Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• This application is directed to ester and ester/amide reaction products which are useful for improving the low-temperature properties of distillate fuels; to concentrates and to fuel compositions containing same.
• kerosene dilutes the wax in the fuel, i.e. lowers the overall weight fraction of wax, and thereby lowers the cloud point, filterability temperature, and pour point simultaneously.
• This invention seeks effectively to lower both the cloud point and CFPP (Cold Filter Plugging Point) of distillate fuel without any appreciable dilution of the wax component of the fuel.
• the novel esters and ester/amides prepared in accordance with this invention have been found to be surprisingly active wax crystal modifier additives for distillate fuels. Distillate fuel compositions containing ⁇ O.l wt % of such additives demonstrate significantly improved low-temperature flow properties, i.e. lower cloud point and lower CFPP filterability temperature.
• an object of this invention is to improve the low-temperature flow properties of distillate fuels.
• the reaction products of this invention are especially effective as additives in lowering the cloud point of distillate fuels, and thus improve the low-temperature flow properties of such fuels without the use of any light hydrocarbon diluent, such as kerosene.
• the filterability properties are improved as demonstrated by lower CFPP temperatures.
• the reaction products of this invention demonstrate multifunctional activity in distillate fuels.
• the reaction products of this invention are ester or ester/amide products which have core-pendant groups (star-like) structures derives from the reaction of an anhydride - or carboxylic acid - containing "core" - former with, as "pendant group” - former : (1) an amino alcohol, suitably the product of reaching an amine and an epoxide or (2) a combination of an amino alcohol and a secondary amine.
• Preferred anhydrides include pyromellitic dianhydride (PMDA) and benzophenone tetracarboxylic dianhydride (BTDA) .
• this invention provides a reaction product preparable by reacting : i) a compound comprising a hydrocarbyl anhydride group, or a hydrocarbyl carboxylic acid group, the latter having at least two carboxylic acid groups; with ii) an aminoalcohol; and iii) optionally, a secondary amine at a temperature from 85" to 250°C and a pressure from ambient to greater than autogenous to obtain the desired ester or ester/amide reaction product.
• Component (i) may include a mixture of such compounds.
• Component (ii) may include a mixture of aminoalcohols and component (iii) , where present, may include a mixture of secondary amines; preferably it is the same secondary amine, or mixture of secondary amines, suitably fatty amines, used to prepare (ii) in accordance with the reaction : O
• reaction products of this invention have core-pendant group (star-like) structures. These reaction products are obtained by combining the core structure and the pendant group(s) in differing ratios using standard techniques for esterification/ a idification. These reaction products which are highly effective as wax crystal modifiers in lowering cloud point are generally characterized by the following structural features: (a) a compact "core" which forces close proximity of the pendant groups (pairs of adjacent carboxyl groups where the pendant groups are attached are generally separated by four or fewer atoms) ;
• Suitable core structures contain two or more reactive carboxyl groups (anhydrides, acids, or acid equivalents) . These structures include, but are not limited to, aromatic, alicyclic, aralkyl, alkaryl, and alkyl hydrocarbons, as well as their corresponding heteroatom-containing analogues.
• the reaction products of this invention are derived from “core” and “pendant group” precursors, and a range of reactant stoichiometries may be used. However, each reaction product requires one “core” derivatized with at least one aminoalcohol "pendant group”; any additional pendant groups may be either aminoalcohols or amines and may be added up to the limit of available reactive carboxyl groups in the core structure.
• Reaction products of this invention may be grouped into categories based on distinct structural and compositional differences, described below.
• Catecrory A Aromatic "Core” (TABLE 2)
• the preferred aminoalcohol, Entry 1, used in the synthesis of the reaction product of this invention, has low cloud point and CFPP activity by itself.
• Successful additives may be prepared from aromatic cores which are difunctional (e.g. phthalic anhydride, Entry 7) , trifunctional (e.g trimesic acid.
• Entries 14-16 or tetrafunctional (e.g. tetrahydrofuran tetracarboxylic dianhydride, Entry 11) .
• Bicyclic cores may be difunctional (e.g. norbornene dicarboxylic anhydride,
• Entry 17 camphoric acid, Entry 19), or tetrafunctional (e.g bicyclooctene tetracarboxylic dianhydride, Entry 18) .
• An example of a suitable alicyclic core is cyclohexane dicarboxylic anhydride (Entry 20) .
• a typical synthesis is illustrated by the preparation of the norbornene diester (Entry 17) in EXAMPLE 26.
• Successful additives may be prepared from non-rigid cores if the density of reactive groups is sufficiently high, i.e. if the core molecule is sufficiently small.
• additives with good cloud point activity were derived from butyl citrate (Entry 21) , and from maleic anhydride (Entry 22) .
• additives derived from large non-rigid alkyl cores such as dimer acid (Hystrene 3695, Entry 23) and trimer acid (Hystrene 5460, 60:40 mixture of trimer:dimer acids, Entry 24) offer little substantial cloud point activity.
• Multifunctional additives may be prepared from the cloud point additives of this invention, and may have advantages as ashless dispersants, detergents, antirust agents, antiwear agents, etc. Multifunctionality may be introduced into the core/pendant group additives whenever a suitably reactive group is available for post-reaction with a secondary chemical agent. In one approach, for example, judicious choice of core/pendant group stoichiometry may leave residual acid and/or anhydride groups available for post-reaction. This strategy was demonstrated with PMDA and BTDA derivatives (Entries 25-30, and 33-34) where only half of the available carboxyl groups were esterified with the aminoalcohol from Armeen 2HT/Vikolox 18, i.e.
• the secondary reactive functionality is chosen so as to be unreactive in the initial esterification process used to prepare the cloud point additive.
• maleic anhydride was esterified with the Armeen 2HT/Vikolox 18 aminoalcohol, and the remaining activated olefin was post-reacted via addition of the polyethyleneamine TEPA (tetraethylenepentaamine) .
• TEPA polyethyleneamine
• Preferred classes of reaction product of this invention have core-pendant group (star-like) structures derived from pyromellitic dianhydride (PMDA) or benzophenone tetracarboxylic diahydride (BTDA) or acid equivalents.
• a general structure for the PMDA/aminoalcohol ester is as follows:
• R 3 R 2 A general structure for the PMDA/aminoalcohol/amine ester/amide is as follows:
• R 3 R 2 R 2 A general structure for the PMDA/mixed aminoalcohol ester is as follows: (PMDA) - (O-CH-CHg-N-R j ⁇ ) (O-CH-CH ⁇ N-R. ⁇ z i t I I
• R., R- C 8 -C 50 linear hydrocarbyl groups, either saturated or unsaturated.
• R 2 R 2 , C 1 -C 100 hydrocarbyl
• olefin oxide Any suitable olefin oxide may be used. Epoxides are especially preferred. Included are such oxides as ethylene oxide, 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxydodecane,
• Suitable amines are secondary amines with at least one long-chain hydrocarbyl group, e.g. C 8 to about C 5Q .
• Highly useful secondary amines include but are not limited to di(hydrogenated tallow) amine, ditallow amine, dioctadecylamine, methyloctadecylamine and the like.
• stoichiometries of amine to epoxide were chosen such that one amine reacted with each available epoxide functional group. Other stoichiometries where the amine is used in lower molar proportions may also be used.
• the reactions can be carried out under widely varying conditions which are not believed to be critical.
• the reaction temperatures can vary from about 100 to 225°C, preferably 120 to 180"C, under ambient or autogenous pressure. However slightly higher pressures may be used if desired.
• the temperatures chosen will depend upon for the most part on the particular reactants and on whether or not a solvent is used. Solvents used will typically be hydrocarbon solvents such as xylene, but any non-polar, unreactive solvent can be used including benzene and toluene and/or mixtures thereof.
• Molar ratios less than molar ratios or more than molar ratios of the reactants can be used. Preferentially a molar ratio of 1:1 to about 8:1 of epoxide to amine is chosen.
• reaction products of the present invention may be employed in any amount effective for imparting the desired degree of activity to improve the low temperature characteristics of distillate fuels. In many applications the products are effectively employed in amounts from about 0.001% to about 10% by weight and preferably from less than 0.01% to about 5% of the total weight of the composition.
• the fuels contemplated are liquid hydrocarbon combustion fuels, including the distillate fuels and fuel oils.
• the fuel oils that may be improved in accordance with the present invention are hydrocarbon fractions having an initial boiling point of at least about 250"F and an end-boiling point no higher than about 750°F and boiling substantially continuously throughout their distillation range.
• Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straight run distillate fractions.
• the distillate fuel oils can be straight run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight run distillate fuel oils, naphthas and the like, with cracked distillate stocks.
• fuel oils can be treated in accordance with well-known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
• distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like.
• the principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 250"F and about 750°F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
• Di(hydrogenated tallow) amine (59.8 g, 0.12 mol; e.g. Armeen 2HT from Akzo Chemie) , and 1,2-epoxyoctadecane (32.2 g, 0.12 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 160"C for 16 hours.
• Pyromellitic dianhydride (6.54 g, 0.03 mol; e.g. PMDA from Allco Chemical Corp.), and xylene (approx. 30 ml) were added and heated at reflux (160-200°C) with azeotropic removal of water for 24 hours. Volatiles were then removed from the reaction medium at 190-200°C, and the reaction mixture was hot filtered to give 94.6 g of the final product as a low melting solid.
• Example 2 According to the procedure used for Example 1 (above), di(hydrogenated tallow) amine (40.0 g, 0.080 mol), and 1,2-epoxyeicosane (28.7 g, 0.088 mol; e.g. Vikolox 20 from Viking Chemical) were combined at 220°C. Pyromellitic dianhydride (9.60 g, 0.044 mol) was then added, and allowed to react in the second step of the sequence. The final product (69.8 g) was obtained as a low-melting solid.
• Di(hydrogenated tallow) amine (50.0 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined and heated at 150°C for 16 hours.
• potassium t-butoxide (0.56 g, 0.005 mol)
• 1,2-epoxybutane (13.5 g, 0.187 mol).
• the mixture was heated to 105-115°C for 20 hours, to 150°C for 1 hour, followed by removal of all volatiles at 150°C.
• Pyromellitic dianhydride (6.00 g, 0.0275 mol)
• xylene (approx.
• Di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie)
• 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking
• Example 15 According to the procedure used for Example 15 (above), di(hydrogenated tallow) amine (50.0 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were first combined. Benzophenone tetracarboxylic dianhydride (10.7 g, 0.0333 mol) was then added, and allowed to react in the second step of the sequence. The final product (86.4 g) was obtained as a low-melting solid.
• di(hydrogenated tallow) amine (62.4 g, 0.125 mol), and 1,2-epoxyoctadecane (21.0 g, 0.078 mol) were first combined.
• Benzophenone tetracarboxylic dianhydride (11.1 g, 0.0343 mol) was then added, and allowed to react in the second step of the sequence.
• the final product (86.6 g) was obtained as a low-melting solid.
• Example 15 According to the procedure used for Example 15 (above), 4 g, 0.125 mol), and 1,2-epoxyoctadecane (21.0 g, 0.078 mol) were first combined. Benzophenone tetracarboxylic dianhydride (22.2 g, 0.0687 mol) was then added, and allowed to react in the second step of the sequence. The final product (95.2 g) was obtained as a low-melting solid.
• Example 15 According to the procedure used for Example 15 (above), di(hydrogenated tallow) amine (40.0 g, 0.080 mol) , and a mixture of C_ 0 -C 24 alpha olefin epoxides (30.4 g, 0.088 mol; e.g. Vikolox 20-24 from Viking Chemical) were combined at 220°C. Benzophenone tetracarboxylic dianhydride (14.2 g, 0.044 mol) was then added, and allowed to react in the second step of the sequence. The final product (75.1 g) was obtained as a low-melting solid.
• Example 15 According to the procedure used for Example 15 (above), di(hydrogenated tallow) amine (35.0 g, 0.070 mol) , and a mixture of C 2 .-C 28 alpha olefin epoxides (33.7 g, 0.077 mol; e.g. Vikolox 24-28 from Viking Chemical) were combined at 220°C. Benzophenone tetracarboxylic dianhydride (12.4 g, 0.0385 mol) was then added, and allowed to react in the second step of the sequence. The final product (74.2 g) was obtained as a low-melting solid.
• 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 160 ⁇ C for 17 hours.
• Trimesic acid (7.71 g, 0.037 mol; e.g. from Amoco Chemical Co.), and xylene (approx. 60 ml) were added and heated at reflux (180-240°C) with azeotropic removal of water for 8 hours. Volatiles were then removed from the reaction medium at 190-200 ⁇ C, and the reaction mixture was hot filtered to give the final product.
• Di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie)
• 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 160°C for 17 hours.
• Norborene dicarboxylic anhydride (9.03 g, 0.055 mol; e.g. from Aldrich Chemical Co.), and xylene (approx. 60 ml) were added and heated at reflux (180-250°C) with azeotropic removal of water for 8 hours. Volatiles were then removed from the reaction medium at 190-200°C, and the reaction mixture was hot filtered to give the final product.
• Di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 190°C for 19 hours.
• Maleic anhydride (5.88 g, 0.060 mol; e.g. from Aldrich Chemical Co.), and xylene (approx. 60 ml) were added and heated at reflux (185-190°C) with azeotropic removal of water for 22 hours. Volatiles were then removed from the reaction medium at 190°C, and the reaction mixture was hot filtered to give 81.1 g of the final product.
• EXAMPLE 28 Preparation of Additive Entry 29 Di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 170°C for 22 hours. Benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol; e.g. BTDA from Allco Chemical Corp.), and xylene (approx. 60 ml) were added and heated at reflux (185-190°C) with azeotropic removal of water for 4.5 hours.
• Di(hydrogenated tallow) amine 50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie
• 1,2-epoxyoctadecane 33.6 g, 0.125 mol; e.g. Viko
• a concentrate solution of 100 ml total volume was prepared by dissolving 10 g of additive in mixed xylenes solvent. Any insoluble particulates in the additive concentrate were removed by filtration before use. Generally speaking however, each 100 ml of concentrate solution may contain from about 1 to about 50 grams of the additive product of reaction.
• the cloud point of the additized distillate fuel was determined using two procedures: (a) an automatic cloud point test based on the commercially available Herzog cloud point tester; test cooling rate is approximately l°C/min. Results of this test protocol correlate well with ASTM D2500 methods.
• the test designation (below) is "HERZOG.”
• the low-temperature filterability was determined using the Cold Filter Plugging Point (CFPP) test. This test procedure is described in "Journal of the Institute of Petroleum,” Volume 52, Number 510, June 1966, pp. 173-185.
• CFPP Cold Filter Plugging Point
• a concentrate solution of 100 ml total volume was prepared by dissolving 10 g of reaction product in mixed xylenes solvent. Any insoluble particulates in the additive concentrate were removed by filtration before use.
• the cloud point of the additized distillate fuel was determined using an automatic cloud point test based on the commercially available Herzog cloud point tester; test cooling rate is approximately l°C/min. Results of this test protocol correlate well with ASTM D2500 methods. The test designation (below) is "HERZOG.”
• the low-temperature filterability was determined using the Cold Filter Plugging Point (CFPP) test. This test procedure is described in "Journal of the Institute of Petroleum,” Volume 52, Number 510, June 1966, pp. 173-185.
• CFPP Cold Filter Plugging Point

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• 1991
  • 1991-12-02 JP JP4508110A patent/JPH06503836A/ja active Pending
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