Diesel Composition and Method of Increasing Biodiesel Oxidation Stability

Abstract

The present invention discloses a diesel composition, which comprises a base diesel and an additive composition, characterized in that said base diesel comprises biodiesel, and said additive composition comprises component (a) and component (b), wherein said component (a) is an arylamine-type antioxidant, and said component (b) is one or more polyamines or derivatives thereof. The diesel composition of the present invention has a superior oxidation stability.

1 . A diesel composition, which comprises a base diesel and an additive composition, characterized in that said base diesel comprises biodiesel, and said additive composition comprises component (a) and component (b), wherein said component (a) is an arylamine-type antioxidant, and said component (b) is one or more polyamines or derivatives thereof. 
     
     
         2 . The diesel composition according to  claim 1 , wherein the weight ratio of said component (b) to said component (a) is 0.01-100:1. 
     
     
         3 . The diesel composition according to  claim 2 , wherein the weight ratio of said component (b) to said component (a) is 0.05-10:1. 
     
     
         4 . The diesel composition according to  claim 1 , wherein the arylamine-type antioxidant of component (a) is at least one selected from the group consisting of a substituted naphthylamine, a substituted diphenylamine, a substituted p-phenylene diamine, and a substituted quinoline. 
     
     
         5 . The diesel composition according to  claim 4 , wherein said substituted naphthylamine is one or more selected from the group consisting of phenyl-α-naphthylamine, phenyl-β-naphthylamine, and N-p-methoxyphenyl-α-naphthylamine, said substituted diphenylamine is one or more selected from the group consisting of alkylated diphenylamines with substituents having between 4 and 10 carbon atoms, and said substituted quinoline is one or more selected from the group consisting of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, and 2,2,4-trimethyl-1,2-dihydroquinoline. 
     
     
         6 . The diesel composition according to  claim 4 , wherein the arylamine-type antioxidant of component (a) is one or more selected from the group consisting of di-substituted p-phenylene diamines with substituents having between 4 and 10 carbon atoms. 
     
     
         7 . The diesel composition according to  claim 6 , wherein said arylamine-type antioxidant is N-phenyl-N′-cyclohexyl-p-phenylene diamine, N,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, N,N′-bis-(1,4-dimethylamyl)-p-phenylene diamine, N-p-tolyl-N′-(1,3-dimethylbutyl)-p-phenylene diamine, N,N′-diheptyl-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-isopropyl-N′-p-tolyl-p-phenylene diamine, N,N′-xylyl-p-phenylene diamine, N,N′-diphenyl-p-phenylene diamine, N,N′-di-(β-naphthyl)-p-phenylene diamine, N,N′-di-sec-butyl-p-phenylene diamine, N,N′-dioctyl-p-phenylene diamine, N,N′-bis-(1-methylheptyl)p-phenylene diamine, N,N′-bis-(1-ethyl-3-methylamyl)p-phenylene diamine, N,N′-bis-(1,4-dimethylbutyl)p-phenylene diamine, N-octyl-N′-phenyl-p-phenylene diamine, N-isobutyl-N′-phenyl-p-phenylene diamine, N,N′-dimethyl-N,N′-bis-(1-methylpropyl)p-phenylene diamine, N-(p-toluene sulfonyl)-N′-phenyl-p-phenylene diamine, N-(3-methylpropenylacryloxo-2-hydroxypropyl)-N′-phenyl-p-phenylene diamine, N-(3-anilinophenyl)methylacrylamide, or N-hexyl-N′-phenyl-p-phenylene diamine. 
     
     
         8 . The diesel composition according to  claim 6 , wherein said arylamine-type antioxidant is one or more of N,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, N-octyl-N′-phenyl-p-phenylene diamine, N,N′-diheptyl-p-phenylene diamine, N,N′-di-sec-butyl-p-phenylene diamine, N,N′-bis-(1-ethyl-3-methylamyl)p-phenylene diamine, N,N′-bis-(1,4-dimethylbutyl)p-phenylene diamine, N,N′-dioctyl-p-phenylene diamine, and N,N′-bis-(1-methylheptyl)p-phenylene diamine. 
     
     
         9 . The diesel composition according to  claim 1 , wherein said polyamine is an organic amine having the structure shown by the following formula (A): 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are each independently H, a hydrocarbyl having from 1 to 30 carbon atoms or a hydrocarbyl having from 1 to 30 carbon atoms and bearing a group selected from carbonyl, hydroxyl, carboxyl, ester group, acyl, alkoxy, nitro, cyano, halo, amine group or amino, wherein said hydrocarbyl having from 1 to 30 carbon atoms and a group selected from carbonyl, hydroxyl, carboxyl, ester group, acyl, alkoxy, nitro, cyano, halo, amine group or amino can be further substituted with a hydrocarbyl having from 1 to 30 carbon atoms or bearing a group selected from carbonyl, hydroxyl, carboxyl, ester group, acyl, alkoxy, nitro, cyano, halo, amine group or amino, or can form a ring; 
         with the proviso that said organic amine comprises two or more N atoms. 
       
     
     
         10 . The diesel composition according to  claim 9 , wherein the polyamine of formula (A) is one or more of the following amines:
 an amine of the structural formula:
   H 2 N—R 3 —NHR 4  
 
   wherein R 3  is an hydrocarbylene having 1 to 30 carbon atoms or a polyether group, and R 4  is a hydrocarbyl having 1 to 30 carbon atoms or a polyether group;   a polyamine of the structural formula:   
       
         
           
           
               
               
           
         
         wherein R 12 , R 13 , R 14 , R 15  and R 16  are each independently H or a hydrocarbyl having 1 to 30 carbon atoms, x7 and x8 are integers from 0 to 10, and y3 and y4 are integers from 0 to 5, 
         wherein one of R 12  and R 13  is H, and either R 12  or R 13  can form a ring together with R 14  or R 15 . 
       
     
     
         11 . The diesel composition according to  claim 9 , wherein the polyamine of formula A is a polyether diamine of formula (A1): 
       
         
           
           
               
               
           
         
         wherein x1 is an integer from 1 to 10, R 4  is H or a hydrocarbyl having 1 to 30 carbon atoms, and R 5  is H or methyl; 
         a polyene polyamine of the structural formula:
   H 2 N[(CH 2 ) x2 NH] y1 R 6    
 
         wherein x2 is an integer from 2 to 4, y1 is an integer from 1 to 8, and R 6  is H or a hydrocarbyl having 1 to 30 carbon atoms, and/or a condensate of said polyene polyamine with ethylene oxide and/or propylene oxide; 
         an imidazoline-type polyamine of the formula (A2); 
       
       
         
           
           
               
               
           
         
         wherein y2 is an integer from 0 to 5, and R 7  is a hydrocarbyl having 1 to 24 carbon atoms; 
         a piperazine-type polyamine of the formula (A3); 
       
       
         
           
           
               
               
           
         
         wherein R 8  is H, a hydrocarbyl having 1 to 24 carbon atoms or (CH 2 ) x3 NH 2 , and x3 is an integer from 0 to 5; 
         a piperidine-type polyamine; 
         a tertiary amine containing polyamine of the formula (A4), (A5) or (A6): 
       
       
         
           
           
               
               
           
         
         wherein R 9  and R 10  are hydrocarbyls having 1 to 24 carbon atoms, and x4 is an integer from 0 to 10; 
       
       
         
           
           
               
               
           
         
         wherein x5 is an integer from 1 to 10; 
       
       
         
           
           
               
               
           
         
         wherein R 11  is a hydrocarbyl having 1 to 24 carbon atoms, and x6 is an integer from 1 to 10, and preferably an integer from 2 to 6. 
       
     
     
         12 . The diesel composition according to  claim 11 , wherein the amine of the structural formula H 2 N—R 3 —NHR 4  is hexanediamine, N-cocoyl-1,3-propylene diamine, N-oleyl-1,3-propylene diamine, or N-tallow-1,3-propylene diamine; the polyene polyamine of the structural formula H 2 N[(CH 2 ) x2 NH] y1 R 6  is one or more of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, propylene diamine, dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, pentapropylene hexamine, hexapropylene heptamine, heptapropylene octamine, and N,N′-bis(3-aminopropyl)-ethylene diamine, or one or more polyene polyamines wherein R 6  is n-butyl, n-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-didodecyl, iso-butyl, tert-butyl, iso-amyl, neo-amyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, iso-dodecyl, iso-tetradecyl, iso-hexadecyl, iso-octadecyl, iso-eicosyl, 9-octadecene, phenylmethyl, phenylethyl or phenylpropyl; a polyamine represented by the formula is a polyether diamine with the CAS number 9046-10-0 and having a Mn of 400; a polyamine represented by the formula (A2) is an imidazoline-type polyamine wherein y2 is an integer from 1 to 3, and R 7  is C 6 -C 20  alkyl or C 6 -C 20  alkenyl; the piperazine-type polyamine of the formula (A3) is N-(2-aminoethyl)piperazine or N,N′-di-(aminoethyl)piperazine, said piperidine-type polyamine is 4-amino-2,2,6,6-tetramethylpiperidine or 1-(2-aminoethyl)piperidine; the tertiary amine containing polyamine of the formula (A4) is one or more of N,N-dimethyl-1,3-propylene diamine, N,N-diethyl-1,3-propylene diamine, N,N-dibutyl-1,3-propylene diamine, N,N-dimethyl-1,4-butylene diamine, N,N-diethyl-1,4-butylene diamine, N,N-dimethyl-1,6-hexanediamine; the tertiary amine containing polyamine of the formula (A5) is tri-(2-aminoethyl)amine; the tertiary amine containing polyamine of the formula (A6) is N,N-bis-(3-aminopropyl)methylamine. 
     
     
         13 . The diesel composition according to  claim 1 , wherein said derivatives of polyamines are the reaction products of the ammonolysis reaction of one or more organic acids having 6 to 40 carbon atoms, acyl halides having 6 to 40 carbon atoms, or organic acid alkyl esters having 6 to 40 carbon atoms with the above-mentioned polyamines. 
     
     
         14 . The diesel composition according to  claim 13 , wherein said derivatives of polyamines are the reaction products of the ammonolysis reaction of one or more fatty acids having 6 to 40 carbon atoms, fatty acyl halides having 6 to 40 carbon atoms, or fatty acid alkyl esters having 6 to 40 carbon atoms with the above-mentioned polyamines. 
     
     
         15 . The diesel composition according to  claim 14 , wherein said fatty acid is one or more selected from the group consisting of caproic acid, adipic acid, octanoic acid, isooctanoic acid (2-ethylcaproic acid), capric acid, dodecanic acid, tetradecanoic acid, hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), oleic acid, linoleic acid, linolenic acid, ricinolic acid, eicosenoic acid, arachidic acid, erucic acid, docosenoic acid, dimer acids (dimers of oleic acid and/or linoleic acid), oleic acid, linoleic acid, linolenic acid, industrial dimer acids, soybean oil acid, peanut oil acid, rapeseed oil acid, ricinoleic acid, and tall oil fatty acid; said fatty acyl halide is an acyl halide of the above-mentioned fatty acid; said fatty acid alkyl ester is a C1-C5 alkyl ester of the above-mentioned fatty acid, in particular biodiesel. 
     
     
         16 . The diesel composition according to  claim 1 , wherein said derivatives of polyamines are the reaction products of the condensation reaction of said polyamines with C1-C6 aldehyde. 
     
     
         17 . The diesel composition according to  claim 16 , wherein conditions for said condensation reaction include a molar ratio of total polyamines to C1-C6 aldehyde of 1: (0.1-10), and a reaction temperature of 80-150° C., wherein said C1-C6 aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde, cyclo-caproaldehyde, and an aqueous solution of one or more of them. 
     
     
         18 . The diesel composition according to  claim 1 , wherein said derives of polyamines are the reaction products of the ammonolysis reaction of an acylating agent containing two acyl groups in a molecule with the above-mentioned polyamines in a molar ratio of 1:(0.5-2), wherein said acylating agent containing two acyl groups in a molecule is one or more of a C6-C30 hydrocarbyl substituted organic dicarboxylic acid, a C6-C30 hydrocarbyl substituted anhydride, and a C6-C30 hydrocarbyl substituted half ester. 
     
     
         19 . The diesel composition according to  claim 18 , wherein said acylating agent is one or more of maleic acid, succinic acid, fumaric acid, itaconic acid, citraconic acid, isatoic acid, phthalic acid, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, isatoic anhydride and phthalic anhydride, and the half esters thereof, all of which are substituted by C6-C30 hydrocarbyl. 
     
     
         20 . The diesel composition according to  claim 18 , wherein said acylating agent is one or more of C6-C30 hydrocarbyl substituted succinic acid, C6-C30 hydrocarbyl substituted succinic anhydride, and the half esters thereof. 
     
     
         21 . The diesel composition according to  claim 18 , wherein said acylating agent is one or more of nonylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid, tridecylsuccinic acid, tetradecylsuccinic acid, pentadecylsuccinic acid, hexadecylsuccinic acid, octadecylsuccinic acid, nonenylsuccinic acid, decenylsuccinic acid, dodecenylsuccinic acid, tetradecenylsuccinic acid, cetenylsuccinic acid, octadecenesuccinic acid, docosenylsuccinic acid, nonylsuccinic anhydride, decylsuccinic anhydride, dodecylsuccinic anhydride, tridecylsuccinic anhydride, tetradecylsuccinic anhydride, pentadecylsuccinic anhydride, hexadecylsuccinic anhydride, octadecylsuccinic anhydride, nonenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, cetenylsuccinic anhydride, octadecenesuccinic anhydride, docosenylsuccinic anhydride, and the half esters thereof. 
     
     
         22 . The diesel composition according to  claim 1 , wherein said diesel composition further comprises component (c), which is a metal deactivator capable of reacting with a metal surface and/or a metal chelator capable of reacting with or binding to a metal or metal ion. 
     
     
         23 . The diesel composition according to  claim 22 , wherein the weight ratio of said component (a) to said component (c) is 1:0.01-1. 
     
     
         24 . The diesel composition according to  claim 22 , wherein said component (c) is one or more of benzotriazole, an ammonium salt formed by benzotriazole and a fatty amine, a product obtained by the Mannich reaction of benzotriazole, formaldehyde and a fatty amine, Schiff's base, and organic polycarboxylic acids. 
     
     
         25 . The diesel composition according to  claim 24 , wherein said Schiff's base may be N,N′-disalicylidene-1,2-propylene diamine; said organic polycarboxylic acid is tartaric acid. 
     
     
         26 . The diesel composition according to  claim 1 , wherein said additive composition is present in an amount of 50-10000 ppm, relative to the amount of the base diesel. 
     
     
         27 . The diesel composition according to  claim 1 , wherein said base diesel further comprises one or more additional diesels selected from the group consisting of petroleum diesel, Fischer-Tropsch synthetic diesel, hydrocracked biodiesel, and an oxygen-containing diesel concoction, wherein the ratio of the volume of said biodiesel to the volume of said additional diesels is 1: 0-99. 
     
     
         28 . A method of increasing the oxidation stability of biodiesel, comprising adding, in a biodiesel-containing base diesel, an additive composition according to  claim 1 .