pyrophcsphoric acid as well as the materials formed by mildly treating these pyrophosphates at elevated temperatures with hydrocarbons, hydrogen, or other reducing gases prior to use as alhylating catalysts. The metal pyrophosphates utilized as alkylating catalysts may be formed by adding an aqueous solution of an’alltall metal pyrophosphate to by the distillation of coal, by the dehydrogenation of naphthenic hydrocarbons, by the dehydrogena~ tion and cyclization of aliphatic hydrocarbons, an aqueous solution oi’ a water=soluble copper alkylated aromatic hydrocarbons, and allrylated naphthenic hydrocarbons, and by other means. 35 or silver salt to e?‘ect precipitation of the desired metal pyrophosphate which may be separated by ; Oleflnic hydrocarbons utilizable' as alkylating filtration from the‘ precipitation mixture, then agents in the present instance comprise mono washed, dried, and formed into particles suitable ole?ns and poly-oleflns. Oleflns which are em for use as a reactor ?lling material. ployed in the present process are either noally gaseous or normally liquid and comprise ethylene 410 Pyrophosphates of copper, "silver, or, mixtures thereof may be used as such or mixed with or de and its higher homologs, both gaseous and liquid, posited upon carriers or supporting materials such the latter including various polymers of normally as silica, diatomaceous earth, alumina, magnesia, gaseous ole?ns, but these di?erent clefinic hydro silica-alumina composites, crushed porcelain, " carbons and those mentioned hereinafter are not necessarilyequivalent in their action as alkyleting 45 pumice, ?rebrick, etc. A composite of a group I metal pyrophosphate, metal acid pyrophosphate, agents. Cyclic ole?ns- may also serve in alkyl and 'a ‘selected carrier in ?nely powdered form ating aromatic hydrocarbons but generally under after thorough ‘mechanical mixing, is subjected , conditions of operation different from those employed when alkylating aromatic hydrocarbons to drying, pelleting, and heating operations, the by non-cylic ole?ns, and this reaction may in 50 latter carried out in a stream of air, nitrogen, hydrogen, or hydrocarbon gases to produce formed volve intermediate formation of ole?ns vfrom particles of catalyst suitable for use as packing cyclopara?ins in they presence of the catalyst. Other ole?nic hydrocarbons which may be inter material in a reactor employed for effecting alkyl atlon of aromatic by ole?nic hydrocarbons, or acted with the above indicated aromatic hydro carbons include conjugated diolenns such as - 55 the metal pyrophosphate itself may be similarly 2,412,229 3 .' ~ ~ 4 . formed into pellets or granules usually by com pressing a mixture of the powdered metal pyro phosphate and a suitable pelleting lubricant such as hydrogenated cocoanut oil, starch, etc. The activity of supported metal pyrophosphate suspension by some method of agitation, catalysts is also controlledto a substantial extent, choice of operating procedure is dependent upon by varying the proportions of active metal pyro- ' the circumstances such as the temperature, pres- . also be effected in a closed vessel in which some of the reacting, constituents are‘in liquid phase and in which the catalyst is preferably in finely divided form and is maintained in dispersion or . The phosphate and carrier. Accordingly, catalytic material of appropriate activity is thus available sure, and activity of catalyst found to‘be most ef fective ‘for producing the desired reaction be-v for use with both substantially straight chain 10 tween particular aromatic and ole?nic hydrocar ole?ns and with the more reactive ole?ns such as those containing a tertiarycarbon atom as is bons. . ' . Metal pyrophosphates as herein described are present in isobutene, tri-methyl ethylene, etc.. preferred catalysts as they permit continuous re-' The di?erentalkylating catalysts which may thus action of aromatic and ole?nichydrocarbons in be prepared and employed in the present process the presence of a ?xed bed of catalyst and thus are not necessarily equivalent in their action. make it possible to avoid mechanical problems as In effecting reaction between aromatic hydro well as oxidation and corrosion di?loulties en carbons and anvalkylating agent, as an ole?nic countered when this reaction is carried out in I hydrocarbon, according to the process of the pres the presence of sulfuric acid which is sometimes ent invention, the exact method of procedure 20 used as an alkylating catalyst. Further, a, pyro phosphate of copper or silver also has the advan varies with the nature of the reacting constitu ents. A simple procedure, utilizable in the case , tage over aluminum chloride utilized as catalyst of an aromatic hydrocarbon which is normally -for alkylating aromatic compounds with ole?nic , liquid, or if solid is readily soluble or easily dis hydrocarbons in that the metal pyrophosphate persible in a substantially inert liquid, and a .forms substantially no addition compounds or normally gaseous or liquid ole?nic hydrocarbon, complexes with aromatic and/or ole?nic hydro-‘ consists in contacting the aromatic and ole?nic - carbons while such formation of addition com hydrocarbons with a catalyst containing a pyro pounds 'is characteristic of catalysts containing. phosphate of a metal selected from the members aluminum chloride. of the right-hand column of group I of ‘the peri 30 Reactions between aromatic and ole?nic hy-, odic table at a temperature of from about 100° _ drocarbons inthe presence of a pyrophosphate of to about 450° C. and preferably between about a‘ non-alkaline metal of ‘group I of the periodic 250° and about 400° C. under a pressure of from table are apparently of a relatively simple char substantially atmospheric to approximately 100 acteralthough they may be accompanied by cer atmospheres. Intimate contact of the reacting tain amounts of polymerization and decomposi components with the catalyst is effected bypass tion, the latter being particularly in evidence ing the reaction mixture through a ?xed bed of when the reaction is carried out at a temperature in the neighborhood of 450° C. While not under granular or pelleted catalyst or the reacting com ponents may be mixed with ?nely divided cat-v. stood completely, a typical alkylation of an arc alyst and reacted in either a batch or continuous 40 matic hydrocarbon by an ole?n apparently in . type of operation. The hydrocarbons subjected volves the addition of the aromatic hydrocarbon to reaction are preferably in the proportion of 1 to a double bondelof an ole?nic hydrocarbon'to , molecular proportion of ole?nic hydrocarbon to ~ produce a higher-boiling alkylated aromatic hy ‘between about 2 and about 20 molecular propor drocarbon which may in turn undergo further tions of aromatic hydrocarbon in order to di reaction with one or more molecular proportions minish polymerization of ole?nic hydrocarbons of ole?nic hydrocarbon to ,form' dialkylatedand ' and to favor interaction of oleflnlchydrocarbons more-highly alkylated aromatic hydrocarbons. with the aromatic hydrocarbon or m'ixture of aro-~ In case the alkylating ole?nic hydrocarbon is, a matic hydrocarbons in the hydrocarbon fraction, diole?n or other poly-ole?n, the interaction with undergoing treatment. The addition of a hy ‘an aromatic hydrocarbon may involve. not only drogen-containing gas to the alkylation mixture the combination of aromatic‘ and ole?nic hydro frequently has a. bene?cial effect upon the re carbons but possibly the polymerization of a high action. ‘ er boiling unsaturated aromatic hydrocarbon re 'Thus a hydrocarbon mixture “comprising es- , sentially normally liquid aromatic hydrocarbons and a fraction containing ole?nic hydrocarbons are commingled and passed‘through a reactor containing a pyrophosphate of copper and/or sil sulting from the primary reaction. ‘ Thus benzene 55 and butadiene give among other products a sub stantial yield of phenyl butenes which polymerize to' form dimers of phenyl butene.- Within cer tain limits it is possible to produce mainly mono-, ver, or at least a portion of thearomatic hydro ' alkylated aromatic hydrocarbons by proper ad carbon is charged to such a reactor while the 60 justment of catalyst activity, ratio of the aromatic fraction containing ole?nic hydrocarbons, as such to ‘the ole?nic hydrocarbons charged, operating ' or preferably diluted. by anotherportion of the aromatic hydrocarbon being treated, is intro duced at various points between the inlet and the outlet of the reaction zone in such a way that conditions such as temperature, pressure, and rate of feed of the reacting'components, etc. The reaction between an aromatic hydrocar ,, bon and a hexene or other normally liquid ole?n the reaction mixture being contacted with the of higher molecular weight may involve not only catalyst will at all 'times contain a relatively low addition of aromatic and ole?nic hydrocarbons but also a depolymerization or splitting of the proportion of the ole?nic hydrocarbon and thus ole?nic hydrocarbon into ole?nic fragments .of favor interaction of aromatic and ole?nic hydro carbons rather than ‘polmerization of the latter. 70 lower molecular weights which react with the _' aromatic hydrocarbons to ‘produce alkylated aro-' While the method of passing the aromatic and matic hydrocarbons. Thus benzene and di-iso ole?nic hydrocarbons, either together-or counter currently, through a suitable reactor containing butene or_tri-isobutene react and yield tertiary butyl benzene and poly-tertiary butyl benzenes, the granular catalyst, is generally customary pro cedure, the interaction of these hydrocarbons may 75 while nonene and benzene yield both butyl and garages amyl benzenes as well as other products by so called depoly-alkylation. weight of mono-isopropyl benzene, and 5 parts by weight of more highly propylated benzenes. Example II‘ I In general, the products formed by interac tion of an ole?nic hydrocarbon with a molal ex cess of an aromatic hydrocarbon are separated A solution consisting of 28 parts by weight (0.07 , from the unreacted aromatic hydrocarbon by molecular proportion) of potassium pyrophos phate trihydrate dissolved in 600 parts by weight suitable means as by distillation, and the unre acted portion of the aromatic hydrocarbon orig of water was added gradually with stirring over inally charged and generally the poly-alkylated a period of 15 minutes to a solution containing 45 ' hydrocarbons formed are returned to the process 10 parts by weight (0.26 molecular proportion) of and mixed with additional quantities of the ole= silver nitrate dissolved in 1250 parts by weight of ?nic and aromatic hydrocarbons being charged water. The precipitated material was washed by to contact with the catalyst. This recycling of v decantation three times using 1000 parts by polyalkylated aromatic hydrocarbons sometimes weight of water in each wash after which the aids in the production of mainly mono-alkylated 1% precipitate was collected on a ?lter and washed aromatic hydrocarbons and depresses the forma= with 1000 parts by weight of water. The washed tion of more-highly alkylated derivatives. The precipitate after drying for 16 hours at 140° C. total alkylated product thus freed from the ex yielded 37 parts ‘by weight of yellowish‘ brown cess of the orignally charged aromatic hydrocar granules of silver pyrophosphate thus equivalent bon is separated into desired fractions by distilla 20 to 93% of the'theoretical based upon the quan tion at ordinary or reduced pressure or by other suitable means. ' tity of potassium pyrophosphate employed. ‘ The excess silver nitrate remaining in the 1 While the process of this invention is particu larly applicable to the production of alkylated mother liquor after precipitation and separation flnic hydrocarbons, it may be utilized also ‘in al ditional quantity of silver pyrophosphate. of the silver pyrophosphate could be treated with aromatic hydrocarbons from aromatic and ole» 25 more potassium, pyrophosphate to produce an ad . kylating other aromatic compounds as in con 10 parts by weight of the silver'pyrophosphate obtained as above described, 80 parts by weight of verting phenols and ole?nic hydrocarbons into alkylated phenols using a catalyst containing a benzene, and 20 parts icy-weight of propane were pyrophosphate of a group I metal hereinabove 30 charged to the rotating autoclave used in Exam set forth and generally operating within the ple I, which was then placed under 50 atmos ranges of temperature and pressure hereinabove pheres pressure of- nitrogen and heated 4 hours * I set forth. , ' at 300° C. After cooling the autoclave, the reac The following examples are given to illustrate tion product removed therefrom was found to the character of results obtainable by thepuse of 35 contain 34 parts by weight of mono-lsopropyl the present process, although the examples benzene and 7 parts by weight of more highly givenv are not introduced with the intention of propylated benzenes. ' unduly restricting the generally broad scope of The nature of the present invention and its the invention. _ ‘ . commercial utility can be seen from the speci? Emmple I 40 cation and examples given, valthough neither sec tion is intended to limit its generally broad scope. A solution of 53 partsby weight (0.14 molecular I claim as my invention: . . proportions) of potassium pyrophosphate trihy 1. A process for producing aromatic compounds drate in 600 parts by weight of water‘ was added having a higher number or carbon atoms per gradually with stirring over a period of 15 min utes to a second solution containing 63 parts by weight (0.25 molecular proportion). of copper sul fate, pentahydrate dissolved in 1250 parts by weight of water. The precipitate so formed was 45 molecule than the aromatic compound from which they are derived which comprises subject ing an aromatic compound and an _o1e?nic hy droearbon to contact under alkylating conditions in the presence of an alkylating catalyst whose washed by decantation three times using 1000 50 alkylating components consist essentially of a parts by weight of water in each wash. iThejpre~ pyrophosphate of a metal selected from the mem cipitated material was then collected on a ?lter, bers of‘ the right-hand column of group I of the washed again with 1000 parts by weight of water, ' periodic table. and afterward dried for 16 hours at 140° to 145° C._ 2. A process for producing alkylated aromatic Thus 38 parts by weight of light blue powdery 55 hydrocarbons which comprises‘ subjecting an aro-' copper pyrophosphate was obtained which repre-i matic hydrocarbon and an ole?nic hydrocarbon sented 90% of the theoretical yield based upon contact under alkylating conditions in the pres the quantity of potassium pyrophosphate used in / to ence of‘ an allrylating catalyst whose alkylatlng ' the precipitation. The excess copper sulfate remaining in the ’ > components consist essentially of a pyrophos mother liquor after precipitation of the copper, 00 phate of a metal selected from the members of zhglrlght-hand column of group I of the periodic pyrophosphate could be treated with more potas a e. sium pyrophosphate to produce an additional 3'. A; process for producing alkylated aromatic quantity of copper pyrophosphate. hydrocarbons which comprises subjecting an aro 10 parts by weight of the copper pyrophosphate 05 matic hydrocarbon and an ole?nic hydrocarbon prepared as hereinabove indicated, 80 parts by to contact at a temperature of from about 100° weight of benzene, and 20 parts by weight ofpro» to about 450° C. in the presence of an alkylating ,pene were charged to a steel autoclave which was catalyst whose alkylating components consist es then placed under 50 atmospheres initial nitro sentially 01’ a pyrophosphate of a metal selected gen pressure and heated for 4 hours at 300° C. 70 irom the members oi’- the right-hand column of The resulting reaction mixture yielded 10 parts by weight of mono-isopropyl benzene and 2 parts group I of the periodic table. > i 4. A process for producing alkylated aromatic by weight .of higher boiling, alkylated benzenes. hydrocarbons which comprises subjecting an aro A likereaction mixture after being heated for 4 matic hydrocarbon and an "ole?nic hydrocarbon hours at 350° C. was found to contain 35 parts by 70 to contact at a temperature of irom about 100°. ‘2,412,329 " a catalyst whose alkylating' components consist es to about450° C. under a pressure of from sub sentially of copper pyrophosphate._ stantially atmospheric to approximately 100 at ‘ ' - 12. .A process for producing alkylated benzenes mospheres in the presence of an alkylating cata which comprises subjecting benzene and an ole lyst whose alkylating components consist essen tially of a pyrophosphate of a metal selected from ' 5» ?nic hydrocarbon to contact at a temperature of from about 100° to about 450° C. under a pres the members of the right-hand column of group sure of from substantially atmospheric to ap _ I ~ 100 atmospheres in the presence of i 5. A process-for producing alkylated aromatic . proximately an alky-lating catalyst consisting essentially of a hydrocarbons which comprises subjecting an aro of a metal selected from the mem matic hydrocarbon and an’ole?nic hydrocarbon lo pyrophospha‘te bers of the right hand column of group I of the to contact at a temperature of from about 100° periodic table. to about 450° C. under a pressure of from sub 13. A‘process for producing alkylated benzenes. stantially atmospheric to approximately 100 at ' . which comprises subjecting benzene and propene mospheres in the presence of a hydrogen-contain is to contact at a temperature of from about 100° II of the periodic‘table. ing gas and of an alkylating catalyst whose a1 to about 450° C. under a pressure of from sub kylating components consist essentially of a pyro phosphate of a‘ metal selected from the members of the right-hand column of. group I or the pe riodic table.‘ stantially atmospheric to approximately 100 at mospheres in the presence of an alkylating cata lyst consisting essentially of copper pyrophos -_ > 6. A process for producing alkylated aromatic 20 phate. 14. A process for producing alkylated benzene hydrocarbons which comprises subjecting an aro ‘ which comprises subjecting benzene and propene matic hydrocarbon and a, normally gaseous ole to contact at a temperature of from about 100° finic hydrocarbon to contact at a temperature of to about 450° C. under a pressure of from. sub from about 100° to about 450° C. under‘a pressurev or from substantially atmospheric to approxi 25 stantially atmospheric-to approximately 100 at mospheres in the presence of an alkylating cata mately 100 atmospheres in the presence of an al lyst consisting essentially of silver pyrophosphate. kylating catalyst whose alkylating components 15. A process for producing alkylated aromatic consist essentially of a pyrophosphate of a metal hydrocarbons which comprises subjecting an arc selected from the members of the right-hand 30 matic hydrocarbon and an oleflnic hydrocarbon column of group I of the periodic table.‘ to contact at a temperature of from about 100° to '7. A process for producing alkylated aromatic about 450° C. under a pressure of from substan hydrocarbons which comprises subjecting an ar0— tially atmospheric to approximately 100 atmos matic hydrocarbon and a normally liquid- ole?nic pheres in the presence of a substantially inert hydrocarbon to contact at a temperature of from carrier supporting an alkylating catalyst consist C. under a pressure of ‘ about 100° to about 450° ing essentially ‘of a pyrophosphate of a metal se from substantially atmospheric to approximately lected from‘ the members of the right hand col 100 atmospheres in the presence of an alkylating catalyst containing a pyrophosphate of a metal selected from the members of the right-hand col umn of group. I of the periodic table. . umn of group I of the periodic table. ‘ 16. An alkylation process which comprises re 40 acting an aromatic compound with an ole?n in the presence of an alkylating catalyst consisting 8. A process. for producing alkylated aromatic hydrocarbons which comprises subjecting an aro matic hydrocarbon and an ole?nic hydrocarbon essentially of a pyrophosphate of a metal ‘from ‘ I$31551right-hand column of group I of the periodic to contact at a temperature of from about 100° to about 450° C. under a pressure of from sub 45 stantially atmospheric to approximately 100 at mospheres in the presence of an alkylating cata lyst containing copper pyrophosphate. e. - - 17. The process as de?ned in claim l?iurther - characterized in that said catalyst is composited with a relatively inert supporting material. 18. An alkylation process which comprises re acting an aromatic compound with an ole?n in 9. A process for producing alkylated aromatic hydrocarbons which comprises subjecting an aro 50 the presence of a sulfuric acid-free alkylating cat- ‘ alyst comprising a pyrophosphate of a metal from ‘ matic hydrocarbon and an ole?nic hydrocarbon to, the-right-hand column of group I of the periodic contact‘ at a temperature of from about 100° to table. . about 450° C. under a pressure of from substan 19. A method for alkylating aromatic hydro tially atmospheric to approximately 100 atmos 55 carbons which comprises ‘contacting an aromatic pheres in the presence of an alkylating catalyst hydrocarbon with an ole?n hydrocarbon at ele whose alkylating- components consist essentially vated temperature in the presence of catalytic . of silver pyrophosphate. _ material comprising as an essential ingredient 10. A process for producing alkylated aromatic copper pyrophosphate. \ / ‘ hydrocarbons which comprises subjecting an aro matic hydrocarbon and a normally gaseous ole 60 .20. A process for producing a mono-alkylated vhydrocarbon which comprises alkylating an arc ?nic hydrocarbon to contact at a temperature of matic hydrocarbon with an ole?n in the presence . from about 110° to about 450° C. under a pressure of from substantially atmospheric to approxi mately 100 atmospheres in the presence of an of a sulfuric acid-free alkylating catalyst com _ prising a pyrophosphate of a metal‘ from the alkylating catalyst whose alkylating components 65 right-hand column vof group I of the periodic table, thereby forming mono-alkylated'and poly alkylated aromatic hydrocarbons, separating the mono-alkylated from the poly-alkylated hydro consist essentially of copper pyrophosphate. 11. A process for producing alkylated aromatic hydrocarbons which comprises subjecting an arc matic hydrocarbon and a normally liquid ole?nic carbons, and returning at least a portion of the _ > hydrocarbon to contact at a temperature of from 70 poly-alkylated aromatic hydrocarbons to the al about 100° to about 450° C. under a pressure of from substantially atmospheric to approximately 100 atmospheres in the presence of an alkylating kylating step. . ‘ RAYMOND E. SCHAAD.