WO2024006694A1

WO2024006694A1 - Diesel fuel composition and method for reducing diesel fuel filter blocking tendency from biodiesel contaminants

Info

Publication number: WO2024006694A1
Application number: PCT/US2023/069067
Authority: WO
Inventors: Hitesh Bagaria; Roberto Gutierrez; Moshood ADEWALE; Nimeshkumar PATEL
Original assignee: Bl Technologies, Inc.
Priority date: 2022-06-30
Filing date: 2023-06-26
Publication date: 2024-01-04
Also published as: EP4547796A1

Abstract

A diesel fuel composition having a diesel fuel blend and at least one additive is provided. A method for reducing biodiesel fuel filter blocking tendency (FBT) is provided, the method adding at least one fuel additive to a diesel fuel blend to obtain a diesel fuel composition. A method for reducing biodiesel fuel filter blocking tendency (FBT) is provided, the method adding a fuel additive combination to a diesel fuel blend to obtain a diesel fuel composition

Description

DIESEL FUEL COMPOSITION AND METHOD FOR REDUCING DIESEL FUEL FILTER BLOCKING TENDENCY FROM BIODIESEL CONTAMINANTS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the priority benefit of Application Serial No. 63/357,239 filed lune 30, 2022, the entirety of which is herein incorporated by reference.

FIELD OF INVENTION

[0002] The disclosed technology provides treatment compositions and methods to reduce diesel fuel filter blocking tendency (FBT), and more specifically, treatment compositions and methods to reduce diesel fuel filter blocking tendency from biodiesel contaminants.

BACKGROUND OF THE INVENTION

[0003] The increased thrust on renewable and sustainable fuels has spurred growth of biodiesel and renewable diesel production. Biodiesel comprises fatty acid methyl esters that are produced by transesterification of plant and animal-based oils with smaller alcohols like methanol, and renewable diesel is a drop-in substitute for traditional petroleum diesel. While there is significant economic incentive for refineries and blenders to use biodiesel and renewable diesel, the fuel filter issues caused by biodiesel contaminants hinder the use of biodiesel blends, especially blends with renewable diesel.

[0004] When biodiesel is blended with petroleum or renewable diesel, biodiesel contaminants, especially saturated monoglycerides and steryl glucosides, cause fuel filter plugging, also referred to as filter blocking tendency (FBT) (where FBT is measured by ASTM D2068/ IP 387). FBT test can be preceded by a pre-treatment such as cold-soak, where the blend is cooled to a temperature above cloud point (e.g., 1 °C or 5 °C) for 16 hours followed by warming to 25 °C (ASTM D7501) to assess impact of cold weather. The contaminants in biodiesel have resulted in several cases of premature diesel fuel filter plugging, which result in poor drivability, long start up times, and increased maintenance of diesel fuel vehicles.

[0005] Thus, what is needed in the art are treatments and methods for reducing filter blocking tendency of biodiesel blends, especially blends with renewable diesel.

SUMMARY OF THE INVENTION

[0006] In one aspect of the disclosed technology, a diesel fuel composition is provided, the composition comprising a diesel fuel blend and at least one additive.

[0007] In some embodiments, the diesel fuel blend comprises a biodiesel component and a renewable diesel component. In some embodiments, the diesel fuel blend comprises a biodiesel component and a petroleum diesel component. In some embodiments, the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component.

[0008] In some embodiments, the additive comprises an organic compound with at least two electronegative atoms. In some embodiments, the at least two electronegative atoms comprise (i) nitrogen, (ii) oxygen, or (iii) nitrogen and oxygen.

[0009] In some embodiments, the additive comprises the Formula (I):

where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure.

[0010] In some embodiments, the additive is a reaction product of Formula (I) and polyisobutylene substituted succinic acid or anhydride. In some embodiments, the additive is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, tnethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, or hexethylene heptamine. In some embodiments, the additive is an alkoxylated amine comprising the structure of Formula (I) as the backbone with an average molecular weight of 400 to 25,000 daltons.

[0011] In some embodiments, the additive comprises the Formula (II):

where R1 is selected from hydrocarbyl groups containing 10-30 carbon atoms, and R2 and R3 are independently selected from a hydrogen or hydrocarbyl groups containing 10-80 carbon atoms, and n is the number of repeating units ranging from 1 to 100.

[0012] In some embodiments, the additive comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20. In some embodiments, the additive is methoxy propylamine, ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, or diglycolamine.

[0013] In some embodiments, the additive comprises the Formula (IV):

where Rl and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. In some embodiments, the additive is a reaction product of Formula (IV) and ammonia.

[0014] Tn some embodiments, the additive comprises the Formula (V):

where Rl, R2, R3 and R4 are independently selected from hydrocarbyl groups containing 1 to 20 carbon atoms with n ranging from 0 to 20, and x, y and z ranging from 0 to 20 such that x + y + z is greater than or equal to 1.

[0015] In some embodiments, the additive is the reaction product of polyisobutylene substituted succinic acid or anhydride with polyalcohol with at least two hydroxyl groups. In some embodiments, the additive is a linear or branched polyethyleneimine with an average molecular weight of 400 to 25000 daltons.

[0016] In some embodiments, the additive comprises the Formula (VI):

where, Rl, R2, R3, R4, R5 and R6 are independently selected from hydrogen or a hydrocarbyl group with 1 to 50 carbon atoms and n = 0 to 50.

[0017] In some embodiments, the additive is present in about 0.00001% wt. to about 1% wt. based on the total weight of the composition.

[0018] In another aspect of the disclosed technology, a method for reducing biodiesel fuel fdter blocking tendency (FBT) is provided, the method comprising adding at least one fuel additive to a diesel fuel blend to obtain a diesel fuel composition.

[0019] In some embodiments, the at least one fuel additive of the present method comprises the Formula (I):

[0020] In some embodiments, the additive is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, triethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, or hexethylene heptamine. In some embodiments, the additive is a reaction product of Formula (1) and polyisobutylene substituted succinic acid or anhydride. In some embodiments, the additive is an alkoxylated amine comprising the structure of Formula (I) as the backbone with an average molecular weight of 400 to 25,000 daltons.

[0021] In some embodiments, the at least one fuel additive of the present method comprises the Formula (II):

[0022] In some embodiments, the at least one fuel additive of the present method comprises the Formula (III):

[0023] In some embodiments, the at least one fuel additive of the present method comprises the Formula (IV):

where R1 and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. In some embodiments, the additive is a reaction product of Formula (IV) and ammonia.

[0024] Tn some embodiments, the at least one fuel additive of the present method comprises the Formula (V):

where Rl, R2, R3 and R4 are independently selected from hydrocarbyl groups containing 1 to 20 carbon atoms with n ranging from 0 to 20, and x, y and z ranging from 0 to 20 such that x + y + z is greater than or equal to 1 . Tn some embodiments, the additive is the reaction product of polyisobutylene substituted succinic acid or anhydride with polyalcohol with at least two hydroxyl groups. [0025] In some embodiments, the at least one fuel additive of the present method comprises the Formula (VI):

[0026] In some embodiments, the diesel fuel blend is a blend of a biodiesel component and a renewable diesel component. In some embodiments, the ratio of the biodiesel component to the renewable diesel component is about 0.001 to about 99. In some embodiments, the diesel fuel blend is a blend of a biodiesel component and a petroleum fuel component. In some embodiments, the ratio of the biodiesel component to the petroleum diesel component is about 0.001 to about 99. In some embodiments, the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component.

[0027] In some embodiments, the at least one fuel additive of the present method is added to the diesel fuel blend by mixing. In some embodiments, the at least one fuel additive is a dispersant and at least 0.1 ppm of the dispersant is added to the diesel fuel blend. In some embodiments, the at least one fuel additive is a polyamine and at least 0.1 ppm of the polyamine is added to the diesel fuel blend. In some embodiments, the diesel fuel composition comprises a fuel blocking tendency (FBT) value of less than about 1.41, where FBT is defined by ASTM D2068 or equivalent methods.

[0028] In another aspect of the disclosed technology, a method for reducing biodiesel fuel filter blocking tendency (FBT) is provided. The method comprises adding a fuel additive combination to a diesel fuel blend to obtain a diesel fuel composition.

[0029] In some embodiments, the fuel additive combination comprises Formula (I), Formula (II), Formula (III), Formula (IV), reaction products of Formula (IV) with ammonia, Formula (V), Formula (VI), polyisobutylene based dispersants, PEI, alkoxylated PEI, Formula (I) with alkoxylation, and/or combinations thereof.

[0030] In some embodiments, the fuel additive combination comprises the Formula (I):

where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure. [0031] In some embodiments, the fuel additive combination comprises the

Formula (II):

where R1 is selected from hydrocarbyl groups containing 10-30 carbon atoms, and R2 and R3 are independently selected from a hydrogen or hydrocarbyl groups containing 10-80 carbon atoms, and n is the number of repeating units ranging from 1 to 100. [0032] In some embodiments, the fuel additive combination comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20.

[0033] In some embodiments, the fuel additive combination comprises the Formula (IV):

where Rl and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both.

[0034] In some embodiments, the fuel additive combination is a reaction product of Formula (IV) and ammonia.

[0035] In some embodiments, the fuel additive combination comprises the Formula (V):

[0036] In some embodiments, the fuel additive combination comprises the

[0037] In some embodiments, the fuel additive combination comprises (i) Formula (I), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. In some embodiments, the fuel additive combination comprises (i) Formula (III), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. In some embodiments, the fuel additive combination comprises (i) Formula (IV), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. In some embodiments, the fuel additive combination comprises (i) reaction products of Formula (IV) with ammonia, and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. In some embodiments, the fuel additive combination comprises (i) Formula (V), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0038] The disclosed technology generally provides for treatment compositions and methods to reduce diesel fuel filter blocking tendency (FBT), and more specifically, treatment compositions and methods to reduce diesel fuel filter blocking tendency from biodiesel contaminants. The compositions and methods provided herein overcome the fuel filter plugging issues caused by biodiesel contaminants that hinder the use of biodiesel blends, especially blends with renewable diesel.

[0039] In one aspect of the present technology, a diesel fuel composition is provided. The diesel fuel composition as described herein comprises a diesel fuel blend and an additive. In some embodiments, the diesel fuel composition further comprises an antioxidant/stabilizer, a corrosion inhibitor, and/or a paraffin cold flow improver.

[0040] In some embodiments, the diesel fuel blend comprises a biodiesel component and a renewable diesel component. It should be understood that “biodiesel” refers to mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats, and “renewable diesel” refers to hydrocarbon produced by hydrotreating vegetable oils, animal fats, greases and algae oil, and pyrolyzed biomass.

[0041] In some embodiments, the diesel fuel blend comprises a biodiesel component and a petroleum diesel component. It should be understood that “petroleum diesel” refers to diesel produced in refineries from petroleum crude oil processing.

[0042] In some embodiments, the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component.

[0043] The diesel fuel composition further comprises an additive. In some embodiments, the additive comprises an organic compound with at least two electronegative atoms. In some embodiments, the at least two electronegative atoms comprise (i) nitrogen, (ii) oxygen, or (iii) nitrogen and oxygen. In some embodiments, the additive is a blend.

[0044] In some embodiments, the additive is a polyamine comprises the Formula (I):

(I), where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure.

[0045] In some embodiments, the additive of Formula (I) is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, triethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, or hexethylene heptamine. In some embodiments, the additive is a reaction product of Formula (I) and polyisobutylene substituted succinic acid or anhydride.

[0046] In some embodiments, the additive is an alpha-olefin maleic anhydride copolymer (AOMA) comprising the Formula (11):

[0047] In some embodiments, the additive is an alkoxy alkyl amine. For example, the alkoxy alkyl amine, includes, but is not limited to methoxy propylamine, ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, or diglycolamine.

[0048] It was surprisingly discovered that disclosed chemistries (e.g. alphaolefin maleic anhydrides (AOMA) and polyamines) removed the filter blocking tendency (i.e. reduced fuel filter plugging) of biodiesel blends. It is believed that these chemistries prevented the biodiesel contaminants (e.g. saturated monoglycerides and steryl glucosides) from precipitating and depositing on the filter, thus reducing premature fuel filter failure and other related issues. The FBT caused by biodiesel contaminants occurs at a temperature higher than cloud point, when no wax/paraffin crystals have precipitated. However, it was surprisingly determined that the disclosed chemistries reduced and/or prevented the FBT above cloud point. It was also surprisingly found that certain polyamines (e.g. diethylene triamine (DETA), which is a very small molecule compared to typical polymeric dispersants), reduced FBT in biodiesel blends.

[0049] In some embodiments, the additive comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20. In some embodiments, the additive of Formula (III) is methoxy propylamine (MOPA), ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, or diglycolamine. Unlike polymeric dispersants, the alkoxy alkyl amines (e.g., MOPA) are small molecules, and yet were surprisingly found to reduce FBT of biodiesel blends.

[0050] In some embodiments, the additive comprises the Formula (IV):

where Rl and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. In some embodiments, the additive is reaction product of Formula (IV) and ammonia.

[0051] In some embodiments, the additive comprises the Formula (V):

[0052] In some embodiments, the additive is a reaction product of polyisobutylene substituted succinic acid or anhydride with polyalcohol with at least two hydroxyl groups. In some embodiments, the additive is present in about 0.0001% wt. to about 1% wt. based on the total weight of the composition.

[0053] In some embodiments, the additive is a linear or branched polyethyleneimine (PEI) with an average molecular weight of 400 to 25000 daltons. In some embodiments, the additive is an alkoxylated PEI comprising a polyethyleneimine backbone with an average molecular weight of 400 to 25,000 daltons. In such embodiments, the polymer further comprises one or two alkoxylation modifications per nitrogen atom by a polyalkoxylene chain having an average of 1 to 30 alkoxy moi eties, wherein the alkoxy moiety is capped with a hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, or mixtures thereof.

[0054] In some embodiments, the additive is an alkoxylated amine comprising the structure of formula (I) as the backbone with an average molecular weight of 400 to 25,000 daltons. In such embodiments, the polymer further comprises of one or two alkoxylation modifications per nitrogen atom by a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties, wherein the alkoxy moiety is capped with a hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, or mixtures thereof.

[0055] In some embodiments, the additive comprises the Formula (VI):

(VI), where, Rl, R2, R3, R4, R5 and R6 are independently selected from hydrogen or a hydrocarbyl group with 1 to 50 carbon atoms and n = 0 to 50.

[0056] In yet another aspect of the disclosed technology, a method for reducing biodiesel fuel filter blocking tendency (FBT) is provided. It should be understood that “reducing biodiesel fuel filter blocking tendency” means reducing biodiesel fuel filter plugging. The method comprises adding at least one fuel additive to a diesel fuel blend to obtain a diesel fuel composition.

[0057] The fuel additive of the present method comprises at least one fuel additive. It should be understood that more than one fuel additive can be added to a diesel fuel blend to obtain the diesel fuel composition.

[0058] In some embodiments, the fuel additive of the present method comprises Formula (I), in other embodiments, Formula (II); in other embodiments, Formula (III); in other embodiments, Formula (IV); in other embodiments, Formula (V), and in other embodiments, Formula (VI).

[0059] In some embodiments, the present method comprises more than one fuel additive, and comprises Formula (I), Formula (II), Formula (III), Formula (IV), reaction products of Formula (IV) with ammonia, Formula (V), Formula (VI), polyisobutylene based dispersants, PEI, alkoxylated PEI, Formula(I) with alkoxylation, or combinations thereof. [0060] In some embodiments, the fuel additive of the present method is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, triethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, hexethylene heptamine, or combinations thereof. In some embodiments, the additive of the present method is methoxy propylamine, ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, diglycolamine, or combinations thereof.

[0061] The method of the present technology further provides for a diesel fuel blend. In some embodiments, the diesel fuel blend is a blend of a biodiesel component and a renewable diesel component. In some embodiments, the ratio of the biodiesel component to the renewable diesel component is about 0.001 to about 99. In some embodiments, the diesel fuel blend is a blend of a biodiesel component and a petroleum fuel component. In some embodiments, the ratio of the biodiesel component to the petroleum diesel component is about 0.001 to about 99. In some embodiments, the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component. In some embodiments, the ratio of biodiesel component to the combined petroleum and renewable diesel components is about 0.001 to 99, wherein the ratio of petroleum diesel to renewable diesel component is 0.001 to 99.

[0062] The method of the present technology further provides for adding a fuel additive to a diesel fuel blend. In some embodiments, the fuel additive is added to the diesel fuel blend by mixing. Mixing can be accomplished according to conventional means recognized within the art. It should be understood that the fuel additive or fuel additives can be (i) individually added to the biodiesel, renewable diesel, or petroleum diesel, or (ii) alternately, can be added to a blend of biodiesel and renewable diesel, a blend of biodiesel and petroleum diesel, or a blend of biodiesel, renewable diesel and petroleum diesel.

[0063] In some embodiments, at least 0.1 ppm of the fuel additive is added to the diesel fuel blend. In some embodiments, about 0.1 ppm to about 10,000 ppm of the fuel additive is added to the diesel fuel blend. In some embodiments, the fuel additive is a polyamine and at least 0.1 ppm of the polyamine is added to the diesel fuel blend. In some embodiments, about 0.1 ppm to about 10,000 ppm of the polyamine is added to the diesel fuel blend.

[0064] The method of the present technology provides for a diesel fuel composition. In some embodiments, the diesel fuel composition comprises a fuel blocking tendency (FBT) value of less than about 1.41. The FBT value is measured/defined by ASTM D2068 or an equivalent method. As one skilled in the art would know and understand, ASTM D2068 is an automated test that flows 300mL of fuel through a 1.6 micron filter at a constant flow rate of 20 mL/min. The pressure is increased, if needed, to maintain the flow rate up to a maximum of 105 kPa. Depending on the final pressure (if all fuel is filtered) or filtered fuel volume (at max pressure), a filter blocking tendency (FBT) number is calculated. A FBT value of 1.41 is considered to be a pass.

EXAMPLES

[0065] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology or limit the scope to any particular embodiments.

[0066] Diesel (Renewable/Recycle diesel (RD), conventional/petroleum diesel, and surrogate renewable diesel) was blended with Biodiesel (Bl 00). The untreated blends were cold soaked as per ASTM D7501, then warmed to room temperature before FBT testing as per ASTM D2068 or as per CGSB-3.0 no. 142.0-2019.

[0067] Table 1 shows the impact of additives on filter blocking tendency (FBT) with RD and biodiesel blends.

TABLE 1

[0068] As shown in Table 1, the untreated BIO and B20 blends, Exp. #2 and Exp. #14, gave a FBT value of 7.6 and 15, respectively. The traditional cloud and pour point additives (such as ethylene vinyl acetate (EVA) terpolymer, polydialkyl fumarate vinyl acetate, polyoctadecenyl maleimide) did not reduce the FBT, but PIBS-based dispersants improved FBT score, and AOMA-ester and polyamines kept the FBT at the lowest value of 1, indicating superior performance in preventing or reducing filter blocking tendency. The AOMA broad ester chemistries were also successful in reducing the FBT of B20 blend from 15 (Exp. #14) to 1 (Exp. #15).

[0069] Table 2 shows the impact of additives on the FBT with conventional/petroleum diesel and biodiesel blends. With petroleum diesel, DETA was found to be the most effective chemistry that reduced FBT from 2.5 (Exp. #16) to 1 (Exp. #18) with only 25ppm dose. Other polymeric chemistries (PIBSI, PIBSE and AOMA) reduced FBT to 1.7 and below, at dose of 125ppm. However, a higher dose of 250ppm led to reduced performance indicating a potential overtreatment with this petroleum diesel blend.

TABLE 2

[0070] Table 3 shows the impact of additives on the FBT with surrogate renewable diesel (Exxsol D60) and biodiesel blends. Here, additional chemistries were tested including Amine C-6 (i.e. reaction product of Formula IV and ammonia), ethyl piperazine (i.e. another variation of Formula I), MOPA (e.g. Formula III), branched nonly phenol and ethylenediamine polymer (e.g. Formula VI), all of which showed reduction in FBT at tested dose of lOOppm. Alkylamines, such as Primene™ (Dow), cyclohexylamine, dimethylisopropylamine, or dimethyl cyclohexylamine, did not show significant reduction in FBT. Dibutylamine-HCHO (Exp. #50) and Dipropylamine- HCHO adducts (Exp. #51) were not effective, and in fact, increased the FBT at the tested dose of lOOppm. TABLE 3

[0071] Table 4 shows the impact of order of additive chemistry on the FBT with surrogate renewable diesel (Exxsol D60) and biodiesel blends. R100 and B100 refers to renewable and biodiesel components, respectively, before blending. TABLE 4

[0072] The data suggests that the treated samples where FBT was significantly reduced likely exhibited very small particles that easily passed through the filter (i.e. no fuel filter blocking/plugging). In contrast, with the untreated samples, it is believed that the large particles were unable to pass through the filter, thus resulting in filter blocking.

[0073] Table 5 shows the impact of a combination of more than one additive to achieve a reduction in FBT value.

TABLE 5

[0074] While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

Claims

CLAIMS A diesel fuel composition, the composition comprising: a. a diesel fuel blend; and b. at least one additive. The composition of Claim 1, wherein the diesel fuel blend comprises a biodiesel component and a renewable diesel component. The composition of Claim 1, wherein the diesel fuel blend comprises a biodiesel component and a petroleum diesel component. The composition of Claim 1, wherein the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component. The composition of Claim 1, wherein the additive comprises an organic compound with at least two electronegative atoms. The composition of Claim 5, wherein the at least two electronegative atoms comprise (i) nitrogen, (ii) oxygen, or (iii) nitrogen and oxygen. The composition of Claim 1, wherein the additive comprises the Formula (I):

where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure. The composition of Claim 7, wherein the additive is a reaction product of Formula (I) and polyisobutylene substituted succinic acid or anhydride. The composition of Claim 7, wherein the additive is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, triethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, or hexethylene heptamine. The composition of Claim 7, wherein the additive is an alkoxylated amine comprising the structure of Formula (I) as the backbone with an average molecular weight of 400 to 25,000 daltons. The composition of Claim 1, wherein the additive comprises the Formula (II):

where R1 is selected from hydrocarbyl groups containing 10-30 carbon atoms, and R2 and R3 are independently selected from a hydrogen or hydrocarbyl groups containing 10-80 carbon atoms, and n is the number of repeating units ranging from 1 to 100. The composition of Claim 1, wherein the additive comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20. The composition of Claim 12, wherein the additive is methoxy propylamine, ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, or diglycolamine. The composition of Claim 1, wherein the additive comprises the Formula (IV):

where Rl and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. The composition of Claim 14, wherein the additive is a reaction product of Formula (IV) and ammonia. The composition of Claim 1, wherein the additive comprises the Formula (V):

17. The composition of Claim 1, wherein the additive is the reaction product of polyisobutylene substituted succinic acid or anhydride with polyalcohol with at least two hydroxyl groups. 18. The composition of Claim 1, wherein the additive is a linear or branched polyethyleneimine with an average molecular weight of 400 to 25000 daltons.

19. The composition of Claim 1, wherein the additive comprises the Formula (VI):

where, Rl, R2, R3, R4, R5 and R6 are independently selected from hydrogen or a hydrocarbyl group with 1 to 50 carbon atoms and n = 0 to 50. The composition of Claim 1, wherein the additive is present in about 0.00001% wt. to about 1% wt. based on the total weight of the composition. A method for reducing biodiesel fuel filter blocking tendency (FBT), the method comprising: adding at least one fuel additive to a diesel fuel blend to obtain a diesel fuel composition. The method of Claim 21, wherein the at least one fuel additive comprises the

where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure. The method of Claim 22, wherein the additive is diethylene triamine (DETA), ethylene diamine, piperazine, aminoethyl piperazine, triethylene tetramine, tetraethylene pentaamine, pentaethylene hexamine, or hexethylene heptamine. The method of Claim 22, wherein the additive is a reaction product of Formula (I) and polyisobutylene substituted succinic acid or anhydride. 25. The method of Claim 22, wherein the additive is an alkoxylated amine comprising the structure of Formula (I) as the backbone with an average molecular weight of 400 to 25,000 daltons. 26. The method of Claim 21, wherein the at least one fuel additive comprises the

Formula (II):

27. The method of Claim 21, wherein the at least one fuel additive comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20. The method of Claim 27, wherein the additive is methoxy propylamine, ethoxy propylamine, propoxy propylamine, monomethyl ethanolamine, dimethyl ethanolamine, ethanolamine, diethanolamine, methyl diethanolamine, or diglycolamine. The method of Claim 21, wherein the at least one fuel additive comprises the Formula (IV):

where R1 and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. The method of Claim 29, wherein the additive is a reaction product of Formula (IV) and ammonia. The method of Claim 21, wherein the at least one fuel additive comprises the Formula (V):

where Rl, R2, R3 and R4 are independently selected from hydrocarbyl groups containing 1 to 20 carbon atoms with n ranging from 0 to 20, and x, y and z ranging from 0 to 20 such that x + y + z is greater than or equal to 1. The method of Claim 21, wherein the additive is the reaction product of polyisobutylene substituted succinic acid or anhydride with polyalcohol with at least two hydroxyl groups. The method of Claim 21, wherein the at least one fuel additive comprises the

where, Rl, R2, R3, R4, R5 and R6 are independently selected from hydrogen or a hydrocarbyl group with 1 to 50 carbon atoms and n = 0 to 50. The method of Claim 21, wherein the diesel fuel blend is a blend of a biodiesel component and a renewable diesel component. The method of Claim 34, wherein the ratio of the biodiesel component to the renewable diesel component is about 0.001 to about 99. The method of Claim 21, wherein the diesel fuel blend is a blend of a biodiesel component and a petroleum fuel component. The method of Claim 36, wherein the ratio of the biodiesel component to the petroleum diesel component is about 0.001 to about 99. The method of Claim 21, wherein the diesel fuel blend comprises a biodiesel component, a renewable diesel component, and a petroleum diesel component. The method of Claim 21, wherein the at least one fuel additive is added to the diesel fuel blend by mixing. The method of Claim 21, wherein the at least one fuel additive is a dispersant and at least 0.1 ppm of the dispersant is added to the diesel fuel blend. The method of Claim 21, wherein the at least one fuel additive is a polyamine and at least 0.1 ppm of the polyamine is added to the diesel fuel blend. The method of Claim 21, wherein the diesel fuel composition comprises a fuel blocking tendency (FBT) value of less than about 1.41, where FBT is defined by ASTM D2068 or equivalent methods. A method for reducing biodiesel fuel filter blocking tendency (FBT), the method comprising: adding a fuel additive combination to a diesel fuel blend to obtain a diesel fuel composition. The method of Claim 43, wherein the fuel additive combination comprises Formula (I), Formula (II), Formula (III), Formula (IV), reaction products of Formula (IV) with ammonia, Formula (V), Formula (VI), polyisobutylene based dispersants, PEI, alkoxylated PEI, Formula (I) with alkoxylation, and/or combinations thereof. The method of Claim 44, wherein the fuel additive combination comprises the

Formula (I):

where a, b and c are the number of repeating units with values for a=0 to 10, b=0 to 10, c=0 to 10 and a+b+c is greater than or equal to 1, wherein the different repeating units may either be present as a block or randomly distributed with other repeating units throughout the structure. The method of Claim 44, wherein the fuel additive combination comprises the

Formula (II):

where R1 is selected from hydrocarbyl groups containing 10-30 carbon atoms, and R2 and R3 are independently selected from a hydrogen or hydrocarbyl groups containing 10-80 carbon atoms, and n is the number of repeating units ranging from 1 to 100. The method of Claim 44, wherein the fuel additive combination comprises the Formula (III):

where Rl, R2 and R3 are independently selected from hydrogen or a hydrocarbyl group and n= 1 to 20. The method of Claim 44, wherein the fuel additive combination comprises the Formula (IV):

where Rl and R3 are independently selected from hydrogen, hydrocarbyl group with 1 to 20 carbon atoms, hydroxyl, alkoxy groups or an amine group, and R2 is selected from hydrocarbyl groups containing 1 to 20 carbon atoms, such that the formula has at least two electronegative atoms selected from nitrogen or oxygen or both. The method of Claim 48, wherein the fuel additive combination is a reaction product of Formula (IV) and ammonia.

50. The method of Claim 44, wherein the fuel additive combination comprises the Formula (V):

51. The method of Claim 44, wherein the fuel additive combination comprises the Formula (VI):

where, Rl, R2, R3, R4, R5 and R6 are independently selected from hydrogen or a hydrocarbyl group with 1 to 50 carbon atoms and n = 0 to 50. 52. The method of Claim 44, wherein the fuel additive combination comprises (i)

Formula (I), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. 53. The method of Claim 44, wherein the fuel additive combination comprises (i) Formula (III), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI. 54. The method of Claim 44, wherein the fuel additive combination comprises (i)

Formula (IV), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI.

55. The method of Claim 44, wherein the fuel additive combination comprises (i) reaction products of Formula (IV) with ammonia, and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI.

56. The method of Claim 44, wherein the fuel additive combination comprises (i) Formula (V), and (ii) Formula (II), polyisobutylene based dispersants, PEI, or alkoxylated PEI.