CA1191833A - Organo transition metal salt/ashless detergent- dispersant combinations - Google Patents
Organo transition metal salt/ashless detergent- dispersant combinationsInfo
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- CA1191833A CA1191833A CA000430946A CA430946A CA1191833A CA 1191833 A CA1191833 A CA 1191833A CA 000430946 A CA000430946 A CA 000430946A CA 430946 A CA430946 A CA 430946A CA 1191833 A CA1191833 A CA 1191833A
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Abstract
Abstract Compositions comprising the combination of a transition metal salt of an organic acid and an ashless hydrocarbon-soluble ashless dispersant are useful in trea-ting lubricants and fuels. Typical compositions comprise manganese carboxylates and acylated nitrogen-containing dispersants.
Description
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ORGANO TRANSITION METAL SALT/ASHLESS
DETERGENT-DISPERSANT COMBINATIONS
Field o~ the Invention This invention relates to hydrocarbon~soluble com~
positions containing a transition metal salt of an organic acid and a hydrocarbon-soluble ashless dispersant. Typi cally, it relates to such compositions wherein the organic acid is a carboxylic, sulfonic or phosphorus acid and the 10 ashless dispersant is a nitrogen or non-nitrogen containing ester dispersant. It also relates to hydrocarbon systems containing the aforesaid compositions, such as lubricants based on oils of lubricating viscosi~y and hydrocarbon fuels.
15 Prior ~rt The treatment of hydrocarbon systems such as lubricants based on lubricating oils of lubricating vis-cosity (e.g., greases, lubricating oils and the like) and hydrocarbon fuels of both the solid and normally liquid type 20 with transition metals and transition metal-containing compounds, both organic and inorganic, is well known to the art. Such treatments are used to increase the systems' resistance to oxidative deterioration, promote ~.heir con-version to cohesive films in the case of paints and lac-25 quers, and improve theix combustion as, for example, fuelsD
Among the organic transition metal compounds thathave been used for such purposes are carboxylate and sul--- 2fonate salts and mixtures of such salts. For example, U.S.
Patent 4,162,986 to ~lkaitis et al. describes transition metal salts of mixed organic carboxylic and sulfonic or second carboxylic acids and their use as catalysts, anti-5 knock agents, combustion improvers, smoke suppressants,curing agents, driers, micronutrient sources, lubricant additives, and the like.
U.S Patent 3,762,~90 to Collins describes hydro-lyzable manganese soaps, stablilized by the inclusion of 10 proprionic acid and the use of such materials as siccatives for paints, varnishes and inks, stabilizers in various plastics and additives for greases and lubricating oils as well as smoke-suppressing and anti-corrosion additives for fuel and fuel oils.
U.S. Patent 3,723,152 to Alkaitis et al. des-c:ribes basic cobalt salts of carboxylic acids and their use as drier compos-itions for oil vehicles.
Other patents such as U.S. Patent 4,202,671 to Diehl et al. describe the use of organic magnesium compounds 20 as fuel conditioners for the reduction of fuel requirements and emissions.
Increasing concern with pollution and the rising cost of hydrocarbon-based fuels and luhricants has promoted continued interest in the use of transition metal compounds 25 in such systems. It has been found, however, that such uses sometimes causes deliterious as well as beneficial effects.
~nong the deliterious effects are promotion of sediment and sludge, particularly in lubricants and fuel oils. Such de-posits can interfere with storage and transport of the oil 30 by promoting corrosion and interferring with pumps, meters and associated equipment.
Therefore, it is an object of the present inven-tlon to provide hydrocarbon-soluble compositions containing organic transition metal salts in combination with ashless 35 dispersants, which provide an optimum balance between bene-ficial and deliterious effects. Other objects will be apparent to those of skill in the ar~ upon reading this di~closure.
Su~ary of the Invention It has now been found that useful hydrocarbon-soluble compositions comprise (A) one or more transition metal salts of at least one or~anic acid; and (B) at least 5 one hydrocarbon-soluble ashless dispersant.
Hydrocarbon systems such as lubricant and fuel compositions (such as distillate fuel compositions com-prising a major amount of hydrocarbon fuel and a minor amount of the aforedescribed salt/dispersant compositions), 10 as well as additive concentrate compositions, are also within the scope of the invention.
Detailed Description of the Invention (A) The transition metal salts.
The transition metals in the organic salts of this 15 invention are chosen from the group consisting of copper, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nic]cel and mixtures of two or more of these. Man-ganese salts and salts containing manganese in admixture with other metals are most commonly used. Often salts 20containing only manganese are used. Lead salts can also be used.
The organic acids used to make the transition metal salts used in this invention contain carbon atoms and include carboxylic acids, particularly those containing from 251 to 30 carbon atoms, sulfonic acids, particularly those containing an aromatic ring structure (e.g., benzene ring) substituted with one or more alkyl groups of 4 to about 22 carbon atoms, and phosphorus acids, containing within their structures one or more organic groups of 1 to about 30 or 30more carbon atoms.
Such carboxylic, sulfonic and phosphorus acids are well known to the art. The carboxylic acids can be mono- or polycarboxylic acids (if the latter, typically they are di-or tricarboxylic acids). Monocarboxylic acids include Cl- 7 35lower acids (acetic, proprionic, etc.) and higher C8+
acids (e.g., octanoic, decanoic, etc.) as well as the well known fatty acids of about 12-30 carbon atoms. The fatty acids are often mixtures or straight and branched chain acids containing, for example, from 5 to about 30% s-traight chain acids and about 70 to about 95% (mole) branched chain acids.
Other commercially available fatty acid mixtures containing mueh higher proportions of s-traight chain acids are also useful.
Mixtures produeed from dimerization of unsaturated Eat-ty acids can also be used.
Higher carboxylic acids include the well known dicarboxylic acids made by alkylating maleic anhydride or its derivatives.
The products of sueh reactions are hydrocarbon substituted succinic aeids, anhydrides, and the like. Lower molecular weight dicarboxylic acids, such as the polymethylene bridged aeids (glutaric, adipie, and the like), can also be used to make the salts of -this invention as well as the lower molecular weight substituted succinic acids such as tetrapropenyl succinic acid and its analogs of to about C30 substituted acids.
Higher molecular weight substituted sueeinie anhydrides, aeids, and analogs useful in making the salts of this invention have been described in a number of patents, partieularly those dealing with aeylated compounds useful as dispersants. ~ypical high molecular weight acids are those made by reaeting a poly(isobutene) fraction having between 30 and 400 (usually 50-250) earbon atoms with maleic anhydride. Such materials are described in U.S. Patents 3,172,892, 3,219,666 and 3,272,746.
Other monocarboxylic acids of similar moleeular weight ean be made by alkylating aerylie aeid and its analogs. Mixtures of sueh aeids can also be used.
Useful salts ean also be made from earboeyclie carboxylic aeid and even aeidic hydroxy compounds such as alkylated phenols. Such materials are diselosed in U.S. Patent 4,100,082, particularly eolumns 15-17.
_c . .
The '082 pa-tent just identified also describes a number of sulfonic acids which are useful in making the salts of this invention, particularly in columns 12-14.
Transition metal salts made from phosphorus acids are also useEul in this invention. Such phosphorus acids have been disclosed in a number of U.S. patents and other literature.
Exemplary of -the former is U.S. Patent 4,191,658 which discloses phosphorus acid salts of the formula R ¦X )a ll P-X M
R (X )b wherein M is a transition metal as described above; each Rl and R is a hydrocarbon radical; each of Xl, X2, X3 and X4 is oxygen or sulfur; and each of a and b is 0 or l.
Typically, the organic acids used to make the salts of this invention are carboxylic acid, sulfonic acid, or mixtures thereof.
A particularly useful group of such salts are those described in U.S. Patent 4,162,986 to Alkaitis et al.
It should be noted that the transition metal salts used in this invention are often overbased; that is, they contain more than sufficient metal to neutralize the acid present. In other words, they contain in excess of one equivalent of metal per equivalent of acid derived moiety. Such salts are known to the 25 art. See, for example, the just cited 4,162,986 patent as well as the following U.S. Patents: 3,827,979 to Piotrowski et al., 3,312,618 to LeSuer et al., 3,616,904 and 3,616,905 to Asseff et al., 2,595,790 to Norman et al., and 3,725,441 to Murphy et al.
.. ..~.
(B) The ashless dispersants.
The ashless dispersants useful in the present invention are }cnown to the art and are those dispersants commonly used in ]ubricants based on oils of lubricating viscosity and hydrocarbon fuels such as normally liquid hydrocarbon fuels. Ashless dispersants are those which leave little or no (metallic) residue or ash on combustion. Generally, this means that they are substantially metal free though they may contain, in addition to carbon, oxygen, hydrogen and, often, nitrogen elements such as phosphorus, sulfur, boron, etc.
Generally, the ashless dispersants of the present invention contain only C, H, O, and N. Occassionally, ester -type dispersants (see below~ can contain only C, H, and O. More complex ashless dispersants, while still metal free, may also contain other elements, such as sulfur, boron, phosphorus, and the like. Typically, however, the ashless dispersan-ts used in this invention are of the nitrogen-containing or nitrogen-free ester type.
Many types of ashless dispersants are known; see, for example, the descriptions in "Lubricant Additives - Recent Developments", the earlier "Lubricant Additives", both by M.W. Ranney, published by Noyes Data Corporation, Park Ridge, New Jersey, 1978 and 1973, respectively, and U.S. Patent 4,136,043.
Among the more commonly available and, therefore, useful hydrocarbon-soluble ashless dispersants are:
(1) Acylated nitrogen-containing dispersants such as those described in U.S. Pa-tent 4,100,082, particularly those at columns 18-20.
i33 These dispersants are made by reaction of an acyla-ting agent (e.g., carboxylic acid or anhydride) with an amino compound such as an amine, polyamine, or other compound containing an -NH- group. Typical acylating agents include the substituted succinic acids descri.bed above and in the '082 patent. Other useful acylating agents have been described in detail in many other patents, such as U.S. Patent 4,234,435 which describes in detail both acylating agents and amino-containing and non-amino-containing compounds which can be used to prepare ashless dispersants.
The acylated ashless dispersants useful in the present invention can be of either the high or low molecular weight type. In addition to portions from amino compounds, they may also incorporate portions from mono- and poly- alcohols, including amino hydroxy compound groups such as the well known amino alcohols. Typical ashless dispersants include those made from alkylene polyamines having 2 to 7 amino groups and 1 to 6 alkylene groups, each containing 2 to 4 carbon atoms. The commercially available ethylene polyamines are useful reagents in this regard.
Lower molecular weight acylated nitrogen containing compounds are also useful as dispersants in the compositions of this invention. Such compounds are made from the aforedescribed amino compounds and mono- and dicarboxylic acid acylating agents containing about 12 to about 20 carbon atoms. Such dispersants often contain imidazoline groups and are known to the art; see, for example, U.S. Patents 3,405,064 and 3,240,575.
High molecular weight acylated nitrogen-containing ashless dispersants wherein an amino and alcohol compound (or amino-alcohol~ both are acylated are also known and useful in thecompositions of this invention; these are described in U.S.
Patent 4,136,043.
ORGANO TRANSITION METAL SALT/ASHLESS
DETERGENT-DISPERSANT COMBINATIONS
Field o~ the Invention This invention relates to hydrocarbon~soluble com~
positions containing a transition metal salt of an organic acid and a hydrocarbon-soluble ashless dispersant. Typi cally, it relates to such compositions wherein the organic acid is a carboxylic, sulfonic or phosphorus acid and the 10 ashless dispersant is a nitrogen or non-nitrogen containing ester dispersant. It also relates to hydrocarbon systems containing the aforesaid compositions, such as lubricants based on oils of lubricating viscosi~y and hydrocarbon fuels.
15 Prior ~rt The treatment of hydrocarbon systems such as lubricants based on lubricating oils of lubricating vis-cosity (e.g., greases, lubricating oils and the like) and hydrocarbon fuels of both the solid and normally liquid type 20 with transition metals and transition metal-containing compounds, both organic and inorganic, is well known to the art. Such treatments are used to increase the systems' resistance to oxidative deterioration, promote ~.heir con-version to cohesive films in the case of paints and lac-25 quers, and improve theix combustion as, for example, fuelsD
Among the organic transition metal compounds thathave been used for such purposes are carboxylate and sul--- 2fonate salts and mixtures of such salts. For example, U.S.
Patent 4,162,986 to ~lkaitis et al. describes transition metal salts of mixed organic carboxylic and sulfonic or second carboxylic acids and their use as catalysts, anti-5 knock agents, combustion improvers, smoke suppressants,curing agents, driers, micronutrient sources, lubricant additives, and the like.
U.S Patent 3,762,~90 to Collins describes hydro-lyzable manganese soaps, stablilized by the inclusion of 10 proprionic acid and the use of such materials as siccatives for paints, varnishes and inks, stabilizers in various plastics and additives for greases and lubricating oils as well as smoke-suppressing and anti-corrosion additives for fuel and fuel oils.
U.S. Patent 3,723,152 to Alkaitis et al. des-c:ribes basic cobalt salts of carboxylic acids and their use as drier compos-itions for oil vehicles.
Other patents such as U.S. Patent 4,202,671 to Diehl et al. describe the use of organic magnesium compounds 20 as fuel conditioners for the reduction of fuel requirements and emissions.
Increasing concern with pollution and the rising cost of hydrocarbon-based fuels and luhricants has promoted continued interest in the use of transition metal compounds 25 in such systems. It has been found, however, that such uses sometimes causes deliterious as well as beneficial effects.
~nong the deliterious effects are promotion of sediment and sludge, particularly in lubricants and fuel oils. Such de-posits can interfere with storage and transport of the oil 30 by promoting corrosion and interferring with pumps, meters and associated equipment.
Therefore, it is an object of the present inven-tlon to provide hydrocarbon-soluble compositions containing organic transition metal salts in combination with ashless 35 dispersants, which provide an optimum balance between bene-ficial and deliterious effects. Other objects will be apparent to those of skill in the ar~ upon reading this di~closure.
Su~ary of the Invention It has now been found that useful hydrocarbon-soluble compositions comprise (A) one or more transition metal salts of at least one or~anic acid; and (B) at least 5 one hydrocarbon-soluble ashless dispersant.
Hydrocarbon systems such as lubricant and fuel compositions (such as distillate fuel compositions com-prising a major amount of hydrocarbon fuel and a minor amount of the aforedescribed salt/dispersant compositions), 10 as well as additive concentrate compositions, are also within the scope of the invention.
Detailed Description of the Invention (A) The transition metal salts.
The transition metals in the organic salts of this 15 invention are chosen from the group consisting of copper, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nic]cel and mixtures of two or more of these. Man-ganese salts and salts containing manganese in admixture with other metals are most commonly used. Often salts 20containing only manganese are used. Lead salts can also be used.
The organic acids used to make the transition metal salts used in this invention contain carbon atoms and include carboxylic acids, particularly those containing from 251 to 30 carbon atoms, sulfonic acids, particularly those containing an aromatic ring structure (e.g., benzene ring) substituted with one or more alkyl groups of 4 to about 22 carbon atoms, and phosphorus acids, containing within their structures one or more organic groups of 1 to about 30 or 30more carbon atoms.
Such carboxylic, sulfonic and phosphorus acids are well known to the art. The carboxylic acids can be mono- or polycarboxylic acids (if the latter, typically they are di-or tricarboxylic acids). Monocarboxylic acids include Cl- 7 35lower acids (acetic, proprionic, etc.) and higher C8+
acids (e.g., octanoic, decanoic, etc.) as well as the well known fatty acids of about 12-30 carbon atoms. The fatty acids are often mixtures or straight and branched chain acids containing, for example, from 5 to about 30% s-traight chain acids and about 70 to about 95% (mole) branched chain acids.
Other commercially available fatty acid mixtures containing mueh higher proportions of s-traight chain acids are also useful.
Mixtures produeed from dimerization of unsaturated Eat-ty acids can also be used.
Higher carboxylic acids include the well known dicarboxylic acids made by alkylating maleic anhydride or its derivatives.
The products of sueh reactions are hydrocarbon substituted succinic aeids, anhydrides, and the like. Lower molecular weight dicarboxylic acids, such as the polymethylene bridged aeids (glutaric, adipie, and the like), can also be used to make the salts of -this invention as well as the lower molecular weight substituted succinic acids such as tetrapropenyl succinic acid and its analogs of to about C30 substituted acids.
Higher molecular weight substituted sueeinie anhydrides, aeids, and analogs useful in making the salts of this invention have been described in a number of patents, partieularly those dealing with aeylated compounds useful as dispersants. ~ypical high molecular weight acids are those made by reaeting a poly(isobutene) fraction having between 30 and 400 (usually 50-250) earbon atoms with maleic anhydride. Such materials are described in U.S. Patents 3,172,892, 3,219,666 and 3,272,746.
Other monocarboxylic acids of similar moleeular weight ean be made by alkylating aerylie aeid and its analogs. Mixtures of sueh aeids can also be used.
Useful salts ean also be made from earboeyclie carboxylic aeid and even aeidic hydroxy compounds such as alkylated phenols. Such materials are diselosed in U.S. Patent 4,100,082, particularly eolumns 15-17.
_c . .
The '082 pa-tent just identified also describes a number of sulfonic acids which are useful in making the salts of this invention, particularly in columns 12-14.
Transition metal salts made from phosphorus acids are also useEul in this invention. Such phosphorus acids have been disclosed in a number of U.S. patents and other literature.
Exemplary of -the former is U.S. Patent 4,191,658 which discloses phosphorus acid salts of the formula R ¦X )a ll P-X M
R (X )b wherein M is a transition metal as described above; each Rl and R is a hydrocarbon radical; each of Xl, X2, X3 and X4 is oxygen or sulfur; and each of a and b is 0 or l.
Typically, the organic acids used to make the salts of this invention are carboxylic acid, sulfonic acid, or mixtures thereof.
A particularly useful group of such salts are those described in U.S. Patent 4,162,986 to Alkaitis et al.
It should be noted that the transition metal salts used in this invention are often overbased; that is, they contain more than sufficient metal to neutralize the acid present. In other words, they contain in excess of one equivalent of metal per equivalent of acid derived moiety. Such salts are known to the 25 art. See, for example, the just cited 4,162,986 patent as well as the following U.S. Patents: 3,827,979 to Piotrowski et al., 3,312,618 to LeSuer et al., 3,616,904 and 3,616,905 to Asseff et al., 2,595,790 to Norman et al., and 3,725,441 to Murphy et al.
.. ..~.
(B) The ashless dispersants.
The ashless dispersants useful in the present invention are }cnown to the art and are those dispersants commonly used in ]ubricants based on oils of lubricating viscosity and hydrocarbon fuels such as normally liquid hydrocarbon fuels. Ashless dispersants are those which leave little or no (metallic) residue or ash on combustion. Generally, this means that they are substantially metal free though they may contain, in addition to carbon, oxygen, hydrogen and, often, nitrogen elements such as phosphorus, sulfur, boron, etc.
Generally, the ashless dispersants of the present invention contain only C, H, O, and N. Occassionally, ester -type dispersants (see below~ can contain only C, H, and O. More complex ashless dispersants, while still metal free, may also contain other elements, such as sulfur, boron, phosphorus, and the like. Typically, however, the ashless dispersan-ts used in this invention are of the nitrogen-containing or nitrogen-free ester type.
Many types of ashless dispersants are known; see, for example, the descriptions in "Lubricant Additives - Recent Developments", the earlier "Lubricant Additives", both by M.W. Ranney, published by Noyes Data Corporation, Park Ridge, New Jersey, 1978 and 1973, respectively, and U.S. Patent 4,136,043.
Among the more commonly available and, therefore, useful hydrocarbon-soluble ashless dispersants are:
(1) Acylated nitrogen-containing dispersants such as those described in U.S. Pa-tent 4,100,082, particularly those at columns 18-20.
i33 These dispersants are made by reaction of an acyla-ting agent (e.g., carboxylic acid or anhydride) with an amino compound such as an amine, polyamine, or other compound containing an -NH- group. Typical acylating agents include the substituted succinic acids descri.bed above and in the '082 patent. Other useful acylating agents have been described in detail in many other patents, such as U.S. Patent 4,234,435 which describes in detail both acylating agents and amino-containing and non-amino-containing compounds which can be used to prepare ashless dispersants.
The acylated ashless dispersants useful in the present invention can be of either the high or low molecular weight type. In addition to portions from amino compounds, they may also incorporate portions from mono- and poly- alcohols, including amino hydroxy compound groups such as the well known amino alcohols. Typical ashless dispersants include those made from alkylene polyamines having 2 to 7 amino groups and 1 to 6 alkylene groups, each containing 2 to 4 carbon atoms. The commercially available ethylene polyamines are useful reagents in this regard.
Lower molecular weight acylated nitrogen containing compounds are also useful as dispersants in the compositions of this invention. Such compounds are made from the aforedescribed amino compounds and mono- and dicarboxylic acid acylating agents containing about 12 to about 20 carbon atoms. Such dispersants often contain imidazoline groups and are known to the art; see, for example, U.S. Patents 3,405,064 and 3,240,575.
High molecular weight acylated nitrogen-containing ashless dispersants wherein an amino and alcohol compound (or amino-alcohol~ both are acylated are also known and useful in thecompositions of this invention; these are described in U.S.
Patent 4,136,043.
(2) ~igh molecular weight nitrogen-free esters.
These esters, as indicated above, are made by reacting the aforedescribed acylating agents (e.g., poly(isobutene)) succinic anhydride with polyols and monoalcohols and are well known; see, for example, U.S. Patent 3,522,179.
These esters, as indicated above, are made by reacting the aforedescribed acylating agents (e.g., poly(isobutene)) succinic anhydride with polyols and monoalcohols and are well known; see, for example, U.S. Patent 3,522,179.
(3) Hydrocarbyl substituted amines.
Hydrocarbyl substituted amines useful as ashless dispersants are known in the art; see, for example, U.S.
Patents 3,275,554, 3,438,757, 3,454,555, and 3,565,804. A
discussion of such materials also appears in the aforementioned '082 patent.
Hydrocarbyl substituted amines useful as ashless dispersants are known in the art; see, for example, U.S.
Patents 3,275,554, 3,438,757, 3,454,555, and 3,565,804. A
discussion of such materials also appears in the aforementioned '082 patent.
(4) Nitrogen-containing condensates of phenols, aldehydes and amino compounds.
Condensates made from reacting a phenol, aldehyde (such as formaldehyde) and amino compounds (such as those described above) are useful as ashless dispersants in the compositions of this invention. These materials are often generically known as Mannich condensatesO Generally, they are made from reacting a hydrocarbon substituted phenol (e.g., an alkylated phenol 20 having an alkyl group of about 34-400 carbon atoms), formalde-hyde and an amino or polyamino compound having at least one -NH- group. A number of such materials are known to the art;
see, for example, the aforementioned '082 patent, particularly columns 21-22, and the references cited therein.
The hydrocarbon-soluble compositions of this in-vention are made by combining (A) one or more of the afore-described transition metal salts of organic acids with ~B) at least one of the aforedescribed hydrocarbon-soluble
Condensates made from reacting a phenol, aldehyde (such as formaldehyde) and amino compounds (such as those described above) are useful as ashless dispersants in the compositions of this invention. These materials are often generically known as Mannich condensatesO Generally, they are made from reacting a hydrocarbon substituted phenol (e.g., an alkylated phenol 20 having an alkyl group of about 34-400 carbon atoms), formalde-hyde and an amino or polyamino compound having at least one -NH- group. A number of such materials are known to the art;
see, for example, the aforementioned '082 patent, particularly columns 21-22, and the references cited therein.
The hydrocarbon-soluble compositions of this in-vention are made by combining (A) one or more of the afore-described transition metal salts of organic acids with ~B) at least one of the aforedescribed hydrocarbon-soluble
5 ashless dispersants. It should be noted that "hydrocarbon soluble" in describing this invention means that the ma-terial in question has a solubility at 25C of at least 0.001 parts by weight in the hydrocarbon system in which it is to function. The combination of the materials (A) and 10 (B) can be effected in any convenient mannerO Usually, it ls advantageous to avoid combining the salt and the dis persant directly since precipitation problems can thus be avoided. Therefore, it is common to combine either the dispersant or the salt with an inert, solvent diluent and 15 then combine this material with the other and/or auxiliary agents. The solvent/diluents used in the composition of this inven~ion are usually hydrocarbyl in nature although they may contain small amounts of other hetero elements and are often highly aromatic to promote solubilityO Auxiliary 20 agents used in the compositions of this invention include dyes, anti-oxidants, metal deactivators, and, paxticularly, demulsifying agents which inhibit the tendency of the dis-persant and/or the salt to promote emulsion formations in the vehicles it is used to treat, such as fuel oils, lu-25 bricants and the like. Many such demulsifying agents areknown; see, for example, Encyclopedia of Chemical Tech-nology - Kir~-Othmer, Volume ~, pages 151 et seq. and Volume 19, pages 507 et seq. (1965). Typical demulsifying agents are surface active agents containing hydrophilic and 30 lipophilic portions in the molecule. Such agents are often made by reacting a hydroxy compound, such as a phenol or alcohol, with materials such as ethylene oxide and propylene oxide and their mixtures in various propor~ions.
As indicated above, the compositions of this 35 invention are used to treat lubricants based on lubricating oils of lubricating viscosity and hydrocarbon fuels. The lubricating oils are typically hydrocarbon in nature al-though they may contain non-hydrocarbyl portions, such as synthetic ester, ether, and similar oils.
The fuels treated with the composi~ions of this invention include both solid and normally liquid fuels.
Among the solid fuels are coal, shale, peat, wood, organic refuse, charcoal and the like. Liquid fuels encompass the lighter petroleum fractions such as gasoline, kerosene, and 10 the like, as well as other fractions such as middle dis-tillate fuel oils. Typical middle distillate fuel oils which can be treated with the compo~sitions in this invention include No. 1, 2, and 4 fuel oils as defined by ANSI/ASTM
Standard D-396-97 and other such materials. ~ombinations of 15 such fuel oils with straight run, vacuum run, and other specially treated residual oils can also be advantageously treated with the combinations of the present invention.
The concentration of the compositions of this invention in the treated lubricant or oil compositions is 20 such that the treated lubricant or sil composition~ contain about 1-500, preferably 5-350 ppm (b~ weight) transition metal* and about 5-1000, preferably 10-800 ppm (by weight) ashless dispersant. In fuel oils, particularly, the com-position is used to produce a transition metal concentration 25 at about 10-200 ppm (by weight) and ashless dispersant concentration of about 15-~50 ppm (by weight).
EXAMP~ES
Example 1 A known ashless acylated nitrogen-containing 30 dispersant is prepared by reacting a mixture of poly(iso-butene) substituted succinic anhydride acylating agent (having a substituent with an Mn equal to about 1,000) with a commercial mixture of ethylene polyamines averaging in composition triethylene tetra-amine. The reaction is 35 carried out in aromatic solvent/diluent and the proportion * The concentration of salt is expressed in terms o~
metal alone.
of acid to polyamine, by weight, is approximately 100 to 9;
water and other low-boiling products and impurities are removed by heating to give the desired ashless dispersant having a nitrogen content of about 2% (by weight).
5 Example 2 A hydrocarbon-soluble composition is prepared by combining by weight the following: an overbased magnesium carboxylate* (containing 40% by weight Mn) - 10.82 parts, the ashless dispersant of Example 1 - 14.43 parts, a first 10 demulsifier** - 0.18 parts, a second demulsifier (3) - 0.14 parts, and aromatic solvent (4) - 74.43 parts. * Sold by the Mooney Chemical Company as Mooney 910. ** An Ethoxylated/
Propylated Hydroxy Compound available as TOLAD 285 from The Treatolite Division of Petroli~e Corporation, St. I,ouis, 15 Missouri. (3) An Ethoxylated Propoxylated Pentaerythritol available as NALCO 5RD-648 from the Nalco Chemical Company of Houston, Texas. (4) HI-SOL Aromatic Solvent having a Kauri Gum-Butanol Value of 95. The above combination is made by using the aromatic solvent in such a way as to avoid 20 direct combination of the concentrated carboxylate and ashless dispersant. The combination has a specific gravity at 15.6 o 0.94, a pour point of -57C., and a manganese content of 4.3 4.6 percent by weight~
Example 3 The composition of Example 2 was used to treat a typical commercially available No. 2 middle distillate fuel oil. The treatment level is 1 part composition to 4600 parts by weight of fuel oil. This treatment level is equivalent to 10.7 parts per million manganese per part of 30 fuel. The treated fuel was used to operate a commercial boiler and compared with use of untreated fuel in the same boiler under comparable conditions. It was found that use of the compositions of this invention in the fuel, as des-cribed above, produced a 1.7 percent efficiency improvement 35 as reflected by reduced fuel consumption.
As indicated above, the compositions of this 35 invention are used to treat lubricants based on lubricating oils of lubricating viscosity and hydrocarbon fuels. The lubricating oils are typically hydrocarbon in nature al-though they may contain non-hydrocarbyl portions, such as synthetic ester, ether, and similar oils.
The fuels treated with the composi~ions of this invention include both solid and normally liquid fuels.
Among the solid fuels are coal, shale, peat, wood, organic refuse, charcoal and the like. Liquid fuels encompass the lighter petroleum fractions such as gasoline, kerosene, and 10 the like, as well as other fractions such as middle dis-tillate fuel oils. Typical middle distillate fuel oils which can be treated with the compo~sitions in this invention include No. 1, 2, and 4 fuel oils as defined by ANSI/ASTM
Standard D-396-97 and other such materials. ~ombinations of 15 such fuel oils with straight run, vacuum run, and other specially treated residual oils can also be advantageously treated with the combinations of the present invention.
The concentration of the compositions of this invention in the treated lubricant or oil compositions is 20 such that the treated lubricant or sil composition~ contain about 1-500, preferably 5-350 ppm (b~ weight) transition metal* and about 5-1000, preferably 10-800 ppm (by weight) ashless dispersant. In fuel oils, particularly, the com-position is used to produce a transition metal concentration 25 at about 10-200 ppm (by weight) and ashless dispersant concentration of about 15-~50 ppm (by weight).
EXAMP~ES
Example 1 A known ashless acylated nitrogen-containing 30 dispersant is prepared by reacting a mixture of poly(iso-butene) substituted succinic anhydride acylating agent (having a substituent with an Mn equal to about 1,000) with a commercial mixture of ethylene polyamines averaging in composition triethylene tetra-amine. The reaction is 35 carried out in aromatic solvent/diluent and the proportion * The concentration of salt is expressed in terms o~
metal alone.
of acid to polyamine, by weight, is approximately 100 to 9;
water and other low-boiling products and impurities are removed by heating to give the desired ashless dispersant having a nitrogen content of about 2% (by weight).
5 Example 2 A hydrocarbon-soluble composition is prepared by combining by weight the following: an overbased magnesium carboxylate* (containing 40% by weight Mn) - 10.82 parts, the ashless dispersant of Example 1 - 14.43 parts, a first 10 demulsifier** - 0.18 parts, a second demulsifier (3) - 0.14 parts, and aromatic solvent (4) - 74.43 parts. * Sold by the Mooney Chemical Company as Mooney 910. ** An Ethoxylated/
Propylated Hydroxy Compound available as TOLAD 285 from The Treatolite Division of Petroli~e Corporation, St. I,ouis, 15 Missouri. (3) An Ethoxylated Propoxylated Pentaerythritol available as NALCO 5RD-648 from the Nalco Chemical Company of Houston, Texas. (4) HI-SOL Aromatic Solvent having a Kauri Gum-Butanol Value of 95. The above combination is made by using the aromatic solvent in such a way as to avoid 20 direct combination of the concentrated carboxylate and ashless dispersant. The combination has a specific gravity at 15.6 o 0.94, a pour point of -57C., and a manganese content of 4.3 4.6 percent by weight~
Example 3 The composition of Example 2 was used to treat a typical commercially available No. 2 middle distillate fuel oil. The treatment level is 1 part composition to 4600 parts by weight of fuel oil. This treatment level is equivalent to 10.7 parts per million manganese per part of 30 fuel. The treated fuel was used to operate a commercial boiler and compared with use of untreated fuel in the same boiler under comparable conditions. It was found that use of the compositions of this invention in the fuel, as des-cribed above, produced a 1.7 percent efficiency improvement 35 as reflected by reduced fuel consumption.
Claims (16)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
A hydrocarbon-soluble composition comprising:
(A) one or more transition metal salts of at least one organic acid; and (B) at least one hydrocarbon-soluble ashless dispersant. - 2. A composition as claimed in claim 1 wherein the organic acid is a carboxylic acid, phosphoric acid, sulfonic acid or mixture of two or more of these.
- 3. A composition as claimed in claim 2 wherein the organic acid contains at least about 7 carbon atoms.
- 4. A composition as claimed in claim 3 wherein the metal is chosen from the group consisting of copper, scan-dium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and mixtures of two or more of these,
- 5. A composition as claimed in claim 4 wherein the acid is a carboxylic acid, sulfonic acid or mixture thereof.
- 6. A composition as claimed in claim 5 wherein the metal is manganese.
- 7. A composition as claimed in claim 6 wherein the salt (A) is an overbased salt.
- 8 A composition as claimed in claim 7 wherein the dispersant (B) is a nitrogen-containing dispersant, a nitrogen-free ester dispersant or a mixture thereof.
- 9. A hydrocarbon-soluble composition consisting essentially of:
(A) one or more transition metal salts of at least one organic acid;
(B) at least one hydrocarbon-soluble ashless dispersant;
(C) at least one demulsifier; and (D) substantially inert solvent-diluent. - 10. A composition as claimed in claim 9 where (A) is an overbased manganese salt of a carboxylic acid, a sulfonic acid or mixture thereof; and (B) is an acylated nitrogen-containing dispersant.
- 11. A fuel composition comprising a major amount of fuel and a minor amount of the composition of claim 1.
- 12. A fuel composition as claimed in claim 11 wherein the fuel is normally liquid.
- 13. A normally liquid fuel composition comprising a major amount of distillate fuel oil and an amount of those compositions of claim 1 sufficient to give the fuel composition a transition metal content of about 1-500 ppm.
- 14. A normally liquid fuel composition comprising a major amount of distillate fuel oil and an amount of those compositions of claim 10 sufficient to give the fuel composition a transition metal content of about 10-200 ppm.
- 15. An additive concentrate comprising about 10-99% by weight of the composition of claim 1 and a substantially inert, normally liquid organic diluent.
- 16. An additive concentrate comprising about 10-99% by weight of the composition of claim 9 and a substantially inert, normally liquid organic diluent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000430946A CA1191833A (en) | 1983-06-22 | 1983-06-22 | Organo transition metal salt/ashless detergent- dispersant combinations |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000430946A CA1191833A (en) | 1983-06-22 | 1983-06-22 | Organo transition metal salt/ashless detergent- dispersant combinations |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1191833A true CA1191833A (en) | 1985-08-13 |
Family
ID=4125526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000430946A Expired CA1191833A (en) | 1983-06-22 | 1983-06-22 | Organo transition metal salt/ashless detergent- dispersant combinations |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1191833A (en) |
-
1983
- 1983-06-22 CA CA000430946A patent/CA1191833A/en not_active Expired
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