United  States  Patent  Office  3,251,895  Patented  May  17,  1966  1  2  3,251,895  ALLYL  ALKYLATION  CATALYST  AND  ALKYLATION  PROCESS  John  B.  Wilkes,  Albany,  Calif.,  assignor  to  Chevron  Research  Company,  a  corporation  of  Delaware  No  Drawing.  Filed  July  20,  1962,  Ser.  No.  211,430  12  Claims,  (CI.  260-668)  This  invention  relates  to the  preparation  and  use  of  alkali  metal  containing  ally!  alkylation  catalysts.  More  particularly,  it  relates  to the  preparation  of a  dispersed  ally!  alkylation  catalyst  complex  containing  a  superfinely  divided  solid  inorganic  nonacidic  oxy-compound  and  a  limited  amount  of a  polar  ,organic  compound.  Alkali  metal  containing  catalyst  materials  useful  in the  .allyl  alkylation  of  hydrocarbons,  as for  example  in the  dimerization  of  olefins,  co-dimerization  of  dissimilar  ole› fins,  side-chain  alkylation  of  aromatics,  and  the  like,  are  necessarily  extremely  chemically  reactive,  are  essentially  insoluble  in the  inert  hyd:mcarbon  media  desirably  em› ployed  in  their  use,  and  because  of  these  characteristics  effective  ally!  alkylation  catalysts  capable  of  long  life  with  high  activity  useful  in  continuous  allyl  alkylation  processes  are  not  known  in the  art.  • It  is  known  to  prepare  allyl  alkylation  catalysts  using  small  amounts  of  organic  dispersing  aids  to  yield  im› proved  catalysts.  These  systems,  however,  are  found  in  practice  to be  metastable.  That  is,  small  variations  or  fluctuations  in the  reaction  conditions  may  cause  a  pre› cipitous  agglomeration  of  the  disperse  phase.  Another  unpredictable  effect  which  is  noted  appears  to  be  an  autocatalytic  tar  and  coke-forming  reaction  as  between  the  dispersing  agent,  catalyst  active  reactants,  and  possi› bly  the  medium.  When  any  of  these  conditions  obtain,  the  reactor,  process  lines,  and  the  like,  must  be  thoroughly  purged  and  a  fresh  start  made.  An  expedient  in  the  ally!  alkylation  .catalyst  art  is to  •  dispose  the  catalyst  ac› tive  upon  a  solid.  This  may  offer  some  degree  of  im› provement,  depending  upon  the  particular  solid  employed,  over  the  dispersed  system.  Nevertheless,  these  catalysts  have  a  tendency  to  agglomerate  under  ally!  alkylation  conditions  which  may  be  counteracted,  but  this  requires  efficient  vigorous  mechanical  mixing  at an  appreciable  energy  and  equipment  cost.  These  disposed  catalysts  fre› quently  are  found  to be  of  limited  life  as a  result  of un› desirable  side  reactions  and  to  suffer  from  unpredictable  variations  in  activity  from  batch  to  batch  in the  catalyst  preparation.  It has  now  been  discovered  that  alkali  metal  containing  ally!  alkylation  catalysts  suitable  for  use  in  continuous  alkylation  processes  may  be  produced  in  an  aprotic  hy› drocarbon  medium  by  contacting  under  dispersh-ig  con› ditions  and  a  temperature  below  about  230°  C.  in the  following  proportions:  ( 1 )  One  gram  atom  of  molten  alkali  metal  having  an  atomic  number  greater  than  3  and  less  than  56;  (2)  From  about  7 to  45 cc.  of an  inorganic,  nonacidic,  solid  oxy-compound  substantially  unreactive  to  alkali  metals  and  aprotic  hydrocarbons  at  temperatures  below  230°  C.  having  a  particle  sizing  in the  range  from  about  0.1  to 10  microns;  (3)  From  about  7X10- 4  to  1.0xI0- 1 .mols  of  an  organic  compound  thermally  stable  up  to at  least  230°  C.  having  a  dipole  moment  of  at  least  1  Debye  unit  (µX  10 $^{18 }$e.s.u.)  and  having  at  least  one  oleophylic  group;  and  (  4)  From  about  0.3  to  7.5  liters  .of  aprotic  hydro› carbon:  Ally!  alkylation  catalyst  complexes  prepared  by  contact› ing  the  above  designated  components  in the  kinds,  pro› portions  and  physical  states  indicated  under  dispersing  conditions  are  found  to be  generally  of  excellent  activity  and  highly  reproducible.  Induction  periods  experienced  in  their  use  are  negligible  or of  short  duration,  and  the  coke  and  tar  formation  problems  of the  prior  art  catalysts  as  well  as  catalyst  meta-stability  are  eliminated.  Especial› ly  advantageous  in the  use  of the  catalysts  of  the  pres› ent  invention  is  the  removal  of  any  particular  require› ment  for  mechanical  mixing.  A  monomer-gas  jet  stream  or  an  inert  gas  stream  is  generally  adequate.  In  general,  the  preparation  of  satisfactory  ally!  alkyla- tion  catalysts  involves  the  contacting  of  a  mixture  of  molten  alkali  metal,  discreetly  sized  solid  particles,  a  polar  organic  compound,  and  an  aprotic  hydrocarbon  medium  under  dispersing  conditions.  By  dispersing  con- ditions  is  meant  high  speed,  high  sheer  stirring  as  by  mechanically  driven  mixing  blades,  high  frequency  vibrators,  and  the  like,  such  as are  known  in the  disper› sion  producing  and  emulsion  producing  art  and  the  equiva› lent.  The  contacting  is  accomplished  at  temperatures  from  about  30°  C.  to  230°  C.  During  the  preparation  of the  catalyst  complex,  temperatures  just  exceeding  the  point  of the  alkali  metal  up  to  20-40°  above  the  melting  point  are  preferred,  because  until  .the  actual  complex  is  established,  the  mutual  stabilizing  effects  of the  associated  components  are  not  available.  Thus,  while  higher  tem› peratures  may  be  employed,  there  is  little  or no  advantage  in so  doing.  As  indicated,  the  particle  size  of the  solid  and  the  relative  amounts  of the  components  used  in pre› paring  the  catalyst  determine  whether  or  not  a  satisfac- tory  allyl  alkylation  catalyst  results.  Thus,  the  inorganic  solid  oxy-compound  must  be of  a  superfine  particle  size,  that  is,  in  general  below  about  10  microns  and  above  about  0.10  micron.  Particle  sizing  in the  range  0.1  to 6  microns  yields  excellent  catalysts.  Solid  particles  of  sizes  somewhat  greater  than  about  10  microns,  as  shown  by  microscopic  examination,  do  not  appear  to  form  the  catalyst  complex.  On  the  other  hand,  particles  sized  below  about  0.1  micron  are  unsatisfactory.  The  inorganic  oxy-compounds  contemplated  for  use  in the  present  process  are  in  general  nonacidic  and  sub› stantially  unreactive  in  superfinely  divided  form  with  alkali  metals  at  temperatures  up  to  200°  C.  and  even  230°  C.  and  higher.  They  are  also  necessarily  substan› tially  unreactive  toward  hydrocarbons  up  to  230°  C.  and  higher,  and  desirably  have  a  density  less  then  5.0  grams/  cc.  In  .a:  preferred  fonm,  these  oxy-compounds  are  crys› taUine  as  contrasted  with  amorphous  matter,  and  have  a  density  less  than  3.0  grams  per  cubic  centimeter.  More  preferably,  the  oxy-compounds  are  crystalline  oxy-salts;  still  more  preferably,  they  ,are  oxy-salts  wherein  the  nega› tive  radical  comprises  elements  having  atomic  numbers  less  than  17;  and  of the  oxy-salts  wherein  the  negative  radical  comprises  elements  having  atomic  numbers  less  than  17,  those  compounds  ,in  which  the  positive  radical  is  the  ,cation  of an  element  having  a  related  electronega› tivity  below  about  1.6  (c.f.  "Nature  of  the  Chemical  Bond,"  Linus  Pauling,  Cornell  Univ.  Press,  1945,  p.  65)  are  most  particularly  preferred  compounds.  By  oxy› compounds  is  meant  both  individual  compounds  and  com- pound  mixtures.  As  an  illustration  of  compounds  embraced  within  the  .scope  of the  inorganic  oxy-compounds  referred  to  herein  are  the  substantially  anhydrous  •compounds  of  aluminum  orthophosphate,  aluminum  silicate,  aluminum  sulfate,  barium  carbonate,  barium  oxide,  barium  hypophosphate,  barium  orthophosphates,  barium  metasilicate,  barium  sulfate,  barium  thiosulfate,  beryllium  aluminate,  beryl› lium  aluminum  silicate,  beryllium  oxide,  beryllium  car› bonate,  beryllium  orthophosphate,  beryllium  orthosili- cate,  beryllium  sulfate,  calcium  aluminate,  calcium  car› bonate,  calcium  oxide,  calcium  metaphosphate,  calcium 