Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties

Abstract

The invention provides a fuel oil composition F) comprising F1) 89-50% by volume of a fuel oil of mineral origin and F2) 11-50% by volume of a fuel oil of vegetable and/or animal origin, and, as a cold additive, the constituents A) at least one copolymer composed of ethylene and 8-21 mol % of at least one acrylic or vinyl ester having a C 1 -C 18 -alkyl radical and B) at least one comb polymer containing structural units composed of B1) at least one olefin as monomer 1 which bears at least one C 8 -C 18 -alkyl radical on the olefinic double bond, and B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which bears at least one C 8 -C 16 -alkyl radical bonded via an ester moiety, where the sum Q Q = ∑ i ⁢ w 1 ⁢ i · n 1 ⁢   ⁢ i + ∑ j ⁢ w 2 ⁢   ⁢ j · n 2 ⁢   ⁢ j of the molar averages of the carbon chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the ester groups of monomer 2 on the other is from 21.0 to 28.0, where w 1 is the molar proportion of the individual chain lengths in the alkyl radicals of monomer 1, w 2 is the molar proportion of the individual chain lengths in the alkyl radicals of the ester groups of monomer 2, n 1 are the individual chain lengths in the alkyl radicals of monomer 1, n 2 are the individual chain lengths in the alkyl radicals of the ester groups of monomer 2, i is the serial variable for the individual chain lengths in the alkyl radicals of monomer 1, and j is the serial variable for the individual chain lengths in the alkyl radicals in the ester groups of monomer 2.

1 . A fuel oil composition F) comprising 
 F1) 89-50% by volume of a fuel oil of mineral origin and    F2) 11-50% by volume of a fuel oil of vegetable and/or animal origin, and a cold additive comprising the constituents    A) at least one copolymer composed of ethylene and 8-21 mol % of a comonomer of at least one acrylic or vinyl ester having a C 1 -C 18 -alkyl radical and    B) at least one comb polymer containing structural units composed of 
 B1) at least one olefin as monomer 1 which bears at least one C 8 -C 18 -alkyl radical on the olefinic double bond, and  
 B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which bears at least one C 8 -C 16 -alkyl radical bonded via an ester moiety,  
 where the sum Q  
         Q   =         ∑   i     ⁢       w     1   ⁢   i       ·     n     1   ⁢           ⁢   i           +       ∑   j     ⁢       w     2   ⁢           ⁢   j       ·     n     2   ⁢           ⁢   j                   
 of molar averages of the carbon chain length distributions in the alkyl radical of monomer 1 on the one hand and the alkyl radical of the ester moiety of monomer 2 on the other is from 21.0 to 28.0, where  
   w 1  is a molar proportion of the individual chain lengths in the alkyl radical of monomer 1,    w 2  is a molar proportion of the individual chain lengths in the alkyl radical of the ester groups of monomer 2,    n 1  are individual chain lengths in the alkyl radical of monomer 1,    n 2  are individual chain lengths in the alkyl radical of the ester moiety of monomer 2,    i is a serial variable for the individual chain lengths in the alkyl radical of monomer 1, and    j is a serial variable for the individual chain lengths in the alkyl radical in the ester moiety of monomer 2.    
     
     
         2 . A fuel oil composition as claimed in  claim 1 , wherein Q is from 22.0 to 27.0.  
     
     
         3 . A fuel oil composition of  claim 1 , wherein the comonomer of constituent A, comprises from 3.5 to 20 mol % of vinyl acetate and from 0.1 to 12 mol % of a vinyl ester selected from the group consisting of vinyl neononanoate, vinyl neodecanoate vinyl 2-ethylhexanoate, and mixtures thereof, the total comonomer content of constituent A) being between 8 and 21 mol %.  
     
     
         4 . A fuel oil composition of  claim 1 , wherein the comonomer of constituent A comprises from 8 to 18 mol % of vinyl esters, and further comprises from 0.5 to 10 mol % of olefins selected from the group consisting of propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene, norbornene, and mixtures thereof.  
     
     
         5 . A fuel oil composition of  claim 1 , wherein the copolymers which make up constituent A have melt viscosities between 20 and 10 000 mPas.  
     
     
         6 . A fuel oil composition of  claim 1 , wherein the copolymers which make up constituent A have a degree of branching between 1 and 9 CH 3 /100 CH 2  groups which do not stem from the comonomers.  
     
     
         7 . A fuel oil composition of  claim 1 , wherein constituent B comprises monomers which are derived from esters or anhydrides or mixtures of esters and anhydrides of an acid selected from the group consisting of maleic acid, fumaric acid itaconic acid, and mixtures thereof.  
     
     
         8 . A fuel oil composition of  claim 1 , wherein the ester moiety of constituent B are derived from alcohols having linear alkyl radicals.  
     
     
         9 . A fuel oil composition of  claim 1 , wherein an average molecular mass of constituent B is between 1200 and 200 000 g/mol.  
     
     
         10 . A fuel oil composition of  claim 1 , wherein constituent B comprises monomers derived from α-olefins.  
     
     
         11 . A fuel oil composition of  claim 1 , wherein a mixing ratio A:B is between 10:1 and 1:10.  
     
     
         12 . A fuel oil composition of  claim 1 , further comprising polar nitrogen-containing paraffin dispersants.  
     
     
         13 . A fuel oil composition of  claim 1 , which comprises 88-65% by volume of F1 and 12-35% by volume of F2.  
     
     
         14 . A fuel oil composition of  claim 1 , wherein the fuel oil of animal or vegetable origin comprises one or more esters of a monocarboxylic acid having from 14 to 24 carbon atoms and alcohol having from 1 to 4 carbon atoms.  
     
     
         15 . A fuel oil composition as claimed in  claim 14 , wherein the alcohol is methanol or ethanol.  
     
     
         16 . A fuel oil composition of  claim 1 , wherein the fuel oil of animal or vegetable origin contains more than 4% by weight of esters of saturated fatty acids.  
     
     
         17 . A process for improving the cold flow properties of mixtures of mineral fuel oils and fuel oils of animal or vegetable origin, said process comprising adding to said mixtures a cold additive comprising the constituents 
 A) at least one copolymer composed of ethylene and 8-21 mol % of a comonomer of at least one acrylic or vinyl ester having a C 1 -C 18 -alkyl radical and    B) at least one comb polymer containing structural units composed of 
 B1) at least one olefin as monomer 1 which bears at least one C 8 -C 18 -alkyl radical on the olefinic double bond, and  
 B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which bears at least one C 8 -C 16 -alkyl radical bonded via an ester moiety,  
 where the sum Q  
         Q   =         ∑   i     ⁢       w     1   ⁢   i       ·     n     1   ⁢           ⁢   i           +       ∑   j     ⁢       w     2   ⁢           ⁢   j       ·     n     2   ⁢           ⁢   j                   
 of molar averages of the carbon chain length distributions in the alkyl radical of monomer 1 on the one hand and the alkyl radical of the ester moiety of monomer 2 on the other is from 21.0 to 28.0, where  
   w 1  is a molar proportion of the individual chain lengths in the alkyl radical of monomer 1,    w 2  is a molar proportion of the individual chain lengths in the alkyl radical of the ester groups of monomer 2,    n 1  are individual chain lengths in the alkyl radical of monomer 1,    n 2  are individual chain lengths in the alkyl radical of the ester moiety of monomer 2,    i is a serial variable for the individual chain lengths in the alkyl radical of monomer 1, and    j is a serial variable for the individual chain lengths in the alkyl radical in the ester moiety of monomer 2.    
     
     
         18 . A process for producing fuel oil compositions F comprising fuel oils of mineral (F1) and animal or vegetable (F2) origin, having improved cold flow properties, by adding an additive to the mixture of fuel oils of mineral (F1) and animal or vegetable (F2) origin, said additive comprising the constituents 
 A) at least one copolymer composed of ethylene and 8-21 mol % of a comonomer of at least one acrylic or vinyl ester having a C 1 -C 18 -alkyl radical and    B) at least one comb polymer containing structural units composed of 
 B1) at least one olefin as monomer 1 which bears at least one C 8 C 18 -alkyl radical on the olefinic double bond, and  
 B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which bears at least one C 8 -C 16 -alkyl radical bonded via an ester moiety,  
 where the sum Q  
         Q   =         ∑   i     ⁢       w     1   ⁢   i       ·     n     1   ⁢           ⁢   i           +       ∑   j     ⁢       w     2   ⁢           ⁢   j       ·     n     2   ⁢           ⁢   j                   
 of molar averages of the carbon chain length distributions in the alkyl radical of monomer 1 on the one hand and the alkyl radical of the ester moiety of monomer 2 on the other is from 21.0 to 28.0, where  
   w 1  is a molar proportion of the individual chain lengths in the alkyl radical of monomer 1,    w 2  is a molar proportion of the individual chain lengths in the alkyl radical of the ester groups of monomer 2,    n 1  are individual chain lengths in the alkyl radical of monomer 1,    n 2  are individual chain lengths in the alkyl radical of the ester moiety of monomer 2,    i is a serial variable for the individual chain lengths in the alkyl radical of monomer 1, and    j is a serial variable for the individual chain lengths in the alkyl radical in the ester moiety of monomer 2.