EP0267674A1 - Zusammensetzungen zur Verhinderung von Inkrustierungen und deren Verwendungen - Google Patents

Zusammensetzungen zur Verhinderung von Inkrustierungen und deren Verwendungen Download PDF

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Publication number
EP0267674A1
EP0267674A1 EP87307863A EP87307863A EP0267674A1 EP 0267674 A1 EP0267674 A1 EP 0267674A1 EP 87307863 A EP87307863 A EP 87307863A EP 87307863 A EP87307863 A EP 87307863A EP 0267674 A1 EP0267674 A1 EP 0267674A1
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Prior art keywords
composition
fouling
acid
metal
inhibiting
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EP87307863A
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English (en)
French (fr)
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Paul E. Eaton
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Baker Petrolite LLC
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Petrolite Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation

Definitions

  • the processes involved in oil, gas and petrochemical refining for example, reforming, hydroforming, absorption, hydrocracking, isomerization, extraction, cracking, fractionation, hydrofining, desalting and the like, expose hydrocarbon streams to relatively elevated temperatures. These temperatures are most commonly attained by the use of heaters and heat exchangers in which the hydrocarbon feeds, products and intermediates are intimately contacted with heated surfaces. These conditions are known to promote the formation of fouling deposits which can drastically limit refining capacities and flow rates.
  • fouling deposits accompanying the thermally initiated physical or chemical modification of hydrocarbons and derivatives is observed any time a hydrocarbon or derivative phase is exposed to a retaining surface, metallic or otherwise, at elevated temperatures in process equipment.
  • Deposits of this nature are known to materially decrease heat transfer characteristics of the affected systems and are generally removed only with considerable difficulty. The consequent increases in operating and maintenance expense accompanying the formation and removal of such deposits is often substantial. Consequently, considerable effort has been devoted to attempts to eliminate fouling problems, with the result that numerous methods have been proposed for either preventing foulant deposition or removing fouling deposits. These methods have met with varying degrees of success but the essential problem remains.
  • the fouling deposits which are encountered as a result of the physical and/or chemical modification of hydrocarbon feeds initiated by elevated process temperatures may consist of sticky, tarry, polymeric or carbonaceous material.
  • the most common foiling deposits can be generally classified as inorganic salts, corrosion products, metal-organic compounds, organic polymers and coke.
  • the inorganic salts such as sodium, calcium and magnesium chloride are probably carried into the process system with the crude feed stock.
  • Metal-organic compounds may also be present in the feed stock or may be formed on heat transfer surfaces by combinations with corrosion products or other metals carried into the system.
  • the formation of organic polymers is most commonly attributed to reaction of unsaturated hydrocarbons. Coke deposition is usually associated with the occurrence of hot spots caused by the accumulation of fouling deposits. Consequently, it can be shown that, in such processes, the metal and organic elements of fouling deposits interact with each other.
  • This invention relates to novel antifoulant compositions and to the use thereof to inhibit fouling of equipment used in the refining of crude oil, gas and petrochemicals and in the thermal processing of other organic materials.
  • the invention relates to the use of colloidally dispersed overbase complex antifoulants in oil refineries, gas plants and petrochemical refineries. More particularly, the invention relates to overbase complexes of metal oxides and/or carbonates with at least one complexing agent and to their use as antifoulants in oil, petrochemical and gas refining operations.
  • antifoulants A wide variety of antifoulants has been used in attempts to inhibit fouling associated with the decomposition of crude and refined oils, gases and petrochemical feed streams.
  • a partial, but representative, listing of patents relating to antifoulant compositions and their uses is set forth below.
  • UK Patent Appln. 2017747 A describes sodium di-2-ethylhexylsulphosuccinates as fouling inhibitors for crude petroleum oil and UK Patent 2021144 B describes polyalkylenoxy sulfoxy salts for preventing and removing fouling deposits on refining equipment for hydrocarbon food streams.
  • Overbased oil-stable, fluid dispersions or “solutions” of complexes containing, e.g., magnesium and calcium, and their preparation and use are well known to those skilled in the art.
  • base historically refers to metal base/acid reaction products containing an amount of metal in stoichiometric excess of that required to form a neutral organic acid salt of such base. Synonomous terms frequently used include “basic”, “highly basic” and “hyperbased”.
  • U.S. Patents which disclose processes for preparing overbased metal complexes include the following: U.S. 2,585,520 discloses the preparation of highly basic magnesium and calcium petrol eum solfonates useful as additives for lubricating oils. U.S. 2,895,913 discloses the preparation of stable oil-dispersible overbased organo-magnesium compounds useful as additives in lubricating oils. U.S. 3,057,896 discloses the preparation of overbased calcium sulfonates useful as additives for lubricating oils. U.S. 3,150,089 discloses stable dispersions of overbased organo-magnesium compounds useful as additives for lubricating oils. U.S.
  • 3,629,109 discloses the preparation of overbased organo-magnesium complexes which are useful as lubricant and fuel additives.
  • U.S. 3,764,536 discloses the preparation of an overbased calcium salt of alkenlsuccinimide which is useful as a dispersant additive for lubricating oils.
  • U.S. 3,776,835 discloses detergent-dispersant compositions used as antifoulants for fouling caused by high temperature hydrocarbon streams.
  • Such compositions include sulfonates, especially normal and basic metal salts of benzene sulfonic acids, normal and basic salts of phosphonic and thiophosphonic acids, the normal and basic salts of phenates and carboxylate and carboxylate-phenate salts, alkenyl succinimides, alkali metal naphthenates and amines and carboxylic acids.
  • U.S. 3,865,737 discloses the preparation of fluid, overbased organomagnesium complex dispersion which is useful as a lubricating composition additive.
  • U.S. 4,129,589 discloses the preparation of overbased magnesium salts of sulfonic acids which are useful as lubricant additives.
  • U.S. 3,865,737 discloses the preparation of fluid, overbased organomagnesium complex dispersion which is useful as a lubricating composition additive.
  • U.S. 4,129,589 discloses the preparation of overbased magnesium salts of sulfonic acids which are useful as lubricant additives.
  • U.S. 4,293,429 discloses the preparation of an overbased mixture of a magnesium carboxylate and magnesium oxide in the form of a fluid dispersion of submicron-sized magnesium oxide. The compounds are useful as additives for lubricants.
  • U.S. 4,295,981 discloses the preparation of overbased magnesium phenates useful as lubricating oil additives.
  • U.S. 4,298,482 describes the preparation of an overbased mixture of magnesium salts and magnesium hydroxide in the form of a dispersion of very small particles.
  • the overbased material is useful as an acid neutralizer for lubricating oils and fuels.
  • U.S. 4,347,147 discloses the preparation of magnesium sulfonates and magnesium oxide having a small particle size.
  • U.S. 4,474,710 discloses the preparation of overbased mixtures of magnesium hydroxide or magnesium carbonate in a liquid magnesium sulfonate dispersant. The materials are useful as lubricant additives.
  • the present invention pertains to novel antifoulant, compositions which are overbase complexes comprising oil-stable colloidal dispersions of fine particles of a metal salt, e.g., a met al oxide or carbonate, and a complexing agent and their use in the inhibition of fouling, particularly high temperature fouling, e.g., 500-1200° F, in refining processes.
  • a metal salt e.g., a met al oxide or carbonate
  • a complexing agent e.g., a complexing agent
  • a fouling problem in one area of a refinery may not necessarily respond to the same antifoulant treatment as does a different area of a refinery. Accordingly, treatment of refining operations must be broken down, unit by unit, and the particular fouling characteristics of each unit must be defined and treated appropriately.
  • Crude unit preheat exchanger Crude unit vacuum resid exchanger Crude unit vacuum distillation heater and resid Fluid catalytic cracker preheat Fluid catalytic cracker slurry pumparound Fluid catalytic cracker furnace Delayed coker Fluid coker Visbreaker Hydrotreater Hydrocracker Reboilers Hydrodesulfurizers Heat exchangers Hot separators Pumparound circuits Process stream tubes
  • an oxide or carbonate of Mg, Ca, Ba, Sr or Mn is prepared in conjunction with at least one complexing agent, a product results which is an overbase complex of a metal oxide or carbonate, in an extremely fine, preferably submicron particle size, and the metal salt of the complexing agent. It is theorized that the presence of the complexing agent, during preparation of the metal oxide or carbonate, protects the fine particles of metal oxide or carbonate from agglomerating and allows the fine particles to remain dispersed in a stable manner in the diluent used in the reaction and, later, in a hydrocarbon stream.
  • overbases comprise dispersions of salts formed by contacting an acidic material with a basically reacting metal compound, e.g., a metal hydroxide. Alternatively, it has been suggested that they comprise "polymeric salts". It is believed that neither theory is incorrect but that neither is completely correct. In accordance with the present invention, it is believed that the preparation of an"overbased” material results in an "overbase complex" of a metal oxide or carbonate with an organic acid dispersant or stabilizer (i.e., "complexing agent"). The nature of the complex so-formed is not completely understood.
  • an "overbase complex” is a complex of an oxide or carbonate of Mg, Ca, Ba, Sr or Mn and a metal salt of an organic acid "complexing agent".
  • the overbase complex contains a stoichiometric excess of metal, relative to the number of equivalents of acid complexing agent which is reacted with a basic metal compound to afford the complex, based on the normal stoichiometry of the particular metal base and acid.
  • a "neutral" or “normal” metal salt of an acid is characterized by an equivalent ratio of metal to acid of 1:1, while an overbased salt is characterized by a higher ratio, e.g., 1.1:1, 2:1, 5:1, 10:1, 15:1, 20:1, 30:1 and the like.
  • the term "metal ratio" is used to designate the ratio of (a) equivalents of metal to acid in an overbased salt to (B) the number of equivalents expected to be present in a normal salt, based on the usual stoichiometry of the metal or metals involved and the acid of acids present.
  • an oil dispersion of an overbased magnesium salt containing two equivalents of acid and twenty equivalents of magnesium would have a metal ratio of 10 (i.e., 20 ⁇ (1+1)).
  • magnesium for example, is regarded as having two equivalents per atomic weight; magnesium oxide (MgO) and magnesium hydroxide (Mg(OH)2), two equivalents per mole.
  • Organic acids are regarded as having one equivalent of acid per acidic hydrogen or acid group.
  • a monocarboxylic acid or monosulfonic acid or their equivalent derivatives such as esters and ammonium and metal salts, have one equivalent per mole of acid, ester or salt; a disulfonic acid or dicarboxylic acid, or equivalent derivative, has two equivalents per mole.
  • the basically reacting metal compounds such as the oxides and carbonates of calcium, barium and manganese have two equivalents per mole (i.e., two equivalents per atomic weight of metal).
  • the complex antifoulants of the invention are overbase complexes of metal oxides and/or carbonates and a metal salt of at least one complexing agent.
  • carboxylate refers to the reaction product of a metal base and an organic carboxylic acid have the general formula R-COOH, where R is a hydrocarbon radical
  • noncarboxylate refers to the reaction product of a metal base and an organic acid other than an organic carboxylic acid, i.e., “noncarboxylic” acids such as organic sulfur acids and organic phosphorus acids, which latter materials have substantially greater dispersant capabilities than do the carboxylates which appear to have more stabilizing capabilities.
  • the role of the complexing agent in the preparation and use of the antifoulants of the invention is not clear. As stated above, some may function as stabilizers while others may function as dispersants. Certainly, some may have both functions or another, unknown, function. It is clear, however, that, during the preparation of the complex, the presence of at least one complexing agent is essential to provide the complex antifoulants of the invention. It is also clear that the preferred an tifoulants are characterized by the presence of a noncarboxylate, especially a sulfonate.
  • the overbase complexes used in the present invention may be prepared in any manner known to the prior art for preparing overbased salts, provided that the overbase complex resulting therefrom is in the form of finally divided, preferably submicron, particles which form form a stable dispersion in oil.
  • a preferred method for preparing the antifoulants of the present invention is to form a mixture of a base of the desired metal, e.g., Mg(OH)2, a complexing agent, e.g., a fatty acid such as a tall oil fatty acid, which is present in a quantity much less than that required to stoichiometrically react with the hydroxide, and a non-volatile diluent.
  • the mixture is heated to a temperature of about 250-350° C, whereby there is afforded the overbase complex of the metal oxide and metal salt of the fatty acid.
  • the metal carbonate/complexing agent overbase complex is prepared in the same manner as described above, except that carbon dioxide is bubbled through the initial reaction mixture.
  • Complexing agents which are used in the present invention are carboxylic acids, phenols, organic phosphorus acids and organic sulfur acids. Included are those acids which are presently used in preparing overbased materials (e.g., those described in U.S. Patents 3,312,618, 2,695,910 and 2,616,904) and constitute an art-recognized class of acids.
  • the carboxylic acids, phenols, organic phosphorus acids and organic sulfur acids which are oil-soluble per se, particularly the oil-soluble sulfonic acids, are especially useful.
  • Oil-soluble derivatives of these organic acidic substances can be utilized in lieu of or in combination with the free acids.
  • organic acidic substances such as their metal salts, ammonium salts, and esters (particularly esters with lower aliphatic alcohols having up to six carbon atoms, such as the lower alkanols)
  • esters particularly esters with lower aliphatic alcohols having up to six carbon atoms, such as the lower alkanols
  • Suitable carboxylic acid complexing agents which may be used herein include aliphatic, cycloaliphatic, and aromatic mono and polybasic carboxylic acids such as the naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids and alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the aliphatic acids generally are long chain acids and contain at least eight carbon atoms and preferably at least twelve carbon atoms.
  • the cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated.
  • Specific examples include 2-ethylhexanoic acid, alphalinolenic acid, propylene-tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures off two or more carboxylic acids such as tall oil fatty acids, rosin acids, and the like.
  • saturated aliphatic monocarboxylic acids e.g. formic, acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, pelargonic, capric, undecylic, lauric, tridecylic, myristic, isoacetic, palmitic, margaric and stearic; alicyclic unsaturated monocarboxylic acids, e.g., hydnocarpic and chaulmoogric; saturated aliphatic dicarboxylic acids, e.g.
  • dicarboxyl acids e.g. cyclohexane dicarboxylic acid
  • unsaturated aliphatic monocarboxylic acids e.g. acrylic. crotonic, decenoic, undecenoic, tridecenoic, pentadecenoic, oleic, lino
  • Aromatic acids which are used herein are represented by the general formula: Where R is a hydrocarbon or essentially hydrocarbon radical containing at least four aliphatic carbon atoms, n is an integer of from one to four, Ar is a polyvalent aromatic hydrocarbon radical having a total of up to fourteen carbon atoms in the aromatic nucleus, each X is independently a divalent sulfur or oxygen group, p is zero or an integer of from one to six and m is an integer of from one to four, with the proviso that R and n are such that there is an average of at least eight aliphatic carbon atoms provided by the R substituents for each acid molecule represented.
  • aromatic radicals represented by the variable Ar are the polyvalent aromatic radicals derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the like.
  • the radical represented by Ar will be a polyvalent radical derived from benzene or naphthalene such as phenylenes and naphthalene, e.g., methylphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylphenylenes, hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, and pentavalent radicals thereof.
  • the R variables are usually hydrocarbon groups, preferably aliphatic hydrocarbon groups such as alkyl or alkenyl radicals.
  • R groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, t-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4-(p-chlorophenyl)-octyl, 2,3,5,-trimethyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized olefins such as polychloroprenes, polyethylenes, propypropylenes, polyisobutylenes, ethylenepropylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like.
  • polymerized olefins such as polychloroprenes, polyethylenes, propypropylenes, polyisobutylenes, ethylenepropylene copoly
  • variable Ar may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than four carbon atoms, hydroxy, mercapto, and the like.
  • R ⁇ is an aliphatic hydrocarbon radical containing at least four carbon atoms
  • a is an integer of from 1 to 3
  • b is 1 or 2
  • c is zero, 1, or 2 and preferably 1, with the proviso that R ⁇ and a are such that the acid molecules contain at least an average of about twelve aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule.
  • Phenols which are used herein include 3,5,5-trimethyl-n-hexyl phenol, n-decyl phenols, cetyl phenols, nonyl phenols, alkylphenyl phenols, resorcinol, octyl catechol, triisobutyl pyrogallol, alkyl alpha naphthol and the like.
  • noncarboxylic acids which may be used in preparing the antifoulants are the organic sulfur acids, e.g., oil-soluble sulfonic acids, includiing the synthetic oil-soluble sulfonic acids.
  • oil-soluble sulfonic acids are represented by the general formulae: R x - T - (SO3H) y I R ⁇ - (SO3H) r II
  • T is a cyclic nucleus of th e mono- or polynuclear type including benzenoid, cycloaliphatic or heterocyclic neuclei such as a benzene, naphthalane, anthracene, 1,2,3,4-tetrahydronaphthalene, thianthrene, cyclopentene, pyridine or biphenylnucleus and the like.
  • T will represent an aromatic hydrocarbon nucleus, especially a benzene or naphthalene nucleus.
  • variable R in the radical R x can be, for example, an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, an aralkyl group, or other hydrocarbon or essentially hydrocarbon groups, while x is at least 1 with the proviso that the variables represented by the group R x are such that the acids are oil-soluble.
  • the groups represented by R x should contain at least about eight aliphatic carbon atoms and preferably at least about twelve aliphatic carbon atoms.
  • x will be an integer of 1-3.
  • the variables 4 and y in Formulae I and II have an average value of one to about four per molecule.
  • variable R ⁇ in Formula II is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hydrocarbon radical.
  • R ⁇ is an aliphatic radical, it should contain at least about 8 to about 20 carbon atoms and where R ⁇ is an aliphatic substituted-cycloaliphatic group, the aliphatic substituents should contain about 4 to 16 carbon atoms.
  • R ⁇ are alkyl, alkenyl, and alkoxyalkyl radicals and aliphatic-substitued cycloaliphatic radicals wherein the aliphatic substituents are alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc.
  • the cycloaliphatic radical will be c cycloalkane nucleus or a cycloalkene nucleus such as cyclopentane, cyclohexane, cyclohexene, cyclopentene, and the like.
  • R ⁇ are cetyl-cyclohexyl, laurylcyclohexyl, cetyl-oxyethyl and octadecenyl radicals, and radicals derived from petroleum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized mono- and diolefins containing from about 1 to 8 carbon atoms per olefin monomer unit.
  • the groups T, R, and R ⁇ in Formulae I and II can also contain other substituents such as hydroxy, mercapto, halogen, nitro, amino, nitroso, carboxy, lower carbalkoxy, etc., as long as the essentially hydrocarbon character of the groups is not destroyed.
  • the sulfonic acids which are preferred for use herein include alkyl sulfonic acids, alkaryl sulfonic acids, aralkyl sulfonic acids, dialkyl sulfonic acids, dialkylaryl sulfonic acids, aryl sulfonic acids, e.g. ethylsulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid and more complex sulfonic acid mixtures such as mohogany sulfonic acids and petroleum sulfonic acids.
  • Fuerther, illustrative examples of the sulfonic acids are mahogany sulfonic acids, petrolatum sulfonic acids, mono- and poly-wax-substituted naphthalene sulfonic acids, cetylchlorobenzenesulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycaprylbenzene sulfonic acids, dicetyl thianthrene sulfonic acids, di-lauryl betanaphthol sulfonic acids, dicapryl nitronaphthylene sulfonic acids, paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chloro-substitute
  • Organic phosphorus acids used herein are characterized by at least one oil-soubilizing group attached directly to phosphorus via a carbon atom, e.g., oil-soluble phosphoric, phosphinic and phosphonic acids including the oil-soluble thiophosphoric, thiophosphinic and thiophosphonic acids.
  • Preferred phosphorus acids are the alkyl- and dialkyl phosphoric and phosphonic acids and those prepared by reacting olefins with phosphorus sulfides (e.g., phosphorus pentasulfide). Steam-treated reaction products of phosphorus pentasulfide and polyolefins, such as polyisobutylene and polypropylene, are also useful.
  • Overbase complex types which are the preferred antifoulants of the invention are the following (wherre M represents Mg, Ca, Ba, Sr or Mn): MO/M carboxylate MCO3/M carboxylate MO/M noncarboxylate MCO3/M noncarboxylate
  • carboxylate and noncarboxylate refers, as stated supra, to the partial reaction product of a base of the desired metal and a carboxylic or noncarboxylic acid complexing agent which afford a complex believed to be a dispersion of finely divided metal oxide (or carbonate) associated with the metal carboxylate or metal noncarboxylate.
  • more than one oxide or carbonate may be associated with a complexing agent to afford complexes, for example, of the type MO/MCO3/M noncarboxylate, and more than one complexing agent may be combined with an oxide or carbonate to afford complexes, for example, of the type MO/M carboxylate/M noncarboxylate and MCO3/M carboxylate/M noncarboxylate.
  • mixed overbase complexes are included in the present invention, e.g. MO/M carboxylate with MO/M noncarboxylate, MCO3/carboxylate with MCO3 noncarboxylate, MO/M carboxylate with MCO3/noncarboxylate, etc.
  • Species which are intended to be excluded from the above-described general types of complexes are CaCO3/Ca sulfonate which is disclosed and claimed in copending application Serial No. , filed , of common ownership herewith and the mixed complex MgO/Mg carboxylate with MgCO3/Mg noncarboxylate which is disclosed and claimed in copending application Serial No. , filed , of common ownership herewith.
  • MO/M carboxylate MCO3/M sulfonate MO/M sulfonate
  • the most preferred complexes are the following: MgO/Mg fatty acid carboxylate (especially "tall oil” fatty acid carboxylates) MgO/Mg benzesulfonate or dodecylbenzenesulfonate MgCO3/Mg fatty acid carboxylate MgCO3/Mg benzenesulfonate or dodecylbenzenesulfonate CaO/Ca fatty acid carboxylate CaO/Ca benzenesulfonate or dodecylbenzenesulfonate CaCO3/Ca fatty acid carboxylate MgO/Mg fatty acid carboxylate + MgO/Mg benzenesulfonate or dodecylbenzene sulfonate MgCO3/Mg fatty acid carboxylate + MgCO3/Mg benzenesulfonate or dodecylbenzenesulfonate MgO/McCO3/Mg fatty acid
  • the mixed overbase complexes e.g., MgO/Mg fatty acid carboxylate + MgO/M g benzenesulfonate, are in a weight ratio to each other of from about 0.25/10 to about 10/0.25.
  • the reaction of metal base and acid affords a product which undergoes decomposition to afford minute particle of metal oxide or carbonate in association with the metal salt of the acid.
  • the minute particles immediately become suspended and stabilized by the metal salt of the acid.
  • the particles of metal oxide or metal carbonate are of a size no greater than about 2 microns in diameter, for example not greater thaan about 1 micron but, preferably, no greater than about 0.1 micron and, especially, should be less than 0.1 micron in diameter.
  • the amount of antifoulant which is used to inhibit fouling in a fouling area will vary, depending on the environment of the area, the degree of fouling and the specific antifoulant used. In general, an amount of antifoulant is used which is effective to inhibit fouling in an area. Accordingly, there may be used an amount of from about 5 ppm to about 1000 ppm or more based on the weight of the hydrocarbon stream, depending on specific circumstances. Ordinarily, from about 25 ppm to about 500 ppm are effective, especially from about 50 to 300 ppm.
  • the best mode contemplated of carrying out the present invention is to add, to appropriate fouling areas of an oil refining process, a gas refining process or petro-chemical refining process, an effective fouling inhibiting amount as set forth above, of the antifoulant compositions herein-described.

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EP87307863A 1986-09-30 1987-09-04 Zusammensetzungen zur Verhinderung von Inkrustierungen und deren Verwendungen Withdrawn EP0267674A1 (de)

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US91345086A 1986-09-30 1986-09-30
US913450 1986-09-30

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EP (1) EP0267674A1 (de)
JP (1) JPS6397679A (de)
KR (1) KR880004067A (de)
CN (1) CN87106634A (de)
AU (1) AU578567B2 (de)
BR (1) BR8704779A (de)
DE (1) DE267674T1 (de)
ES (1) ES2008061A4 (de)

Cited By (14)

* Cited by examiner, † Cited by third party
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US5851377A (en) * 1997-03-10 1998-12-22 The Lubrizol Corporation Process of using acylated nitrogen compound petrochemical antifoulants
WO1998055563A3 (en) * 1997-06-05 1999-03-18 Atf Resources Inc Method and apparatus for removing and suppressing coke formation during pyrolysis
US5954945A (en) * 1997-03-27 1999-09-21 Bp Amoco Corporation Fluid hydrocracking catalyst precursor and method
US7416654B2 (en) 2004-03-09 2008-08-26 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7935246B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7935247B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7951758B2 (en) 2007-06-22 2011-05-31 Baker Hughes Incorporated Method of increasing hydrolytic stability of magnesium overbased products
US8518238B2 (en) 2009-04-09 2013-08-27 General Electric Company Processes for inhibiting fouling in hydrocarbon processing
US11697756B2 (en) 2019-07-29 2023-07-11 Ecolab Usa Inc. Oil soluble molybdenum complexes as high temperature fouling inhibitors
US11767596B2 (en) 2019-07-29 2023-09-26 Ecolab Usa Inc. Oil soluble molybdenum complexes for inhibiting high temperature corrosion and related applications in petroleum refineries
US11999915B2 (en) 2020-07-29 2024-06-04 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes as high temperature fouling inhibitors
US12006483B2 (en) 2020-07-29 2024-06-11 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes for high temperature naphthenic acid corrosion inhibition
WO2025068150A1 (en) * 2023-09-26 2025-04-03 Totalenergies Onetech Additive composition comprising a mixture of carboxylic acids as scale inhibitor in petroleum products and/or oil production installation
US12365845B2 (en) 2024-04-25 2025-07-22 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes as high temperature fouling inhibitors

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267673A1 (de) * 1986-09-30 1988-05-18 Petrolite Corporation Zusammensetzungen von gemischten überbasischen Komplexen zur Verhinderung von Inkrustierungen und deren Verwendung
US5919741A (en) * 1998-01-20 1999-07-06 The Lubrizol Corporation Overbased carboxylate gels
CN102399621B (zh) * 2011-10-09 2013-11-20 上海宝钢废旧油处理有限公司 一种防垢剂及其在废机油加工中的应用
KR102374179B1 (ko) * 2017-05-09 2022-03-14 카타야마 케미칼, 인코포레이티드 석유 프로세스에 있어서의 열 교환기의 오염 방지 방법
EP3795660B1 (de) * 2019-09-17 2022-03-09 Infineum International Limited Bewuchshemmerverfahren für raffinerie

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328284A (en) * 1965-01-06 1967-06-27 Petrolite Corp Oxyalkylate-sulfonate hydrocarbon inhibitor
US4024051A (en) * 1975-01-07 1977-05-17 Nalco Chemical Company Using an antifoulant in a crude oil heating process
US4347147A (en) * 1980-09-04 1982-08-31 Nalco Chemical Company Process for preparing overbased magnesium sulfonates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4663018A (en) * 1985-06-27 1987-05-05 Betz Laboratories, Inc. Method for coke retardant during hydrocarbon processing
US4756820A (en) * 1985-09-06 1988-07-12 Betz Laboratories, Inc. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing
US4775458A (en) * 1986-12-18 1988-10-04 Betz Laboratories, Inc. Multifunctional antifoulant compositions and methods of use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328284A (en) * 1965-01-06 1967-06-27 Petrolite Corp Oxyalkylate-sulfonate hydrocarbon inhibitor
US4024051A (en) * 1975-01-07 1977-05-17 Nalco Chemical Company Using an antifoulant in a crude oil heating process
US4347147A (en) * 1980-09-04 1982-08-31 Nalco Chemical Company Process for preparing overbased magnesium sulfonates

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851377A (en) * 1997-03-10 1998-12-22 The Lubrizol Corporation Process of using acylated nitrogen compound petrochemical antifoulants
US5954945A (en) * 1997-03-27 1999-09-21 Bp Amoco Corporation Fluid hydrocracking catalyst precursor and method
US6274530B1 (en) 1997-03-27 2001-08-14 Bp Corporation North America Inc. Fluid hydrocracking catalyst precursor and method
WO1998055563A3 (en) * 1997-06-05 1999-03-18 Atf Resources Inc Method and apparatus for removing and suppressing coke formation during pyrolysis
US6228253B1 (en) 1997-06-05 2001-05-08 Zalman Gandman Method for removing and suppressing coke formation during pyrolysis
US7935247B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7425259B2 (en) 2004-03-09 2008-09-16 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7935246B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7416654B2 (en) 2004-03-09 2008-08-26 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7951758B2 (en) 2007-06-22 2011-05-31 Baker Hughes Incorporated Method of increasing hydrolytic stability of magnesium overbased products
US8518238B2 (en) 2009-04-09 2013-08-27 General Electric Company Processes for inhibiting fouling in hydrocarbon processing
US11697756B2 (en) 2019-07-29 2023-07-11 Ecolab Usa Inc. Oil soluble molybdenum complexes as high temperature fouling inhibitors
US11767596B2 (en) 2019-07-29 2023-09-26 Ecolab Usa Inc. Oil soluble molybdenum complexes for inhibiting high temperature corrosion and related applications in petroleum refineries
US11999915B2 (en) 2020-07-29 2024-06-04 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes as high temperature fouling inhibitors
US12006483B2 (en) 2020-07-29 2024-06-11 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes for high temperature naphthenic acid corrosion inhibition
WO2025068150A1 (en) * 2023-09-26 2025-04-03 Totalenergies Onetech Additive composition comprising a mixture of carboxylic acids as scale inhibitor in petroleum products and/or oil production installation
US12365845B2 (en) 2024-04-25 2025-07-22 Ecolab Usa Inc. Phosphorous-free oil soluble molybdenum complexes as high temperature fouling inhibitors

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ES2008061A4 (es) 1989-07-16
JPS6397679A (ja) 1988-04-28
BR8704779A (pt) 1988-05-17
KR880004067A (ko) 1988-06-01
AU7904587A (en) 1988-03-03
CN87106634A (zh) 1988-06-15
AU578567B2 (en) 1988-10-27

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