Classifications

• • 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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F15/00—Other methods of preventing corrosion or incrustation
  • C23F15/005—Inhibiting incrustation
• • 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.
• 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 fouling 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 combination 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, ga and petrochemicals and in the thermal processing of other organic materials.
• the invention relates to the use of colloidally dispersed overbase complex calcium antifoulants in oil refineries, gas plants and petrochemical refineries. More particularly, the invention relates to an overbase complex of calcium carbonate with a sulfonic acid complexing agent and to its use as an antifoulant in oil, petrochemical and gas refining operations.
• 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 feed streams.
• Overbased oil-stable, fluid dispersion 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 petroleum sulf onates 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.
• 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 in fouling caused by high temperature hydrocarbon streams.
• 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.
• Various commercial antifoulants are also mentioned, including ethoxylated catechol, polyhydroxyl ethoxylated amines, combination of a metal deactivator, a phenolic amine and a succinimide, and a combination of morpholine and a water soluble salt of an ethoxylated imidazoline.
• U. S. 4,129,589 discloses the preparation of overbased magnesium salts of sulfonic acids which are useful as lubricant additives.
• U. S. 4,163,728 discloses the preparation of a stable, fluid organomagnesium complex dispersion useful as an acidic neutralization additive for lubricating oils. The compounds disclosed are overbased.
• 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. 4,129,589 discloses the preparation of overbased magnesium salts of sulfonic acids which are useful as lubricant additives.
• U. S. 4,163,728 discloses the preparation of a stable, fluid organomagnesium complex dispersion useful as an acidic neutralization additive for lubricating oils. The compounds disclosed are overbased.
• U. S. 4,293,429 disclose
• 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 mnesium oxide having a small particle size.
• U. S. 4,474,710 discloses the preparation of overbased mixtures of magnesium 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 calcium carbonate and a sulfonic acid complexing agent and i ts use in the inhibition of fouling, particularly high temperature fouling, e.g., 500-1200°F., in refining processes.
• 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.
• overbases comprise dispersions of salts formed by contacting an acidic material with a basically reacting metal compound, e.g., a metal hydroxide.
• a basically reacting metal compound e.g., a metal hydroxide.
• they comrpise "polymeric salts”. It is believed that neither theory is incorrect but that neither is completely correct.
• the preparation of an "overbased” material results in an "overbase complex" of calcium carbonate with a sulfonic acid dispersant or stabilizer (i.e., "complexing agent"). The nature of the complex so-formed is not completely under stood.
• an "overbase complex” is a complex of calcium carbonate and the calcium salt of a sulfonic acid "complexing agent".
• the overbase complex contains a stoichiometric excess of Ca, relative to the number of equivalents of sulfonic acid complexing agent which is reaced with a basic aclcium compound to afford the complex, based on the normal stoichiometry of a calcium base and a sulfonic 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 or acids present.
• an oil dispersion of an overbased calcium salt containing two equivalents of acid and twenty equivalents of calcium would have a metal ratio of 10 (i.e., 20 ⁇ (1+1)).
• calcium for example, is regarded as having two equivalents per atomic weight; calcium oxide (CaO) and calcium hydroxide (Ca(OH)2), two equivalents per mole.
• Sulfonic acids are regarded as having one equivalent of acid per acidic hydrogen or acid group.
• a monosulfonic acid or its equivalent derivatives such as esters and ammonium and metal salts, have one equivalent per mole of acid, ester or salt;
• a disulfonic acid or equivalent derivative has two equivalents per mole.
• the basically reacting calcium compounds, such as the oxides and carbonates, have two equivalents per mole (i.e., two equivalents per atomic weight of metal).
• the complex antifoulants of the invention are overbase complexes of calcium carbonate and the calcium salt of at least one sulfonic acid complexing agent.
• 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 capable of forming a stable dispersion in oil.
• one method for preparing the antifoulants of the present invention is to form a mixture of a base of calcium, e.g., Ca(OH)2, a sulfonic acid complexing agent 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. while introducing CO2 whereby there is afforded the overbase complex of calcium carbonate associated with the calcium salt of the sulfonic acid.
• Complexing agents which are used in the present invention are organic sulfur acids. Oil-soluble derivatives of these organic acids, 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), can be utilized in lieu of or in combination with the free acids. When reference is made to the acid, its equivalent derivatives are implicitly included unless it is clear tha t only the acid is intended.
• T is a cyclic nucleus of the mono- or polynuclear type including benzenoid, cycloaliphatic or heterocyclic neuclei such as a benzene, naphthalene, 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 r and y 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 alioxyalkyl radicals and aliphatic-substituted cycloaliphatic radicals wherein the aliphatic substituents are alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc.
• the cycloaliphatic radical will be a 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, 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 mahogany sulfonic acids and petroleum sulfonic acids.
• 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 beta-naphthol 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-substituted paraffin
• Witco C300 overbased calcium carbonate/calcium sulfonate was tested to demonstrate its usefulness as an antifoulant. It is believed to be an overbased dispersion of CaCO3 in Ca dodecylbenzene sulfonate and Ca didodecylbenzene sulfonate.
• a fouling problem was simulated in the laboratory in a Refinery Antifoulant Test Apparatus (RAFT). It is designed to simulate a heat exchanger tube exposed to a hydrocarbon media. Deposits accumulate on the electrically heated surface of a probe in a fashion similar to an actual system. Fluid velocity is simulated by rotating a hollow cylinder filled with the test fluid around the heated probe. The apparatus is capable of achieving 1000°F. probe temperature, 350-500°F. oil temperature and 350 psi. The oil is introduced into the autoclave under conditions in which the gas exposure is controlled. The probe operates with a constant current applied which produces a heat flux condition. Therefore, as fouling deposit accumulates on the probe, the surface temperature of the probe increases and is an in-situ measure of deposit formation.
• RAFT Refinery Antifoulant Test Apparatus
• a fouling factor is assigned after each run.
• the foling factor is calculated as the change in temperature of the probe over a period of time.
• the initial probe temperature divided by the final probe temperature i.e., ⁇ T
• a zero fouling factor indicates no fouling.
• the RAFT was used to determine effectiveness of Witco C300 overbased calcium carbonate/calcium sulfonate.
• the control run was repeated except that 500 ppm of the Witco C300 material was introduced into the RAFT. After 20 hours, the fouling factor was 30, a reduction, over the untreated control run, of 81%.
• the minute particles immediately become suspended and stabilized by the metal salt of the acid.
• the particles of calcium carbonate are of a size no greater than about 2 microns in diameter, for example no greater than about 1 micron but, preferably, are 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 about 300 ppm.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• Metallurgy (AREA)
• Materials Engineering (AREA)
• Lubricants (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Detergent Compositions (AREA)
• Fats And Perfumes (AREA)

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• 1987
  • 1987-09-04 DE DE198787307862T patent/DE267673T1/de active Pending
  • 1987-09-04 ES ES87307864T patent/ES2008054A4/es active Pending
  • 1987-09-04 EP EP87307862A patent/EP0267673A1/de not_active Withdrawn
  • 1987-09-16 BR BR8704778A patent/BR8704778A/pt unknown
  • 1987-09-25 JP JP62239122A patent/JPS63146988A/ja active Pending
  • 1987-09-25 KR KR870010638A patent/KR880004069A/ko not_active Application Discontinuation
  • 1987-09-28 AU AU79046/87A patent/AU577983B2/en not_active Ceased
  • 1987-09-30 CN CN198787106648A patent/CN87106648A/zh active Pending

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