JPS6397679A - Antistaining composition and its use - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Background of the Invention Processes involved in the refining of oil, gas and petrochemicals;
For example, during reforming, hydroforming, rejuvenation, hydrocracking, isomerization, extraction, cracking, fractionation, hydrorefining, desalination, etc., hydrocarbon streams are exposed to relatively high temperatures. These temperatures are most commonly achieved through the use of heaters and heat exchangers, among which are hydrocarbon feedstocks,
The products and intermediate products are in intimate contact with the heated surface. These conditions are known to promote the formation of fouling deposits that can severely limit purification capacity and flow rates.

Fouling occurs in many areas of refining operations, such as crude oil unit preheat exchangers, hydrodesulfurizers, fluid catalytic cracking units, overhead condensers, reforming reboilers, coking ovens, vacuum columns, and alkylation reboilers. .

Although problems with fouling are most severe in the oil refining industry, the problem is also persistent in gas plant refining operations and in petrochemical processes involving, for example, ethylene, styrene, butadiene, isoprene, acrylonitrile, and other chemicals. That's a problem.

The formation of fouling deposits that occurs with thermally initiated physical or chemical modification of hydrocarbons and derivatives occurs when the hydrocarbon or derivative phase is held at elevated temperatures in processing equipment on surfaces, metallic or otherwise. Observed whenever exposed to. Deposits of this nature are known to substantially reduce the thermal conductivity properties of the device in which they are deposited, and their removal is generally quite difficult. As a result, operating and maintenance costs associated with the formation and removal of such deposits are often considerable. For this reason, considerable effort has been devoted to attempting to solve the problem of stains, and as a result, numerous methods have been proposed for preventing stain buildup and removing stain deposits. . Although these methods have met with varying degrees of success, essential problems remain unsolved.

Fouling deposits resulting from physical and/or chemical modification of hydrocarbon feedstocks, initiated at elevated operating temperatures, consist of sticky, tarry, polymeric or carbonaceous materials. The most common fouling deposits are usually divided into inorganic salts, corrosion products, metal-organic compounds, organic polymers, and coke.

Inorganic salts, such as sodium chloride, calcium chloride, and magnesium chloride, are likely introduced into the working system by raw feedstocks. Metal-organic compounds may also be present in the feedstock or may be formed on heat-conducting surfaces by combining with corrosion products or other metals introduced into the system. Formation of organic polymers most often occurs by reaction of unsaturated hydrocarbons.

Coked greens are often accompanied by the formation of hot spots caused by the accumulation of dirt deposits. Ultimately, in these processes the metal and organic elements of the soil deposit can be described as interacting with each other.

Several methods have been used to reduce the accumulation of fouling materials in processing equipment. Some methods polish or coat processing equipment to reduce its affinity for contaminants. However, it is practically impossible to prevent the formation of dirt deposits by covering metal surfaces with a permanent protective coating without loss of processing efficiency due to loss of heat transfer capacity due to the coating itself. be.

Another method that does not require the expense of coating the processing equipment and does not involve loss of heat transfer capacity is to coat the hydrocarbon feed material with a coating that either prevents the formation of fouling material or smuggles fouling material into the processing equipment. Adding chemicals that have the effect of preventing A number of compositions have been suggested for the purpose of preventing or reducing the effects of soil deposit formation on processing equipment, none of which are considered to be completely successful.

FIELD OF THE INVENTION The present invention relates to novel antifouling compositions and the use of said compositions for preventing fouling of equipment used in the refining of crude oil, gas and petrochemicals, and in the thermal processing of other organic materials. . The present invention relates more particularly to the use of colloidally dispersed overbased complex antifouling agents in oil refineries, gas plants and petrochemical refineries. The invention more particularly relates to overbase complexes of metal oxides and/or carbonates with at least one complexing agent and their use as antifouling agents in petroleum, petrochemical and gas refining operations. Regarding.

BACKGROUND OF THE INVENTION A wide variety of antifouling agents have been used to prevent fouling associated with the degradation of crude oil and refined oil, gas, and petrochemical feed streams. A partial but representative list of patents relating to anti-soiling compositions and uses thereof is set forth below.

2.895.913 4.410,4183
．． 384.130 4.425.2233.
492.219 4.431.5143.5
48.097 4,440.8253.68
8.856 4,444.8493.77
2.182 4.458.5284.024
,051 4.469.5884,107.
Q30 4.510,0414.200.5
18 4,511.4574.319.0B
3 4,529.5004.397.737
4,552.6434.404.087
No. 4,556.47, these patents describe the use of oil-dispersible magnesium-containing organic compositions in: Lubricating oil (2,895,913)
, amide condensation products from petroleum processing equipment, metal deactivators used in high-temperature petroleum charging feedstocks, mixtures of methacrylate polymers and nitrogen-containing substances, oil-soluble additive copolymers, nitrogen-containing methacrylate polymers, Schiff bases and diarylamines, phosphorus-containing inorganic acids and salts, sulfanilic acid amine salts, polyalkylene amines, sulfonates, mixtures of amines and phenylhydrazines, poly(oxyalkylene) carbamates, metals such as tin, antimony and germanium, halogens Silicon-containing compounds, mixtures of phosphites and hydrocarbon sulfonic acids, reaction products of polyalkylene amines and hydroxy fatty acids, mixtures of hydroxylamine and organic surfactants, phosphates, mixtures of hydroxylamine and catechol, saturated sulfoxides, phenothiazines and mixtures of phenols, phenothiazines, mixtures of catechol and hydroquinone, phenothiazine dimers, combinations of tin, copper and antimony, mixtures of phenothiazines and hydroxylamines. Additionally, GB Patent Application No. 2017747A describes sodium di-2-ethylhexyl sulfosuccinate as an antifouling agent for petroleum crudes, and GB2021144B describes antifouling agents for hydrocarbon feed stream refinery. Polyalkyleneoxysulfoxy salts are described for the prevention and removal of

Overbased, stable fluid dispersions or "solutions" of complexes containing, for example, magnesium and calcium, and their preparation and use, are well known to those skilled in the art.

“The term overbasic J has historically been used to describe the metal base/acid reaction product in stoichiometric excess of the amount required to form a neutral organic acid salt of this type of base. Frequently used synonyms include "basic,""highlybasic," and "hyperbased."

Many methods are known for producing overbased metal-containing dispersions. Discloses a method for producing a base-rich metal complex;
Representative US patents include the following:

U.S. Pat. No. 2,585,520 discloses the production of highly basic magnesium and calcium petroleum sulfonates useful as lubricating oil additives.

U.S. Pat. No. 2,895,913 discloses the preparation of stable, oil-dispersible, overbased organomagnesium compounds useful as lubricating oil additives.

U.S. Pat. No. 3,057,896 discloses the production of overbased calcium sulfonates useful as lubricating oil additives.

U.S. Pat. No. 3,150.089 discloses stable dispersions of overbased organomagnesium compounds useful as lubricating oil additives.

US Patent No. L829,109 discloses the preparation of overbased organomagnesium complexes useful as lubricant and fuel additives.

U.S. Pat. No. 3,784,536 discloses the preparation of overbased calcium salts of alkenyl succinimides useful as dispersant additives in lubricating oils.

Additionally, U.S. Pat. No. 3,778,835 discloses detergent-dispersant compositions for use as antifouling agents with soils caused by hot hydrocarbon streams.

Such compositions include sulfonates, especially the neutral and basic metal salts of benzenesulfonic acid, the neutral and basic metal salts of phosphonic and thiophosphonic acids, fenates and carboxylates and carboxylic acid salts. Neutral and basic salts of phenate salts, alkenyl succinimides,
There are naphthenic acids and alkali metal salts of amines and carboxylic acids. Various commercial antifouling agents are also mentioned, such as ethoxylated catechols, polyhydroxyl ethoxylated amines, metal deactivators, combinations of phenolic amines and succinimide, and combinations of water-soluble salts of morpholine and ethoxylated imidacillin.

No. 3,885,737 discloses fluid, overbased organomagnesium complex dispersions useful as additives in lubricating compositions.

U.S. Pat. No. 4,129,589 discloses the preparation of overbased magnesium salts of sulfonic acids useful as lubricant additives.

U.S. Pat. No. 4,183,728 discloses the production of stable, fluid organomagnesium complex dispersions useful as acid-neutralizing additives in lubricating oils. The disclosed compounds are overbased.

US Pat. No. 4,293,429 discloses the production of a base-rich mixture of magnesium carboxylate and magnesium oxide in the form of a fluid dispersion of submicron-sized magnesium oxide. This compound is useful as an additive in lubricants.

U.S. Pat. No. 4,295,981 discloses overbased magnesium carbonate useful as a lubricating oil additive.

US Pat. No. 4,298,482 describes the preparation of overbased mixtures of magnesium salts and magnesium hydroxide in the form of very small particle dispersions. This overbased material is useful as an acid neutralizer in lubricating oils and fuels.

US Pat. No. 4,347,147 discloses the production of magnesium sulfonates and oxides with small particle sizes.

U.S. Pat. No. 4,474,710 discloses the preparation of dispersions of overbased mixtures of magnesium hydroxide or carbonate in liquid magnesium sulfonate dispersants. This material is useful as a lubricant additive.

None of the above-mentioned patents disclose the use of overbased metal complexes as described in the present invention to alleviate the fouling problems associated with purification operations.

Among the above-mentioned patents, U.S. Patent No. 3.8B5.137;
The disclosures of Nos. 4.183.728, 4.293.429 and 4.298.482 relate to the state of the art and to the description of the preparation of overbased metal complexes in the form of dispersions. Particularly useful. The disclosures of these patents are therefore incorporated by reference into the present invention with respect to the description of the preparation and composition of overbased metal compounds. Specifically, column 1 of U.S. Patent No. 8,885,737.
~9, and column 1 of U.S. Pat. No. 4.16L728.
~4, columns 1-3 of U.S. Patent No. 4.293.429
, and columns 1-- of U.S. Pat. No. 4,298,482.
4 is similarly incorporated into the present invention as reference content.

SUMMARY OF THE INVENTION The present invention provides novel antifouling compositions which are overbased complexes consisting of a stable, colloidal dispersion of fine particles of a metal salt, such as a metal oxide or carbonate, and a complexing agent. , and dirt during the refining process, especially 500-1200"l
” relates to the use of anti-stain compositions in preventing stains at high temperatures.

DETAILED DESCRIPTION OF THE INVENTION As explained above, fouling prevention in oil, gas and petrochemical refining has been a particularly troublesome problem.

This problem is complicated not only because of the nature of the fouling material, but also because different areas of the refining operation present different environments, different feedstocks, and different targets.

Fouling problems in one area of the refinery may not necessarily correspond to antifouling treatments for different areas of the refinery. Therefore, treatment in refining operations must be divided into units, and it is necessary to clarify the characteristics of dirt specific to each unit and treat it appropriately.

The use of antifouling chemicals in petroleum refineries is of particular importance in the following areas:

1. Addition of an antifouling agent to the raw crude oil stream after desalination operations but before entering the crude unit, i.e., to the desalted processing stream that is entering the preheating train.

2. Addition of antifouling agents to the effluent from the effluent exchanger series (atmospheric resid), ie the atmospheric crude column of the crude oil unit.

3. Addition of antifouling agents to the reactor inlet and outlet streams to the hydrotreating and hydroprocessing units.

4. Addition of antifouling agents to the effluent (bottom oil) from atmospheric crude oil columns, including pump circulation circuits, and to gas and oil vacuum furnaces and columns.

5. Addition of antifouling agents to the feed to the coking oven (delayed or fluidized) and to the coking oven itself, as well as to the transfer lines and pump circulation circuits fitted to the coking oven.

B. Addition of antifouling agent to the effluent from the main purification column of the alkylation unit before entering the reboiler and the reboiler pump circuit. Antifouling agents must also be added to the boiler itself.

7. Feed to the preheater of the fluid catalytic cracking unit, and from the cracking unit to the slurry exchange equipment, including the bottom oil from the main fractionator and pump circulation circuit and from the pump circulation circuit of the catalytic cracking unit. Addition of antifouling agents to the effluent.

8. Addition of antifouling agents to the visbreaking unit furnace preheater and feed and to the effluent from the visbreaking unit main rectification column.

Each of the above areas of a refinery operates in a unique manner depending on the specific environment of each area. The environment in each area does not necessarily have the same characteristics as other areas of the refinery.

The following outlines examples of important units in petroleum refineries that require the addition of antifouling chemicals.

Crude oil unit preheating exchanger, hydrogen refining equipment, crude oil unit vacuum residual oil exchanger, hydrocracking equipment, crude oil unit vacuum distillation heater and residual oil, reboiler, fluid catalytic cracking preheating, hydrogen desulfurization equipment, heat exchanger, fluid catalytic Cracking Slurry Pump Circulation, Fluid Catalytic Cracking Furnace, High Temperature Separator, Derate Coking Device, Pump Circulation Circuit, Fluid Coking Device, Processing Flow Pipe Visbreaking Device, According to the present invention, M g SCas Bas S
At least 1 oxide or carbonate of r or Mn
8 with a complexing agent, a product can be obtained which is an overbased complex of an oxide or carbonate of a metal with a metal salt of a complexing agent of extremely fine, preferably submicron particle size. discovered.

Theoretically, the presence of a complexing agent during the production of metal oxides or carbonates prevents the metal oxide or carbonate microparticles from agglomerating, allowing the microparticles to react with the dispersant used in the reaction. during and after which it is possible to remain stably dispersed in the hydrocarbon flow.

The exact nature of the excess base is unknown. - theory suggests that these are dispersions of salts formed by contacting acidic substances with metal compounds that react as bases, such as metal hydroxides. The - theory also suggests that these are composed of ``salt-type combinations''. Neither theory is wrong, but neither is completely correct.

According to the invention, as a result of producing an "overbased" substance,
It is believed that an "overbased complex" of the metal oxide or carbonate and the organic acid dispersant or stabilizer (ie, the "complexing agent") is formed. The nature of the complex thus formed is not completely understood.

As used herein, therefore, an "overbased complex" is a complex of an oxide or carbonate of Mgs Ca, Bas Sr or Mn with a metal salt of an organic acid "complexing agent". . A base-excessive complex is a stoichiometric excess based on the normal stoichiometry of a particular metal base and acid relative to the number of equivalents of the acid complexing agent that reacts with the basic metal compound to form the complex. Contains metals. For example, "neutral" or "positive" metal salts of acids are characterized by a metal to acid equivalent ratio of l=1, whereas overbased salts are characterized by a much higher ratio, e.g. 1.1:1. ．． 2: l.

5: 1.10: 1.15: 1.20: 1.
30: Characterized by l, etc. The term "metal ratio" refers to (a) the equivalents of metal to acid in the overbased salt, to (
b) Used to indicate the ratio of the number of equivalents expected to be present in a normal salt based on the normal stoichiometry of the metal contained in the salt and the acid present in the salt. Therefore, the metal ratio of an overbased magnesium salt oil dispersion containing 2 equivalents of acid and 20 equivalents of magnesium is 10 (i.e. 20
+ (1+1) ).

In this specification, for example, magnesium is
Magnesium oxide (Mg
O) and magnesium hydroxide (Mg (OH)2) are 1
It is considered to have 2 equivalents per mole. Organic acids are considered to have one equivalent of acid per acidic hydrogen or acid group. Thus, monocarboxylic or monosulfonic acids or equivalent derivatives thereof, such as esters and ammonium salts and metal salts, have 1 equivalent per mole of acid, ester or salt, and disulfonic or dicarboxylic acids or equivalent derivatives. has 2 equivalents per mole. Metal compounds that react as bases, such as oxides and carbonates of calcium, barium and manganese, are
It has 2 equivalents per mole (ie 2 equivalents per atomic weight of metal).

The complex antifouling agent of the present invention is an overbased complex of a metal oxide and/or carbonate and a metal salt of at least one complexing agent. Therefore, it can generally be expressed as shown in the table below.

Table 1 Metal oxides/carbonates Mg s Ca s Ba s S r, Mn oxides and 10 Carboxylic acids/or carbonates Mg s ca s Ba SS r sMn oxides + non-carboxylic acids M g SCa SB
a s S r sMn carbonate dry
Due to the need for a better terminology for non-carboxylic acids, "carboxylate" refers to the reaction product of a metal base and an organic carboxylic acid having the general formula R-COOH (where R is a hydrocarbon group). "Non-carboxylate" refers to the reaction product of a metal base and an organic acid other than an organic carboxylic acid, that is, an acid that is a "non-carboxylic acid," such as an organosulfur acid and an organophosphorus acid. That's it. Non-carboxylate materials have a substantially higher dispersing ability than carboxylate salts, which have a higher stabilizing ability.

The role of complexing agents in making and using the antifouling agents of this invention is unclear. As mentioned earlier,
Some function as stabilizers, while others function as dispersants. It is certain that some have both functions, and others have other unknown functions. What is clear, however, is that in order to obtain the complex antifouling agents of the invention, the presence of at least one complexing agent during the preparation of the complex is essential. It is also clear that suitable antifouling agents are characterized by the presence of non-carboxylate salts, especially sulfonate salts.

The overbased complexes used in the present invention can be prepared according to the prior art, as long as the overbased complexes obtained are in the form of fine particles, preferably submicron particles, which form stable dispersions in petroleum. It can be produced by any known method for producing overbased salts. Accordingly, a preferred method of making the antifouling agents of the present invention involves forming a mixture of a base of the desired metal, e.g. Mg(OH)2, a complexing agent, a fatty acid such as tall oil fatty acid, and a non-volatile diluent. do. The amount of complexing agent used here is much lower than the amount schematically required to react with the hydroxide. Heating the mixture to a temperature of about 250-350°C results in a superbased complex of metal oxide and metal salt of fatty acid. Metal carbonate/complexing agent overbased complexes are
It is prepared in the same manner as described above, except that carbon dioxide is bubbled through the initial reaction mixture.

The above-described method for preparing the overbased complexes of the present invention is described in detail in US Pat. No. 4,183,728, which is incorporated herein by reference.

In this patent, for example, a mixture of Mg (OH) 2 and a carboxylic acid complexing agent is heated to a temperature of about 280-330°C in a suitable non-volatile diluent.

The complexing agents used in the present invention are carboxylic acids, phenols, organophosphorus acids, and organosulfur acids. Examples of these include those currently used in the production of base-excess materials (
For example, U.S. Pat.
No. 5,910 and No. 2,616,904), which constitute an art-recognized family of acids. Carboxylic acids, phenols, organophosphorus acids, and essentially oil-soluble organosulfur acids, especially oil-soluble sulfonic acids, are particularly useful.

Oil-soluble derivatives of these organic acidic substances, such as their metal salts, ammonium salts, and esters (particularly esters with lower aliphatic alcohols having up to 6 carbon atoms, such as lower alkanols), can be used in place of the free acids or It can also be used in combination with acids. When referring to an acid, the corresponding derivatives of the acid are also implicitly included, unless it is clear that only the acid is meant.

Suitable carboxylic acids that can be used in the present invention include:
Aliphatic carboxylic acids, cycloaliphatic carboxylic acids 1, and aromatic-basic carboxylic acids and aromatic polybasic carboxylic acids, such as naphthenic acid, alkyl- or alkenyl-substituted cyclopentanoic acid, alkyl- or alkenyl-substituted cyclohexanoic acid, and alkyl- or alkenyl-substituted cyclohexanoic acid. There are substituted aromatic carboxylic acids. Fatty acids are generally long chain acids having 8 or more carbon atoms, preferably 12 or more carbon atoms. Alicyclic carboxylic acids and aliphatic carboxylic acids may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, α-lylunic 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, dioctylcyclopencune carboxylic acid, myristic acid, dilauryl decahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, balmitic acid, commercially available mixtures of two or more carboxylic acids, such as tall oil fatty acids , rosin acid, etc. Typical acids include saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyl Acids, myristic acid, isoacetic acid, palmitic acid, margaric acid and stearic acid; cycloaliphatic unsaturated monocarboxylic acids, such as human tucarpic acid and sholmubric acid; saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid , glutaric acid, adipic acid, pimelic acid, superic acid, azelaic acid and sebacic acid; cycloaliphatic saturated dicarboxylic acids such as cyclohexanedicarboxylic acid; unsaturated aliphatic monocarboxylic acids such as acrylic acid, crotonic acid, decenoic acid, undecene acids, tridecenoic acid, pentadecenoic acid, oleic acid, linoleic acid and linuric acid; unsaturated dicarboxylic acids such as fumaric acid and maleic acid.

The aromatic acid used in the present invention is represented by the general formula: %Formula %), where R is a hydrocarbon group containing 4 or more aliphatic carbon atoms or a group that is essentially hydrocarbon, and n is I
An integer of ~4, A is a polyvalent aromatic hydrocarbon group having a total of 14 or less carbon atoms in the aromatic nucleus, each X is independently a divalent sulfur or oxygen group, p is 0 or an integer from 1 to G, and m is an integer from 1 to 4, where R and n are selected to have an average of 8 or more aliphatic carbon atoms from the R substituent per each acid molecule. Examples of aromatic groups represented by include benzene, naphthalene, anthracene,
There are polyvalent aromatic groups derived from phenanthrene, indene, fluorene, biphenyl, etc.

Groups generally represented by Ar include benzene or naphthalene, such as phenylene and naphthalene, in particular methylphenylene, ethoxyphenylene, nitrophenylene, isopropylphenylene, hydroxyphenylene, mercaptophenylene, N,N-diethylaminophenylene, chlorophenylene, propoxynaphthylene,
It is a polyvalent group derived from triethylnaphthylene and its trivalent, tetravalent and pentavalent groups.

The R group is usually a hydrocarbon group, preferably an aliphatic hydrocarbon group,
For example, an alkyl or alkenyl group. But R
The group may contain substituents such as phenyl, cycloalkyl (
e.g., cyclohexyl, cyclopentyl, etc.), and non-hydrocarbon groups such as nitro, amino, halo (e.g., chloro, bromo, etc.), lower alkoxy, lower alkylmercapto, oxo-substituted 7i! i (i.e. -0), a thio group (i.e. -S), an intervening group such as -NH-1-〇-1-
8- etc. Examples of RM include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, tocosyl, tetracontyl, t-chlorohexyl, 4-ethoxypentyl, 4-hexekyl, 3-cyclohexyl octyl, 4
-(p-chlorophenyl)-octyl, 2.3.5-
Substitutions derived from trimethyl, 4-ethyl-5-methyloctyl, and polymerized olefins such as polychloroprene, polyethylene, polypropylene, polyisobutylene, ethylene propylene copolymers, chlorinated olefin polymers, ethylene oxide-propylene copolymers, etc. There is a base. Similarly, the Ar group can also contain non-hydrocarbon substituents such as lower alkoxy, lower alkyl mercapto, nitro, halo,
It can contain a wide variety of substituents, such as alkyl or alkenyl groups having less than 4 carbon atoms, hydroxy, mercapto, and the like.

Another group of aromatic carboxylic acids is represented by the following formula: where R' is an aliphatic hydrocarbon group having 4 or more carbon atoms, a is an integer from 1 to 3, b is 1 or 2, C is 0
．． 1 or 2, preferably 1, with R' and a selected such that the acid molecule contains an average of about 12 or more aliphatic carbons per aliphatic hydrocarbon substituent per acid molecule.

The phenolic compounds used in the present invention include 3.5.5-trimethyl-n-hexylphenol, n-decylphenol, zetylenphenol, nonylphenol, alkylphenylphenol, resorcinol, octylcatechol, triisobutylpyrogallol, alkyl- α−
These include naphthol.

Other acids such as phenols (ie, "non-carboxylic acids") that can be used in the preparation of antifouling agents include organic sulfur-based acids such as oil-soluble sulfonic acids (including synthetic oil-soluble sulfonic acids). Suitable oil-soluble sulfonic acids have the general formula: % Formula %. In formula I, T is a cyclic nucleus of mononuclear or polynuclear type, such as a benzenoid, alicyclic nucleus or a heterocyclic nucleus;
For example, benzene, naphthalene, anthracene, 1.2
．． 3.4-tetrahydronaphthalene, thianthrene, cyclopentene, pyridine or biphenyl core. Usually, however, T represents an aromatic hydrocarbon nucleus, in particular a benzene or naphthalene nucleus. The R group in the R8 group is, for example, an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl,
It can be an aralkyl group, or another hydrocarbon or essentially hydrocarbon group, where X is 1 or more, with the proviso that R, the group represented by the group is such that the acid is oil-soluble. . This means that the group represented by Rx contains about 8 or more aliphatic carbon atoms, preferably about 12 or more aliphatic carbon atoms. Generally, X is an integer from 1 to 3. The variables r and y in formulas I and 1 have an average value of 1 to about 4 per molecule.

The R' group in formula (1) is an aliphatic, aliphatic-substituted alicyclic hydrocarbon, or a group that is hydrocarbon in nature.

When R' is an aliphatic group, R' must contain from 8 to about 20 carbon atoms, and when R' is an aliphatic substituted alicyclic group, an aliphatic substituent. is about 4 to 16
Must contain carbon atoms.

Examples of R' include alkyl, alkenyl and aryoxyalkyl groups, and aliphatic substituted alicyclic groups where the aliphatic substituent is alkoxy, alkoxyalkyl, carbalkoxyalkyl, and the like. Generally, the alicyclic group is a cycloalkane or cycloalkene nucleus, such as cyclopentane, cyclohexane, cyclohexene, cyclopentene, and the like. Examples of R' include cetyl-cyclohexyl, laurylcyclohexyl, cetyl-oxyethyl, and octadecenyl groups, and groups derived from petroleum, saturated and unsaturated paraffin waxes, and polyolefins, e.g. 8
There are polymerized monoolefins and diolefins containing 5 carbon atoms. T, R and R in formulas ■ and ■
' group may be substituted with other substituents, such as hydroxy, mercapto,
It can also include halogen, nitro, amino, nitroso, carboxy, lower carbalkoxy, and the like.

Sulfonic acids preferred for use in the present invention include alkylsulfonic acids, alkarylsulfonic acids, dialkylsulfonic acids, dialkylarylsulfonic acids, arylsulfonic acids such as ethylsulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and There are more complex sulfonic acid mixtures, such as mahogany sulfonic acid and petroleum sulfonic acid.

Additionally, specific examples of sulfonic acids include mahogany sulfonic acid, petrolatum sulfonic acid, mono- and poly-wax-substituted naphthalene sulfonic acid, cetylchlorobenzene sulfonic acid, cetylphenol sulfonic acid, cetylphenol disulfide sulfonic acid, cetoxylactam sulfonic acid, , dicetylthianthrene sulfonic acid, dilauryl-β-naphthol sulfonic acid, cicapril nitronaphthylene sulfonic acid, paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetraisobutylene sulfonic acid, tetraamide Examples include renesulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitrosyl-substituted paraffin wax sulfonic acid, petroleum naphthene sulfonic acid, cetylcyclopentyl sulfonic acid, laurylcyclohexyl sulfonic acid, mono- and poly-wax substituted cyclohexyl sulfonic acid.

"Petroleum sulfonic acid (petroleum 5ull'o)
nic acid or pcLrosul'onjc
acld) When the term J is used in the present invention,
It includes some of the well known sulfonic acids derived by conventional methods from petroleum products. Conventional methods of this type are described in U.S. Pat.
No. 2.717.285, No. 2.728.281, No. 2,794.829, No. 2.832.801,
No. 3,225.086, No. 3.337,613, No. 3.351,855, etc. Sulfonic acids falling within the scope of formulas I and II are described in prior U.S. Pat.
．． No. 723,234, No. 2゜723.235, No. 2,
No. 723.23 [1], No. 2.777.874, and other US patents cited in each of these patents. Accordingly, these oil-soluble sulfonic acids are well known in the art and need not be further explained herein.

The organophosphorus acids used in the present invention are characterized by at least one oil-solubilizing group directly bonded to phosphorus via a carbon atom, and include, for example, oil-soluble phosphoric acids, phosphinic acids,
and phosphonic acids, including oil-soluble thiophosphoric acids, thiophosphinic acids, and thiophosphonic acids. Preferred phosphorus-based acids are alkyl- and dialkyl phosphoric acids and phosphonic acids, and acids prepared by reacting olefins with phosphorus sulfide (eg, phosphorus pentasulfide). Steamed reaction products of phosphorus pentasulfide and polyolefins such as polyisobutylene and polypropylene are also useful. Acids of this type are well known and are described in US Pat. No. 2.310.078.
No. 2.316,080, No. 2.310゜091, No. 2.367.488, No. 2.375.315,
No. 2.377.955, No. 2,496.508, No. 2.507,731, No. 2.51[i, No. 119, No. 2,597,750, No. 2.647,889, Second
．． 688. [Disclosed in No. i12 and No. 2,915,517.

Of course, mixtures of the above-mentioned organic acids and their derivatives can be used in the production of the antifouling agents of the invention.

The types of base-excessive complexes (see Table 1) preferred as antifouling agents of the present invention are as follows.

(M represents Mg, Ca, Ba, Sr or Mn.) MO/M carbonate M CO3/ M carbonate MO/M non-carbonate MCO, 7M non-carbonate "carboxylate" or "non-carboxylate" As mentioned above, the term ``is used to refer to a portion of the reaction product of a base of a desired metal with a carboxylic acid or non-carboxylic acid complexing agent, whereby the complex is formed of a metal. It is believed that a dispersion of oxide (or carbonate) particles with a metal carboxylate or a metal non-carboxylate will result.

Of course, it is also possible to use two or more oxides or carbonates together with a complexing agent to obtain complexes of the type MO/MCO3/M non-carboxylate salts, or to combine two or more complexing agents with an oxide or carbonate. Alternatively, it is also possible to obtain complexes of the type MO/M carboxylate/M non-carboxylate and MCO3/M carboxylate/M non-carboxylate in combination with carbonates.

Additionally, the present invention includes mixtures of overbased complexes, such as MO/M carboxylates and MO/M non-carboxylate salts, MC
O3/carboxylate and MCO3 non-carboxylate, MO/
Also included are M carboxylates and MC03/non-carboxylate salts.

Species intended to be excluded from the general class of complexes described above are the Ca CO3/Ca sulfonate salts disclosed and claimed in pending U.S. patent application Ser. and Mg CO3/Mg non-carboxylate salts as disclosed and claimed in pending US patent application Ser.

Particularly preferred complexes of the type mentioned above are:

MO/M carboxylate MCOi/M sulfonate MO/M sulfonate M CO3/ M carboxylate MO/M sulfonate + MCO3/M carboxylate M O/ M CO3/ M carboxylate MO/MCO
The most preferred 3/M sulfonate complexes are:

MgO/Mg fatty acid carboxylates (especially "tall oil" fatty acid carboxylates) Mg O/Mg benzosulfonates or dodecylbenzenesulfonates MgCO3/Mg fatty acid carboxylates Mg CO3/Mg benzenesulfonates or dodecylbenzenes Sulfonate Cab/Ca Fatty acid carboxylate Ca O/Ca Benzene sulfonate or dodecylbenzenesulfonate Ca co,/Ca Fatty acid carboxylate Mg O/Mg
Fatty acid carboxylate + MgO/Mg benzenesulfonate or dodecylbenzenesulfonate MgCO3/Mg fatty acid carboxylate 10MgCO) /
Mg benzene sulfonate or dodecylbenzenesulfonate Mg O/ Mg CO3/ Mg fatty acid carboxylate Mg O/ Mg CO3/ Mg benzene sulfonate or dodecyl benzene sulfonate base excess complex mixture, e.g. MgO/Mg fatty acid Carboxylic acid + Mg
O/Mg benzenesulfonic acid has a weight ratio of about 0 between the complexes.
．． 25/10 to about 10/0.25.

As described in the above-mentioned U.S. Pat. No. 4,163,728, the products resulting from the reaction of the metal base with the acid are further decomposed to form particulate metal oxides or carbonates; Accompanying metal salts of the acid are formed. The microparticles are immediately suspended and stabilized by the metal salt of the acid. The particle size of the metal oxide or metal carbonate should be less than about 2μ in diameter, such as less than about 1μ, preferably less than about 0.1μ, and especially less than 0.1μ in diameter.

The amount of antifouling agent used to prevent soiling in an area of soiling will vary depending on the environment of the area, the degree of soiling, and the particular antifouling agent used.

Generally, the amount of antifouling agent used is an amount sufficient to prevent staining in an area. Therefore, depending on the specific situation, based on the weight of the hydrocarbon stream, approximately 51)
I)T! Amounts of up to about 1,000 ppm or more can be used. Approximately 25 ppn+ to approximately 5001)[)In
is usually effective, from about 50 ppffi to about 300 ppm
is particularly effective.

Therefore, in the best mode of carrying out the present invention, an effective amount of the antifouling agent as described above is applied to a suitable spill area of an oil refining process, a gas refining process, or a petrochemical refining process. Add the anti-stain composition described in the invention.

Claims (1)

[Claims] 1. (A) an oxide of a metal selected from the group consisting of Mg, Ca, Ba, Sr and Mn and mixtures thereof;
B) Antifouling compositions comprising at least one overbased complex of at least one organic acid complexing agent with a metal salt. 2. Claim 1, wherein the metal is magnesium
Compositions as described in Section. 3. The composition according to claim 1, wherein the metal is calcium. 4. The composition according to claim 1, wherein the metal is barium. 5. The composition according to claim 1, wherein the metal is strontium. 6. The composition according to claim 1, wherein the metal is manganese. 7. The composition according to claim 1, wherein the complexing agent is selected from the group consisting of carboxylic acids and organic acids other than carboxylic acids. 8. The composition according to claim 7, wherein the complexing agent is a carboxylic acid. 9. The composition according to claim 8, wherein the acid is a fatty acid. 10. The composition according to claim 7, wherein the complexing agent which is an organic acid other than carboxylic acid is an organic sulfur acid. 11. Claim 10, wherein the acid is a sulfonic acid.
Compositions as described in Section. 12. The composition according to claim 11, wherein the sulfonic acid is benzenesulfonic acid. 13. The composition according to claim 7, wherein the complexing agent which is an organic acid other than carboxylic acid is an organic phosphorus acid. 14. Claim 13, wherein the acid is a phosphonic acid.
Compositions as described in Section. 15, containing at least one complex with excess base of (A) a carbonate of a metal selected from the group consisting of Mg, Ca, Ba, Sr and Mn and (B) a metal salt of an organic acid complex forming agent; An antifouling composition in which the complex is not a complex of calcium carbonate and a calcium salt of sulfonic acid. 16. At least one overbasic complex of (A) a carbonate of a metal selected from the group consisting of Mg, Ca, Ba, Sr and Mn and (B) a metal salt of at least one carboxylic acid complex forming agent. Antifouling composition containing seeds. 17. The composition according to claim 16, wherein the metal is magnesium. 18. Claim 1, wherein the metal is calcium.
Composition according to item 6. 19. Claim 16, wherein the metal is barium.
Compositions as described in Section. 20. The composition according to claim 16, wherein the metal is strontium. 21. Claim 16, wherein the metal is manganese
Compositions as described in Section. 22. Claim 1, wherein the complexing agent is a fatty acid.
Composition according to item 6. 23. A stain containing at least one type of excess base complex of (A) a carbonate of a metal selected from the group consisting of Mg, Ba, Sr, and Mn and (B) a metal salt of an organic sulfur acid complexing agent. Prevention composition. 24. The composition according to claim 23, wherein the metal is magnesium. 25. Claim 23, wherein the metal is barium
Compositions as described in Section. 26. The composition according to claim 23, wherein the metal is strontium. 27. Claim 23, wherein the metal is manganese
Compositions as described in Section. 28. Claim 23, wherein the acid is a sulfonic acid
Compositions as described in Section. 29. The composition according to claim 24, wherein the acid is benzenesulfonic acid. 30. A base-excessive complex of (A) a metal oxide or carbonate selected from the group consisting of Mg, Ca, Ba, Sr and Mn and (B) a metal salt of an organophosphorus acid complexing agent. An anti-stain composition comprising at least one. 31. The composition according to claim 30, wherein the metal is magnesium. 32. Claim 3, wherein the metal is calcium.
Composition according to item 0. 33. Claim 30, wherein the metal is barium
Compositions as described in Section. 34. The composition according to claim 30, wherein the metal is strontium. 35. Claim 30, wherein the metal is manganese
Compositions as described in Section. 36. Claim 30, wherein the acid is a phosphonic acid.
Compositions as described in Section. 37, (A) at least one base-excessive complex of (1) an oxide of a metal selected from the group consisting of Ca, Ba, Sr and Mn and (2) a metal salt of a carboxylic acid complex forming agent;
B) At least one overbasic complex of (1) a carbonate of a metal selected from the group consisting of Mg, Ca, Ba, Sr, and Mn and (2) a metal salt of a complexing agent of an organic sulfur-based acid. Antifouling composition containing seeds. 38. The composition according to claim 37, wherein the carboxylic acid is a tall oil fatty acid, and the sulfur-based acid is a sulfonic acid. 39. The composition according to claim 38, wherein the sulfonic acid is benzenesulfonic acid. 40, (A) (1) Mg, Ca, Ba, Sr and Mn
A metal oxide or carbonate selected from the group consisting of (
2) at least one overbased complex of a metal salt of a carboxylic acid complex-forming agent, and (B) (1) an oxide or carbonate of a metal selected from the group consisting of Mg, Ca, Ba, Sr, and Mn; (2) An antifouling composition containing at least one base-excessive complex of an organophosphorus acid complexing agent with a metal salt. 41. The composition according to claim 40, wherein the carboxylic acid is tall oil fatty acid. 42. The composition according to claim 40, wherein the organic phosphorus acid is phosphonic acid. 43, (A) (1) Mg, Ca, Ba, Sr and Mn
and (B) at least one base-excessive complex of a metal oxide selected from the group consisting of (2) a metal salt of a carboxylic acid complex-forming agent; An antifouling composition comprising at least one overbasic complex of a metal carbonate selected from (2) a metal salt of an organic sulfur acid complexing agent. 44. The composition according to claim 43, wherein the carboxylic acid is a fatty acid. 45. The composition according to claim 43, wherein the sulfur-based acid is a sulfonic acid. 46. The composition according to claim 44, wherein the sulfonic acid is benzenesulfonic acid. 47. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 1 to the fouled area of the petroleum refining process in an amount effective for preventing fouling. 48. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 15 to the fouled area of the petroleum refining process in an oil refining process. 49. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 16 to the fouled area of the oil refining process in an oil refining process. 50. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 23 to the fouled area of the petroleum refining process. 51. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 30 to the fouled area of the petroleum refining process in an oil refining process. 52. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 37 to a fouled region of the petroleum refining process. 53. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 40 to the fouled area of the petroleum refining process. 54. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 43 to the fouled area of the petroleum refining process in an amount effective for preventing fouling. 55. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 1 to the fouled area of the gas purification process in an amount effective for preventing fouling. 56. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 15 to a fouled region of the gas purification process in an amount effective for preventing fouling. 57. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 16 to the fouled area of the gas purification process in an amount effective for preventing fouling. 58. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 23 to the fouled region of the gas purification process in an amount effective for preventing fouling. 59. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 30 to a fouled region of the gas purification process in an amount effective for preventing fouling. 60. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 37 to the fouled area of the gas purification process in an amount effective for preventing fouling. 61. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 40 to the fouled area of the gas purification process in an amount effective for preventing fouling. 62. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 43 to a fouled region of the gas purification process in an amount effective for preventing fouling. 63. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 1 to a fouled area in the refining process of petrochemicals. 64. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 15 to a fouled area in the refining process of petrochemicals. 65. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 16 to the fouled area of the refining process of petrochemicals. 66. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 23 to the fouled region of the refining process of petrochemicals. 67. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 30 to a fouled area in the refining process of petrochemicals. 68. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 37 to a fouled area in the refining process of petrochemicals. 69. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 40 to the fouled area of the refining process of petrochemicals. 70. A method for preventing fouling, which comprises the step of adding an effective amount of the composition according to claim 43 to a fouled area in the refining process of petrochemicals. 71, an antifouling composition containing a base-excessive complex reaction product of a compound that reacts as a base of a metal selected from the group consisting of Mg, Ca, Ba, Sr, and Mn and at least one organic acid complexing agent. . 72. The composition of claim 71, wherein carbon dioxide is introduced during said reaction.