The  Development  of  Green  Chemistry  in  the  Oil  and  Gas  

Produc:on  Industry  

UK  North  Sea  Sector  

Outline  

•  What  is  ‘green  chemistry’?  

•  The  oilfield  chemical  market  

•  UK  North  Sea  •  Regulatory  and  economic  drivers  

•  Examples  of  “greening”  

•  Challenges  remaining  

•  A  new  approach?  

Green  Chemistry  Defini:ons  "Design  of  chemical  products  and  processes   that   reduce  or  eliminate  the   use   or   genera:on   of   substances   hazardous   to   humans,   animals,  plants,  and  the  environment.”  (IUPAC)  

The  12  principles  of  green  chemistry  –  Warner  and  Anastas:  

–  8.   Use   safer   solvents   and   reac:on   condi:ons:   Avoid   using  solvents,   separa:on   agents,   or   other   auxiliary   chemicals.   If  these  chemicals  are  necessary,  use  innocuous  chemicals.  

–  10.  Design  chemicals  and  products  to  degrade  a[er  use:  Design  chemical  products  to  break  down  to  innocuous  substances  a[er  use  so  that  they  do  not  accumulate  in  the  environment.  

Green  Chemistry  in  the  Oilfield  

•  Focus  is  on  biodegradable,  less  environmentally  harmful  materials.  

•  Li^le  is  on  sustainability  or  the  life-­‐cycle  of  producing  these  materials.  

•  An  end  of  pipe  vision  not  an  holis:c  approach.  •  This  is  really  only  applied  in  certain  geographic  loca:ons.  

Oilfield  Speciality  Chemical  Market  •  Expected  to  reach  $6.5  Billion  by  2016  

 Specialty  Oilfield  Chemicals  Market  by  Types,  Applica9ons,  Trends  &  Global  Forecasts      (2011  –  2016)    

•  Dominated  by  interna:onal  service  companies.  –  Large  amount  of  addi:onal  service  is  required  in  applica:on.  –  In  the  main  products  are  formulated  for  applica:on.  

•  Chemical  manufacturers  do  not  supply  directly.  

•  UK  North  Sea  –  less  oil,  more  water.  

 

Making  Chemistry  Green  In  general,  two  complementary  approaches  have  been  adopted:  

– Deriva:on  of  the  exis:ng  chemical  type  to  provide  a  more  biodegradable  and  less  harmful  structure.  

– Examina:on   of   other   chemical   structures   which  are   know  or   presumed   to  be   less   harmful   to   the  environment   e.g.   use   of   natural   product   type  chemistry.  

“BP  pipeline  leaked  'oily  mist'  onto  27  acres  of  snow-­‐covered    

tundra  in  Alaska.”    (1st  May  2014)  

Corrosion  Inhibitors  •  Produc:on  fluids  contain  corrosive  gases:  

–   CO2  and  H2S.    

•  Retarda:on  of  corrosion  on  metal  surfaces:    

–  Corrosion  inhibitors.  –  Film  forming  surfactants.  

•  Four  main  types:  

–  Fa^y  amines  and  their  adducts.  

–  Quaternary  ammonium  salts  of  a  variety  of  amines  and  amides.  

–  Imidazolines.  

–  Alkyl  pyridine  and  alkyl  quinolones  and  ammonium  salts  thereof.  

Imidazolines  

Studies  have  shown  that  op:mum  performance  is  related  to  the  chain  length,  with  the  oleic  C18  providing  

an  op:mum  performance.  

More  Water  Soluble  

Reac:on  of  pendant  alkyl  amine  group  of  an  imidazoline  with  stoichiometric  amounts  of  acrylic  acid  gives  the  structure  below,  which  is  more  water  soluble.  

Different  Chemistry  

Aspar:c  Acid   Alkyl  Polyglucoside  

!

Scale  Inhibitors  

•  Three  main  types  of  chemistry:  

–  Polycarboxylates  

–  Other  polymers  

–  Phosphonates  

•  Generally,  chemistry  is  recognised  as  environmentally  

acceptable,  however,  some  authori:es  legislate  against  

phosphonates  regarding  them  as  not  sufficiently  

biodegradable.  

Halite  and  Other  Scales  

•  Halite  (  NaCl)  and  sulphides,  lead,  zinc  etc.  •  Hexacyanoferrate  salts  and  nitrilotrialkanamides:    

– nitrilotriacetamide  

 

Demulsifiers  

•  Offshore  oil  and  water  separa:on  in  minutes.  

•  2  or  3  components,  usually  surfactants  formulated  in  

a  solvent.  

•  Many  are  not  environmentally  acceptable:  

– Biodegrada:on  – Endocrine  disrup:on  – Toxic  monomer  residues  

Green  Demulsifiers  

•  Epoxidised  fa^y  acid,  such  as  soya.  •  Polyglycols  

•  Polyglycerols  •  Terpene  alkoxylates  •  Alkoxylated  alkyl  polyglucosides  

•  Most  of  above  is  revisi:ng  old,  less  efficient  chemistries.  

Green  Demulsifiers  

•  Tradi:onal  demulsifiers  biodegrada:on:    

–  Many  are  polyalkoxylate  chains.  EO  and  PO  alkoxyla:on  EO  chains  more  degradable  than  PO  chains.  

–  Polybutoxylate  chains  made  from  ring  opening  of  butylene  oxide  are  even  less  degradable.  

–  Straight  polybutoxylate  chains  (polytetra  methylene  glycol)  made  from  ring  opening  tetrahydrofuran  are  more  

biodegradable.  (P.  S  Newman,  C.  Han  and  R.D.McClain,  Interna:onal  patent  

Applica:on  WO/2006/068702)  

•   Return  to  THF.  

Biocides  

•  By  nature  and  effect  they  are  highly  toxic.  •  Highly  regulated  through  BPR  –  no  innova:on  or  new  biocides.  

•  Formaldehyde  releasers  being  examined  but  being  

considered  for  formaldehyde  labeling.  

•  Where  can  we  find  an  effec:ve  green  biocide?  

•  Alterna:ve  methods  of  microbial  control.  

Wax  Control  

•  Inhibitors,  dispersants  and  PPD’s  used  to  control  the  forma:on  and  deposi:on  of  petroleum  waxes  as  crude  oils  cool.  

•  Chemistries  are  generally  polymeric  and  oil  soluble.  

•  Heat  and  flow  can  eliminate  their  use  (most  of  the  :me).  

•  New  crudes  are  now  being  discovered  and  exploited,  mainly  in  deepwater  or  harsh  environments  and  may  of  these  have  high  wax  contents.    

•  Many  of  these  ecosystems,  such  as  arc:c  Norway,  are  regarded  as  environmentally  sensi:ve  and  require  chemicals  to  meet  stringent  regulatory  controls.  

•  Most  chemistries  are  not  very  biodegradable  and  can  have  toxic  proper:es.  The  solvent  systems  are  also  of  high  concern.  

Wax  Control  Agents  Chemistry  

•  Various  polymers  and  co-­‐polymers:  

– Ethyl  vinyl  acetate  polymers  and  co-­‐polymers.  

– Acrylate  polymers  and  co-­‐polymers.  

– Maleic  anhydride  co-­‐polymers.  

•  Alkyl  subs:tuted  phenols  –  dispersants.  

•  Low  concentra:ons  of  polymers  in  aroma:c  solvents.    

Green  Solvents  •  Glycols,  Methanol  and  Xylene.  

•  In  the  main  non-­‐polar,  very  few  aroma:cs  and  o[en  low  solvency.  

•  Some  have  health  and  safety  risks.  

•  Ester  solvents:  

–  good  solvency.  –  good  environmental  proper:es.    

–  low  health  and  safety  risks.  –  desirable  physical  proper:es  such  as  a  high  boiling  point,  reasonable  

viscosity  and  high  flash  point.  

•  Ester  Alcohols  (mainly  in  drilling  applica:ons).  

•  Oleates,  par:cularly  for  corrosion  inhibitors.  

An:foams  and  Defoamers  •  Main  class  of  product  used:  

–  Oil  soluble  silicone  defoamers  and  an:foams.  

–  Are  given  a  poor  environmental  profile  due  to  their  poor  rates  of  biodegrada:on.    

–  Not  bioavailable.  •  Polyglycol  materials  are  in  this  use  as  alterna:ves:  

–  Biodegradable.    –  Dose  rates  of  100  fold  plus  compared  to  the  previous  silicon  materials,  if  

they  work  at  all.  

–  Are  the  silicon  materials  as  harmful?  

•  This  is  an  area  where  an  efficient,  useful  and  green  defoamer  and/or  an:foam  would  have  a  poten:al  immediate  impact.    

Regula:on  and  the  Environment  

•  Regula:on,   par:cularly   in   the   North   Sea,   has  been  a  primary  driver  in  “greening”.  

•  Regula:on  has  been  primarily  hazard  based  and  

biodegrada:on   focused   –   does   this   protect   the  

environment?  

•  Risk  based  approaches  used  in  other  industries.  

Sustainability  –  a  way  forward?  •  The  approaches  in  oil  and  gas  industry  are  reac:ve.  •  Sustainability,  although  counter-­‐intui:ve,  may  provide  

an  alterna:ve  greening  approach.  

•  Examples:  

– Demulsifiers  from  polybutoxylates  are  environmentally  acceptable  when  derived  from  THF.    

–  BASF  -­‐  THF  can  be  bioderived  and  be  sustainable.  – Henkel  -­‐  LCA  of  all  surfactant  manufacture.  

Work  Con:nues  •  Examina:on   of   natural   products   for   cri:cal   proper:es   but  

also  ensuring  they  are  sustainably  derived  and/or  synthesised  in  a  green  fashion.    –  An    example:  Hydrate  inhibitors.  

•  Glycoproteins  in  ar:c  fish.  •  current  inhibitors.  •  New  pseudo  protein  like  materials,  dendri:c  products  etc.  

•  Apply  the  green  principles  of  Anastas  and  Warner.  

•  Examine  how  chemicals  purchased  are  made.  

•  Conduct  life  cycle  analysis.  

The  Future  

More  Regula:on?  Global  regula:on?    

More  Environmental  Awareness?    

More  Pressure  from  Policy  Makers  and  Public?          Be  proac:ve  –  think  sustainably.  

 

Many  Thanks    

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