Use of cold flow improver compositions for fuels, blends thereof with biofuels and formulations thereof

Abstract

The present invention relates to the use of polyalkyl(meth)acrylates as an additive to fuels, especially middle distillate fuels and blends thereof. The present invention further relates to the use of a composition comprising polyalkyl(meth)acrylates as dispersing species susceptible to disperse waxes and sludgy material at low temperatures and a hydrocarbon solvent/an oil for improving the cold flow properties of fuel oil and fuel oil compositions. The present invention further relates to the use of these compositions as an additive to fuels, especially in the function of paraffin dispersant, to such fuels themselves and to fuel additive concentrates which comprise this composition dissolved in a hydrocarbon solvent or an oil.

1 . A method for improving the cold flow properties of a fuel oil composition, said method comprising
 mixing a polyalkyl(meth)acrylate with a fuel oil, wherein said polyalkyl(meth)acrylate comprises monomer units of:   (a) from 0% to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I)   
       
         
           
           
               
               
           
         
         wherein 
         R is H or CH 3 , 
         R 1  represents a linear or branched, saturated or unsaturated alkyl group with 1 to 9 carbon atoms or a cycloalkyl group with 3 to 9 carbon atoms, 
         R 2  and R 3  independently represent H or a group of the formula —COOR′, wherein R′ is H or a linear or branched, saturated or unsaturated alkyl group with 1 to 9 carbon atoms or a cycloalkyl group with 3 to 9 carbon atoms, 
         (b) from 20% to 98% by weight of one or more ethylenically unsaturated ester compounds of formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R is H or CH 3 , 
         R 4  represents a linear or branched, saturated or unsaturated alkyl group with 10 to 22 carbon atoms, 
         R 5  and R 6  independently represent H or a group of the formula —COOR″, wherein R″ is H or a linear or branched, saturated or unsaturated alkyl group with 10 to 22 carbon atoms, 
         (c) from 0% to 10% by weight of one or more ethylenically unsaturated ester compounds of formula (III) 
       
       
         
           
           
               
               
           
         
         wherein 
         R is H or CH 3 , 
         R 7  represents a linear or branched, saturated or unsaturated alkyl group with 23 to 40 carbon atoms, 
         R 8  and R 9  independently represent H or a group of the formula —COOR′″ wherein R′″ is H or a linear or branched, saturated or unsaturated alkyl group with 23 to 40 carbon atoms, 
         (d) from 0% to 30% by weight of vinyl aromatic monomers, and 
         (e) from 2% to 80% by weight of at least one N-dispersant monomer, 
         wherein components (a) to (e) add up to 100% by weight. 
       
     
     
         2 . The method according to  claim 1 , wherein the polyalkyl(meth)acrylate has a number average molecular weight M n  of from 2500 to 100000. 
     
     
         3 . The method according to  claim 1 , wherein the polyalkyl(meth)acrylate has a number average molecular weight M n  of from 4000 to 20000. 
     
     
         4 . The method according to  claim 1 , wherein the polydispersity M w /M n  of the polyalkyl(meth)acrylate is from 1 to 8. 
     
     
         5 . The method according to  claim 1 , wherein the polydispersity M w /M n  of the polyalkyl(meth)acrylate is from 1.3 to 2.5. 
     
     
         6 . The method according to  claim 1 , wherein there is a positive amount of the vinyl aromatic monomer (d) which is selected from the group consisting of styrene and substituted styrene. 
     
     
         7 . The method according to  claim 1 , wherein the N-dispersant monomer of component (e) is a monomer of the formula (IV) 
       
         
           
           
               
               
           
         
         wherein 
         R 10 , R 11  and R 12  independently are H or a linear or branched, saturated or unsaturated alkyl group with from 1 to 5 carbon atoms, and 
         R 13  is either a group selected from —C(O)—O—R 14 , —C(O)—NH—R 14 , —C(NR 15 )—O—R 14 , —C(NR 15 )—NH—R 14  and —C(O)—[NH—C 2-10 -alkylene] x -NR 16 R 17 , wherein 
         R 15  represents a linear or branched, saturated or unsaturated alkyl group with from 1 to 5 carbon atoms or an aryl group, and 
         R 14  represents a linear or branched alkyl group with 1 to 20 carbon atoms which is unsubstituted or substituted by a group —NR 16 R 17 , wherein R 16  and R 17  independently represent H or a linear or branched alkyl group with 1 to 8 carbon atoms, or wherein R 16  and R 17  are part of a 4- to 8-membered saturated or unsaturated ring comprising optionally one or more hetero atoms chosen from the group consisting of nitrogen, oxygen and sulphur, wherein said ring may be further substituted with alkyl or aryl groups, and x represents a number 1, 2, 3 or 4, 
         or 
         R 13  is a group —NR 18 R 19 , wherein R 18  and R 19  are part of a 4- to 8-membered saturated or unsaturated ring, comprising at least one carbon atom as part of the ring which forms a double bond to a hetero atom chosen from the group consisting of nitrogen, oxygen and sulphur, wherein said ring may be further substituted with alkyl or aryl groups. 
       
     
     
         8 . The method according to  claim 1 , wherein the N-dispersant monomer of component (e) is selected from the group consisting of vinyl substituted nitrogen heterocyclic monomers, N-vinyl-substituted nitrogen heterocyclic monomers, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate monomers, methacrylamide monomers, N-tertiary alkyl acrylamides and corresponding methacrylamides, vinyl substituted amines and N-vinyl lactams. 
     
     
         9 . A method for improving the cold flow properties of a fuel oil composition, said method comprising:
 mixing a concentration composition with a fuel oil, wherein said concentrate composition comprises   (A) from 30% to 90% by weight of a polyalkyl(meth)acrylate which comprises monomer units of:
 (a) from 0% to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I) 
   
       
         
           
           
               
               
           
         
         
           wherein 
           R is H or CH 3 , 
           R 1  represents a linear or branched, saturated or unsaturated alkyl group with 1 to 9 carbon atoms or a cycloalkyl group with 3 to 9 carbon atoms, 
           R 2  and R 3  independently represent H or a group of the formula —COOR′, wherein R′ is H or a linear or branched, saturated or unsaturated alkyl group with 1 to 9 carbon atoms or a cycloalkyl group with 3 to 9 carbon atoms, 
           (b) from 20% to 98% by weight of one or more ethylenically unsaturated ester compounds of formula (II) 
         
       
       
         
           
           
               
               
           
         
         
           wherein 
           R is H or CH 3 , 
           R 4  represents a linear or branched, saturated or unsaturated alkyl group with 10 to 22 carbon atoms, 
           R 5  and R 6  independently represent H or a group of the formula —COOR″, wherein R″ is H or a linear or branched, saturated or unsaturated alkyl group with 10 to 22 carbon atoms, 
           (c) from 0% to 10% by weight of one or more ethylenically unsaturated ester compounds of formula (III) 
         
       
       
         
           
           
               
               
           
         
         
           wherein 
           R is H or CH 3 , 
           R 7  represents a linear or branched, saturated or unsaturated alkyl group with 23 to 40 carbon atoms, 
           R 8  and R 9  independently represent H or a group of the formula —COOR′″ wherein R′″ is H or a linear or branched, saturated or unsaturated alkyl group with 23 to 40 carbon atoms, 
           (d) from 0% to 30% by weight vinyl aromatic monomers, and 
           (e) from 2% to 80% by weight of at least one N-dispersant monomer, wherein components (a) to (e) add up to 100 weight %; and 
         
         (B) from 10% to 70% by weight of a hydrocarbon solvent or oil. 
       
     
     
         10 . A method for improving the cold flow properties of a fuel oil composition, the method comprising:
 mixing
 (a) from 0% to 99% by weight of at least one biofuel oil which is based on fatty acid esters, 
 (b) from 1% to 100% by weight of middle distillates of fossil origin and/or of vegetable and/or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters, and 
 (c) the concentrate according to  claim 9 . 
   
     
     
         11 . The method according to  claim 1 , wherein the fuel oil composition further comprises one or more additives selected from the group consisting of additional cold flow improvers, dispersants, conductivity improvers, demulsifiers, defoamers, lubricity additives, antioxidants, cetane number improvers, detergents, dyes, corrosion inhibitors, metal deactivators, metal passivators and odourants. 
     
     
         12 . The method according to  claim 2 , wherein the fuel oil composition further comprises one or more additives selected from the group consisting of additional cold flow improvers, dispersants, conductivity improvers, demulsifiers, defoamers, lubricity additives, antioxidants, cetane number improvers, detergents, dyes, corrosion inhibitors, metal deactivators, metal passivators and odourants. 
     
     
         13 . The method according to  claim 7 , wherein the fuel oil composition further comprises one or more additives selected from the group consisting of additional cold flow improvers, dispersants, conductivity improvers, demulsifiers, defoamers, lubricity additives, antioxidants, cetane number improvers, detergents, dyes, corrosion inhibitors, metal deactivators, metal passivators and odourants. 
     
     
         14 . The fuel composition according to  claim 10  further comprising one or more additives selected from the group consisting of additional cold flow improvers, dispersants, conductivity improvers, demulsifiers, defoamers, lubricity additives, antioxidants, cetane number improvers, detergents, dyes, corrosion inhibitors, metal deactivators, metal passivators and odourants. 
     
     
         15 . The method according to  claim 1  wherein the fuel in the fuel oil composition is a middle distillate fuel. 
     
     
         16 . The method according to  claim 1  wherein the polyalkyl(meth)acrylate polymer is a random copolymer, gradient copolymer, block copolymer and/or graft copolymer.