Method for reducing hydrolysis in hydrocarbon streams

FIELD: petrochemical processes.

SUBSTANCE: invention relates to reducing hydrolysis in hydrocarbon streams including addition to hydrocarbon stream, containing a chloride compound hydrolysable at elevated temperature in presence of water to form hydrochloric acid, of an effective amount of treating agent, namely at least one superbasic metal salt complex and organoacid complexion reagent. The agent is added when temperature of stream is below temperature at which considerable hydrolysis chloride-containing compound can occur.

EFFECT: increased chloride-containing compound hydrolysis reduction efficiency to formation of minimum amount of hydrochloric acid.

16 cl, 5 dwg, 2 ex

 

This application has a priority of the first application, serial No. 60/376631, filed April 30, 2000.

This invention relates to the reduction of the hydrolysis of hydrocarbon streams such as crude oil subjected to processing at elevated temperatures, and, more specifically, to reduce the level of hydrolysis and subsequent formation of hydrochloric acid by adding to such threads inhibitors of hydrolysis.

Typical refinery includes tank station or storage site, where the feedstock, i.e. crude oil, shale oil, kerosene, and some intermediate petroleum products processing of oil for their optimal use in a refinery. Often this feedstock contains chlorides, above all the chlorides of the metals, and, more specifically, chlorides of alkali and alkaline earth metals, in an amount of from 1 to 2000 ppm. It is known that hydrocarbon products containing chloride impurities, at elevated temperatures and in the presence of water hydrolyzed with the formation of hydrochloric acid, which, as is well known to specialists in this field of technology can cause severe corrosion of process equipment.

In conventional refinery crude oil of Vacha the e process in the plant for desalination, i.e. the Watermaker. The purpose of the desalination plant is to remove as many salts and other water soluble contaminants prior to further hydrocarbon feed stream, i.e. crude oil, heat exchangers, furnaces, distillation columns, cracking installation and associated process equipment such as pumps, valves, pipelines and other devices commonly used in oil refineries and other petrochemical facilities. Usually supplied to the desalination plant and the raw material is pre-heated, typically to a temperature of from about 200 to 250°F. After passing the feedstock through a desalination plant, which typically operates at a temperature of from 200 to 250°F is passed through a second heating zone having a temperature of from about 200 to 600°F. Then heated stream is served in a furnace where it is heated to a temperature of from 600 to 700°F. thereafter, the flow is served in a distillation column operating at atmospheric pressure, together with steam for the implementation of pre-fractionation, as a rule, four factions: the top stream containing light hydrocarbons, for example, With1-C8the hydrocarbon; the first intermediate fraction including kerosene, jet and diesel fuel; second, the intermediate fraction, aderasa the gasoil; and the bottom fraction containing the heavy components that are present in raw materials. As stated above, usually share the flow of raw material in the distillation column at atmospheric pressure. Thus, all of the hydrochloric acid formed to the specified column, falls into a light fraction and condensed water. Subsequent processing such condensed fraction leads to the contact of hydrochloric acid with the technological equipment used for processing the condensed fraction, and thus to the corrosive destruction.

The usual way to prevent corrosion, called the top fraction in the reaction of hydrolysis, is the use of neutralizing agents and corrosion inhibitors. Such inhibitors are expensive and in many cases cause foaming and deposition, which can be more destructive than corrosion.

In accordance with a preferred aspect of the present invention, a method of reducing hydrolysis in the hydrocarbon stream, in accordance with which a hydrocarbon stream containing chloride compound which is hydrolyzed at elevated temperatures in the presence of water with the formation of hydrochloric acid is treated with an effective amount of an agent comprising at least one nadona the hydrated complex of a metal salt and a complexing agent based on organic acids. The processing agent is preferably injected into the hydrocarbon flow when the specified flow has a temperature below which there is a substantial hydrolysis containing chloride compounds.

BRIEF DESCRIPTION of FIGURES

Figure 1 is a graph showing the hydrolysis of various chlorides of metals in mineral oil, depending on the temperature.

Figure 2 is a graph showing the effect of various contaminants on the hydrolysis of calcium chloride in mineral oil, depending on the temperature.

Figure 3 is a graph showing the hydrolysis of sodium chloride in mineral oil in the presence of naphthenic acids depending on the temperature.

Figure 4 is a graph showing the inhibition of the hydrolysis of calcium chloride according to the method in accordance with the invention.

Figure 5 is a graph showing the inhibition of the mixed chlorides in mineral oil according to the method in accordance with the invention.

Description of the PREFERRED OPTIONS

Despite the fact that the method according to the invention relates to a feedstock for the refinery, it can be used for any of the hydrocarbon stream and any process in which a hydrocarbon stream contains hydrolyzable chloride compounds able to form hydrochloric acid with ychenih temperatures and in the presence of water. Non-limiting examples of suitable hydrocarbon streams include crude oil, shale oil, kerosene, and various hydrocarbon products resulting from the refining of oil and, as a rule, used as intermediates for other, more desirable products. Chloride-containing compound can be any compound, usually inorganic nature, gidrolizuacy at elevated temperatures and in the presence of water with the formation of hydrochloric acid. Usually chloride-containing compounds are metal salts and, more specifically, salts of alkali and alkaline earth metals, such as sodium chloride, calcium chloride, magnesium chloride, etc. As indicated above, it was found that when injected into contaminated with chlorides hydrocarbon streams agent comprising a complex of adenosine of the metal salt and described below complexing agent based on organic acids, before the stream will be in conditions where there is a substantial hydrolysis, the hydrolysis of the chloride formed is greatly reduced, often to the point at which there is minimal corrosion.

Hydrolysis of chloride-containing compounds with the formation of hydrochloric acid is typically in the temperature interval savinase the specific conditions, specific chloride (chloride) and other similar parameters. In General, however, significant hydrolysis does not usually occur until such time as the temperature of the hydrocarbon stream reaches approximately 300°F, although depending on the chloride compounds and other conditions, some hydrolysis may occur at such low temperatures, 250°. Accordingly, although in the above-mentioned reasons, the exact temperature cannot be specified in General, the agent is injected into the hydrocarbon stream in the moment when he has a temperature below approximately 400°F. as an example, may be provided above the oil-refining process in which the feedstock is passed through a first preheating section, a desalination plant, the second heating section, then through the furnace to feed to a distillation column operating at atmospheric pressure, because the second heating section raises the temperature of the raw material up to a level of approximately from 250 to 600°F, and in this moment there is substantial hydrolysis of the chloride impurities. Accordingly, the processing agent according to the invention is preferably introduced into the flow of raw materials to supply to the second heating section, i.e. the heating section after the desalination plant and in front of the furnace. However, it should be noted that machining the Gent can be introduced well before the second heating section, and in fact, can be introduced from a raw material having an ambient temperature or a lower temperature, i.e. up to the first heating section. Thus, there are many opportunities for injection box, starting with the introduction of raw materials in oil refining process to the heating system as a whole, after desalination plant and in front of the furnace when the temperature is still insufficient for significant hydrolysis or when the agent can be introduced to prevent such hydrolysis. The processing agent can also be introduced into the heating section between the desalination plant and oven, although it is preferable to the introduction of this agent in the thread before filing the second heating section.

It is also expected that the method according to the invention can be used to reduce corrosion caused by naphthenic acid, which is well known in the refining processes. Caused by naphthenic acid corrosion usually occurs at a temperature from 400 to 600°F, i.e. at a temperature substantially higher than the temperature at which hydrolysis occurs chloride impurities. Thus, with reference to the above, with the introduction of the processing agent in the stream at any time before the flow reaches the second heating section, i.e. naked is eutalloy section between the desalination plant and oven, he will have a effective effect in reducing corrosion caused by naphthenic acid, and hydrolysis of the chloride impurities. It should also be noted that the naphthenic acid significantly increases the hydrolysis of chlorides such as sodium chloride.

In accordance with the description of U.S. patent 5858208, the agent used in this invention includes at least one nadobny complex salt and a complexing agent based on organic acids. The exact structure of radonaway not well understood. It is assumed that they include dispersions of salts, resulting from the interaction of acidic compounds with an excess amount of the compound of the metal; for example, the hydroxide or oxide of the metal. Alternatively, it was suggested that they contain a polymer and salt". Probably correct both theories, but none of them is completely correct. According to the invention, it is assumed that obtaining "naconalnogo" product leads to the production of "naconalnogo complex oxide or carbonate of the metal with a dispersing agent or a stabilizer based on organic acids; i.e., "complexing reagent". The nature of the thus obtained complex is not yet fully understood.

Accordingly, according to this description, the processing agent is a n is Osnovnye complex oxide or carbonate of Mg, Ca, Ba, Sr or Mn, and salts of Mg, Ca, Ba, Sr or Mn organogelator "complexing reagent". The authors of this invention have found that compounds of magnesium are especially effective results; can be expressed by theoretical assumption that aluminum compounds as such or in combination with Mg also give good results. Thus, in this invention it is assumed that adenosine include aluminum compounds. The agent contains a stoichiometric excess of a compound of the base metal is relatively equivalent to the amount of acid complexing reagent exposed to the interaction with the connection of the base metal to obtain the complex relative to the normal stoichiometry of the particular metal base and acid. For example, "neutral" or "normal" metal salt of the acid is characterized by the equivalent ratio of base or metal to acid is 1:1; while nadonna salt characterized by a higher ratio, for example, 1,1:1, 2:1, 5:1, 10:1, 15:1, 20:1, 30:1 and so the Term "metal ratio" means the ratio of equivalents of metal or of base to acid in adonovski salt (b) the number of equivalents in normal salt in the calculation on the normal stoichiometry of the used metal or metals present in the acid and the acids. Thus, a metal ratio of oil dispersion adonovski magnesium salt containing two equivalents of acid and twenty equivalents of magnesium, will be 10, i.e 20/(1+1).

According to this description, for example, it is believed that magnesium has two equivalent bases on atomic mass, and magnesium oxide (MgO) and magnesium hydroxide (Mg(SLEEP2two equivalents per mole. It is considered that the monobasic organic acids have one equivalent of acid in the acidic hydrogen or an acid group. Thus, monocarboxylic acid or monosulfonic acid or their equivalent derivatives, such as esters and ammonium and metal salts, have one equivalent per mole of acid of ester or salt; desulfonema acid or dicarboxylic acid or their equivalent derivative has two equivalents per mole. Basic metal compounds such as oxides and carbonates of calcium, barium and magnesium, have two equivalents per mole, i.e., two equivalent atomic mass of metal.

The agents used in the method according to the invention, are nadobny complexes of metal oxides and/or carbonates and metal salt, at least one complexing agent. Oxides or carbonates can also be a combination of compounds of metals, for example, a mixture of 1:1 is AC. Likewise, a salt can be a combination of metal salts, for example, a mixture of 1:1 wt. However, compounds of magnesium, calcium or aluminum are highly preferred.

Further, the term "carboxylate" refers to the product of the interaction of a metal base and an organic carboxylic acid of General formula R-COOH, in which R represents a hydrocarbon radical, and the term "not-carboxylate" refers to the product of the interaction of a metal base and an organic acid other than organic carboxylic acids; for example, "non-carboxylic acids, such as organic sulfuric acid and organic phosphoric acid having a much better dispersing properties than carboxylates, however, carboxylates have stabilizing properties.

The role of the complexing agent in the acquisition and application processing agents according to the invention is not clear. As indicated above, some agents can act as stabilizers, while other agents can act as dispersers. Undoubtedly, some agents can perform both functions, or other, unknown function. However, it appears that during retrieval of the complex, the presence of at least one complexing agent is essential for obtaining agent used is about in the method according to the invention. It was also found that the preferred agents are characterized by the presence of not-carboxylate salts, for example, sulfonate.

The agents used in the present invention, can be obtained in accordance with any method of obtaining nadobny salts known in the art, provided that we receive from them carboxypropanoyl nadobny complex magnesium oxide/magnesium looks fine, preferably submicron particles, forming a stable dispersion in oil. Thus, the method of obtaining carboxylating naconalnogo complex magnesium oxide/magnesium includes obtaining a mixture of the Foundation of the desired metal; for example, Mg(HE2), complexing agent; for example, fatty acids such as fatty acid tall oil present in quantities much smaller quantity necessary for stoichiometric interaction with hydroxide, and non-volatile diluent. The mixture is heated to a temperature of approximately from 250 to 350°thus nadobny complex metal oxide and metal salts of fatty acids described in U.S. patent No. 4163728 (patent '728). Nadobny complex carbonate/metal complexing reagent, for example, magnesium carbonate/magnesium sulfonate, commercially available or can be obtained in the above way, excluded the eat that carbon dioxide is bubbled through the original reaction mixture.

The above method of obtaining naconalnogo carboxylate agent magnesium oxide/magnesium carboxylate used in the present invention is particularly well described in the patent '728 cited in this description by reference in full and forming part of the description, in which, for example, a mixture of complexing agent of Mg(OH)2and carboxylic acid are heated at a temperature of from 280 to 330°in a suitable non-volatile diluent.

Complexing agents are carboxylic acids, phenols, organic phosphoric acid and organic sulfuric acid. This group includes the acid used to obtain nadobny compounds, for example, acid, described in U.S. patent No. 3312618, 2695910 and 2616904, and related to recognized in the art class of acids. Particularly suitable are carboxylic acids, phenols, organic phosphoric acid and organic sulfuric acids, which are soluble in the oil per se, especially soluble in oil sulfonic acid. Soluble in oil derivatives of organic acids, such as their metal salts, ammonium salts and esters (especially esters with lower aliphatic alcohols containing up to six carbon atoms, such to the to the lower alkanols), can be used in lieu or in conjunction with the free acids. When referring to acid indirectly refers to its equivalent derivative, if not obviously, can only be used with acid.

Suitable complexing agents of carboxylic acids that can be used to obtain a processing agent include aliphatic, cycloaliphatic and aromatic single and politonalnye carboxylic acids such as naphthenic acids, alkyl - or alkenyl-substituted cyclopentane acid, alkyl - or alkenyl-substituted cyclohexane acid and alkyl - or alkenyl-substituted aromatic carboxylic acid. Typically, aliphatic acids are long-chain acid and contain at least eight carbon atoms, preferably at least twelve carbon atoms. Cycloaliphatic and aliphatic carboxylic acids can be saturated and unsaturated. Specific examples include 2-ethylhexanol acid, alpha-linolenic acid, propylene-tetramer-substituted maleic acid, beenbuy acid, isostearoyl acid, pelargonium acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecisive acid, dioctyl kapetanova carboxylic acid, myristic acid, draudingekvider-naftalanovoy carboxylic acid, stearyl-octahedronparty acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as fatty acids of tall oil, resin acids, etc. as typical acids can also be mentioned saturated aliphatic monocarboxylic acids, e.g. formic, acetic, propionic, butyric, Valerian, nylon, heptane, Caprylic, pelargonia, capric, undecisive, lauriola, traditiona, myristic, INOXPA, palmitic, margaric and stearic; alicyclic unsaturated monocarboxylic acid, for example, hydracarina and chaulmoogra; saturated aliphatic dicarboxylic acids, e.g. oxalic, malonic, succinic, glutaric, adipic, Emelyanova, cork, azelaic and sabotinova; alicyclic saturated dicarboxylic acid, such as acrylic, crotonic, detinova, undecenoate, tridecanoate, pentadecanol, oleic, linoleic and linolenic acid; unsaturated dicarboxylic acids, for example, fumaric and maleic.

Aromatic acid used for obtaining agent represented by the General formula:

where R is a hydrocarbon or essentially uglev the portly radical, containing at least four aliphatic carbon atoms, R' represents hydrogen or C(X)HN, n is an integer from one to four, Ar is a polyvalent aromatic hydrocarbon radical generally containing up to fourteen carbon atoms in the aromatic ring, each X independently represents a divalent sulfur or oxygen group and p is zero or an integer from one to six, provided that R and n have the meanings involving the contents, on average, at least eight aliphatic carbon atoms, provide the substituents R presents for each molecule of acid. Examples of aromatic radicals represented by Ar balance, are polyvalent aromatic radicals derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, etc. As a rule, the radical represented by Ar, means polyvalent radical derived from benzene or naphthalene such as phenylene and naphthalene, for example methylphenylene, mercaptopurine, N,N-diethylaminophenyl, chloraniline, disproportionately, triethylenediamine and similar tri-, Tetra - and pentavalent radicals.

The residues R are usually a hydrocarbon group, preferably aliphatic hydrocarbon groups such as alkyl or alkenyl the s radicals. However, the residues R can contain such substituents as phenyl, cycloalkyl, for example, cyclohexyl, cyclopentyl etc. and non-hydrocarbon groups such as nitro, amino, halo, for example, chlorine, bromine, etc., lower alkoxy, lower allylmercaptan, oxazolidine, ie =O, tigroup; i.e., =S group, which interrupt the chain, such as --NH--, --O--, --S-- and the like, provided that the essentially hydrocarbon character of the remainder R is stored. Examples of the residue R include butyl, isobutyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, tert-chlorhex, 4-ethoxyphenyl, 4-hexenyl, 3-cyclohexyloxy, 4-(p-chlorophenyl)octyl, 2,3,5-trimethyl, 4-ethyl-5-metrotel, and the Deputy obtained from depolimerization olefins, such as polychloroprene, polyethylene, popypropylene, polyisobutylene, copolymers of ethylene and propylene, polymers of olefins, chlorinated, oxidized copolymers of ethylene and propylene, etc. Similarly, the remainder of the Ar may contain non-hydrocarbon substituents for example, different substituents, such as lower alkoxy, lower allylmercaptan, nitro, halo, alkyl or altergroup containing less than four carbon atoms, hydroxy, mercapto, etc.

Another group of aromatic carboxylic acids are acids of the formula:

where R' represents an aliphatic hydrocarbon radical, aderrasi at least four carbon atoms, andan integer from 1 to 3,bis 1 or 2,withis zero, 1 or 2, preferably 1, provided that R' andamatter involving the content of the acid molecules, at least, on average, about twelve aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule.

Applied phenols include 3,5,5-trimethyl-n-hexylphenyl-dellvery, atillery, nonylphenols, alkylphenolate, resorcinol, actication, triisobutylene, alkyl-alpha-naphthol, etc.

Other acids, such as phenols, i.e. the "not-carboxylic acid", which can be used for improving the processing properties of the compounds are organic sulfuric acids, for example, soluble in oil sulfonic acids, including synthetic sulfonic acid, soluble in oil. Suitable soluble in oil sulfonic acid represented by the General formula:

I. Rx- T - (SO3H)y

II. R1- (SO3H)y

In the formula ITrepresents a cyclic ring mono - or polynuclear, including benzene, cycloaliphatic or heterocyclic rings, such as benzene, naphthalene, anthracene, 1,2,3,4-tetrahydronaphthalen, tianren, cyclopentene, pyridine or biphenyl, etc. However, as a rule,Txmay, for example, be aliphaticity group, such as alkyl, Alchemilla, alkoxylalkyl, carboalkoxylation, kalkilya group or other hydrocarbon or essentially hydrocarbon groups, whilexequal to at least 1, provided that the residues represented by the group Rxensure the solubility of the acids in the oil. This means that the groups represented by Rxmust contain at least about eight aliphatic carbon atoms, preferably at least about twelve aliphatic carbon atoms. As a rule,xis an integer of 1-3. Variablesrandyin formulas I and II, on average, have a value of one to about four molecule.

Balance R' in formula II is an aliphatic or alifaticheskii substituted cycloaliphatic hydrocarbon or essentially hydrocarbon radical. If R' represents an aliphatic radical, it should contain at least about 8 to 20 carbon atoms, and when R' represents alifaticheskii substituted cycloaliphatic group, an aliphatic substituents should contain from about 4 to 16 carbon atoms. Examples of R' include alkyl, alkene the performance communications and alkoxyalkyl radicals and alifaticheskii substituted cycloaliphatic radicals, in which the aliphatic substituents are alkoxy, alkoxyalkyl, carbalkoxy etc. In General, a cycloaliphatic radical is cycloalkane ring or cycloalkene ring, such as cyclopentane, cyclohexane, cyclohexene, cyclopentene and the like, Specific examples of R' include etiltsiklogeksana, laurylsarcosine, catrocsitre and octadecenyl radicals, and radicals derived from petroleum hydrocarbons, saturated and unsaturated paraffin wax, and polyolefins, including depolimerizovannogo mono - and diolefin containing from about 1 to 8 carbon atoms in Monomeric olefinic link. The groups T, R and R' in formulas I and II can also contain other substituents, such as hydroxy, mercapto, halogen, nitro, amino, nitroso, carboxy, lower carbalkoxy etc., provided that the hydrocarbon character of the group is essentially not impaired.

Preferably used in this invention sulfonic acid include alkylsulfonate acid, alkalicarbonate acid, aralkylamines acid, dialkylamino acid, dialchilarilsulfonai acid, arylsulfonic acid, for example, ethylsulfonyl acid, benzolsulfonat acid, dodecylbenzenesulfonic acid and more complex mixture of sulfonic acids, such as sulfonyl is you, soluble in petroleum products, and petroleum sulfonic acids.

In addition, illustrative examples of sulfonic acids include soluble petroleum sulfonic acids, petroleum sulfonic acids, mono - and palivos-substituted naphthalene sulfonic acids, catergorisation acid, cetylmeristoleate acid, citifinancialmortgage acid, setaxisorientation acid, dietilentriaminom acid, di-lauryl-beta-naphthol-sulfonic acid, disabilityinsurance acid, paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, replacement of paraffin wax sulfonic acids, tetraisostearate, tetraaminoanthraquinone, chloro-substituted paraffin wax sulfonic acids, nicrosil-substituted paraffin wax sulfonic acids, oil, naphthene sulfonic acids, citizenmetalloyscom, laurilsulfate, mono and palivos-substituted cyclohexylsulfamate etc.

In this description, the term "petroleum sulfonic acids or pyrasulfotole" means well-known class of sulfonic acids derived from petroleum products in accordance with known methods, for example, described in U.S. patents№№ 2490638, 2483800, 2717265, 2726261, 2794829, 2832801, 3225086, 3337613, 3351655 and the like, Sulfonic acids falling under formula I and II, described in the U.S. patents 2616904, 2616905, 2273234, 2723235, 2723236, 2777874, as well as in other U.S. patents cited in each of these patents. Thus, it is obvious that the said soluble in oil sulfonic acids are well known in the art and there is no need for further clarification.

Used in this invention, organic phosphorus acids characterized by the presence of at least one oil-soluble group attached directly to the phosphorus via a carbon atom, for example, soluble in oil, phosphoric, phosphinic and phosphonic acids, including soluble in oil tiofosfornoy, thiophosphonate and thiophosphorous acid. Preferred phosphoric acid are alkyl - and dialkylphosphinate and phosphonic acid, and the acid resulting from the interaction of olefins with sulfides of phosphorus, for example, pentasulfide phosphorus. Can also be used steamed products pentasulfide and polyolefins phosphorus, such as polyisobutylene and polypropylene. As follows from the U.S. patent№№ 2316078, 2315080, 2316091, 2367468, 2375315, 2377955, 2496508, 2507731, 2516119, 2597750, 2647889, 2688612 and 2915517, such acids are well known.

Of course, to get the agents used in the methods according to the invention, can be used mixtures of the above organic is the slot and their derivatives.

The following types nadobny complexes are preferred agents used in this invention is:

MgO/Mg carboxylate

MgCO3/Mg carboxylate

MgO/Mg not-carboxylate

MgCO3/Mg not-carboxylate

It is noted that the corresponding variation of aluminum are also suitable.

The term "carboxylate" and "not-carboxylate" refers, as indicated above, to the partial product of the interaction of the Foundation of the desired metal and complexing reagent carboxylic or not-carboxylic acid, leading to the complex, which probably represents a fine dispersion of oxide (or carbonate) metal associated with carboxylate or not-carboxylate metal.

Of course, with the complexing agent can be associated with several oxides or carbonates, forming complexes, for example, of MgO/MgCO3/Mg-no-carboxylate, and several complexing reagents can be connected to the oxide or carbonate, forming complexes, for example, of MgO/Mg carboxylate/Mg-no-carboxylate and MgCO3/carboxylate/Mg-no-carboxylate. Possible alternatives are probably the corresponding aluminum compounds.

Also suitable are mixed nadobny complexes, for example MgO/Mg carboxylate with MgO/Mg-no-carboxylate, MgCO3/carboxylates MgCO 3not-carboxylate, MgO/Mg carboxylate with MgCO3/not-carboxylate, etc. Possible alternatives also are the corresponding aluminum compounds.

Particularly preferred of the above types are the following:

MgO/Mg carboxylate

MgCO3/Mg sulfonate

MgCO3/Mg carboxylate

MgO/Mg sulfonate+MgCO3Mg carboxylate

MgO/MgCO3Mg carboxylate

MgO/MgCO3/Mg sulfonate

Most preferred complexes are the following:

MgO/Mg carboxylate fatty acids (especially carboxylates of fatty acids "tall oil")

MgO/Mg bansilalpet or dodecylbenzensulfonate

MgCO3/Mg carboxylate of the fatty acid MgCO3/Mg bansilalpet or dodecylbenzensulfonate

MgO/Mg carboxylate of the fatty acid+MgO/Mg bansilalpet or dodecylbenzensulfonate

MgCO3/Mg carboxylate of the fatty acid+MgCO3/Mg bansilalpet or dodecylbenzensulfonate

MgO/MgCO3/Mg carboxylate fatty acids

MgO/MgCO3/Mg bansilalpet or dodecylbenzensulfonate

The mass ratio of mixed nadobny complexes, for example, MgO/Mg carboxylate of the fatty acid + MgCO3/Mg bansilalpet approximately 0.25/10 to 10/0,25.

As described in the cited above patent '728, the result of the interaction of metal base and KIS is the notes receive the product, decomposes to obtain fine particles of oxide or carbonate of the metal due to metal salt of the acid. Fine particles immediately suspendered and stabilize the metal salts of the acid. The particle size of the metal oxide or carbonate of the metal in diameter does not exceed about 2 microns, for example, about 1 micron, however, preferably is not more than about 0.1 micron, and more preferably, less than 0.1 micron in diameter.

As described in patent '728, obtaining a stable liquid dispersion of magnesium involves the decomposition of the magnesium carboxylate to MgO in a non-volatile liquid medium, which can be heated to the temperature of decomposition of the magnesium carboxylate, also containing a dispersing agent, is able to maintain the magnesium oxide formed by decomposition in stable suspension at a temperature above about 230°in this way the number of carboxylate per Mg(OH)2or its equivalent is less than the stoichiometric quantity. Dispersion of magnesium oxide upon decomposition can be subjected to interact with to obtain dispersions MgCO3with water to obtain a dispersion of Mg(OH)2etc.

So adenosine, by their nature, are colloidal dispersions, which can be added to the when asked "liquids" to the above-described hydrocarbon streams. It was found that after adding to the hydrocarbon flow adenosine easily disperse and retain a similar trend. In this sense, adenosine are soluble in oil, because they form a well-dispersed colloidal suspensions in hydrocarbon streams such as crude oil.

The amount of agent used varies depending on the environment, type of chloride concentration in the treated hydrocarbon stream. Generally, it is desirable concentration constituting at least about 0.5 ppm of available metal 1 ppm chloride. However, due to the possible failure of a preferred concentration, component, at least 1 ppm of available metal 1 ppm chloride. In General, apply such amount of the cleaning agent, which is effective to reduce hydrolysis. This description is called the "effective amount". Accordingly, the specified number may be from about 5 ppm to 1000 ppm or more, depending on the concentration and type of chloride contained in the hydrocarbon stream, taking into account the specific circumstances. Typically, the effective amount from about 25 ppm to 500 ppm, especially from approximately 50 to 300 ppm.

The concentration of the above-described agent usually maintain constant the level. Thus, the agent is added continuously in an amount necessary to maintain a constant concentration of, for example, from about 25 to 500 ppm, especially from approximately 50 to 300 ppm. However, in some cases the agent may be added as a single dose or semi-continuous manner. The agent can be added in liquid form or, when added to the gas stream in the form of a spray jet.

EXPERIMENTAL PART

The method in accordance with the present invention was investigated in the laboratory using the mineral oil and synthetic raw oil consisting of a mineral oil with a variety of contaminating impurities usually present in crude oil. Used distiller to steam distillation for the implementation of the steam distillation of synthetic raw oil at a temperature of from 300 to 650°F at atmospheric pressure. In addition to mineral oils and chloride, synthetic raw oil contains iron oxide, silicon dioxide, iron sulfide, drilling mud and naphthenic acid. Were selected impurities corresponding to field conditions. In this regard, it is known that the oxide and iron sulfide are formed by corrosion of the equipment used to implement the first stages of the process. Usually in damp n the PTI is silicon because of the fault rocks. Drilling mud is usually present in crude oil as a result of tumors or development wells. Naphthenic acids are present in varying amounts in almost all types of crude oil.

Used metal salts, including sodium chloride, magnesium chloride and calcium chloride, is added to mineral oil in the form of a fine powder and stirred for five minutes in a high speed mixer to obtain a stable suspension. Was selected hexahydrate form of magnesium chloride and digitata form of calcium chloride, because these forms are likely to be present in different types of crude oil that has been exposed to water. Was used anhydrous sodium chloride, because, most likely, hydrates of sodium chloride are not present in crude oil.

Then oil-salt suspension is heated together with the test contaminating impurities to a temperature of studies, then start blowing at the rate of 1 g/min, continue to obtain 10 g of the condensate. The condensation is then analyzed for chloride by titration nitrate of mercury and ionoobmennoi chromatography. In all cases, the results are presented as percentage of initial chloride added to the synthetic crude or mineral oil in the form of salt into three who, calcium or magnesium. Samples of the steam condensate is collected with an interval of 50°F at a temperature of from 300 to 650°F. the Results are presented on the figures in the form of charts, showing the total percentage of chloride in 10 g of steam condensate (axisyagainst temperature (axisx)).

In the presence of water at high temperature (300 to 650° (F) hydrolysis of salts of metal chlorides in accordance with the following three typical responses:

Magnesium chloride:MgCl2+ 2H2O → Mg(OH)2+ 2HCl
Calcium chloride:CaCl2+ 2H2O → Ca(OH)2+ 2HCl
Sodium chloride:NaCl+ H2O → NaOH + HCl

The hydrolysis of the three chlorides of metals in mineral oil is shown in figure 1. Samples containing 210 ppm Cl in the form of MgCl2.6H2O, 244 ppm Cl in the form of CaCl2.2H2O and 1450 ppm Cl as NaCl. There are very low rates of hydrolysis of the chlorides of sodium and calcium, while the rate of hydrolysis of uranyl chloride magnesium reaches its maximum at a temperature of from 400 to 500°F and is probably the result of the formation of hydroxychloride magnesium, education which slows down the rate of hydrolysis.

The overall efficiency of hydrolysis of the metal chloride to chlorotoluron the Oh of the acid is determined relative to the contaminants, which can act either as catalysts or inhibitors of the reaction. The most significant contaminating impurity is naphthenic acid, which is ten times increases the hydrolysis of sodium chloride and calcium. As shown in figure 2, the effect of all other contaminants presents- - - -. In addition to the naphthenic acid content of other pollutants is as follows: 0.7 wt.% FeO, 1.0 wt.% FeS, 0.6 wt.% SiO2and 2.0 wt.% drilling pollution.

Figure 3 shows the ability of the naphthenic acids to accelerate the hydrolysis of sodium chloride, as a rule, a stable salt.

Example 1

This example shows the effectiveness of the application of the method according to the invention for reducing hydrolysis of calcium chloride in hydrocarbons, such as diluted bitumen. In one case, the diluted bitumen containing 0,291 g of calcium chloride, but not containing the processing agent (inhibitor), is subjected to steam distillation as described above. In another case, the same diluted bitumen together with 4 g inhibitory agent, which is najosnovnija calcium, having a common main room 400, also subjected to steam distillation. The obtained results are presented graphically in figure 4. As can be seen, in the absence of inhibitor substantial hydrolysis of chlorine is IDA calcium occurs at a temperature of 450° . Conversely, in the sample containing the processing agent, no significant hydrolysis of calcium chloride.

Example 2

This example shows the ability of the method according to the invention to prevent the hydrolysis of the mixed chlorides in synthetic raw materials. Synthetic raw material has the above composition, such as mineral oil containing iron oxide, iron sulfide, silicon oxide and drilling pollution in quantities indicated in figure 2. The total amount of mineral oil containing 3.5 g of sodium chloride, 1.0 g of calcium chloride, 0.5 g of magnesium chloride and 8 g of naphthenic acid, 800 ml of the Applied agent is a compound of adenosine magnesium, having a total basic number 600. A sample of synthetic raw materials containing chlorides and not containing agent, is subjected to the above distillation with water vapor. The second sample is also subjected to distillation with water vapor, except when contained three parts of the inhibitor in five parts total chloride content. Was conducted a third experiment in which the content of the inhibitor is six parts to five parts of common salt content. The results are shown in figure 5. As follows from the data shown in figure 5, without the use of any processing agent hydrolysis of chlorides in synthetic raw materials on inalsa at a temperature of approximately 250 to 300° F. When using the three parts of the agent in five parts salt hydrolysis is greatly reduced, while its peak is at the level of approximately 400°F. using six parts agent in five parts salt hydrolysis is reduced to the point at which produces a minimal amount of hydrochloric acid.

1. The way to reduce hydrolysis of the hydrocarbon stream, comprising introducing a hydrocarbon stream containing chloride compound, a hydrolyzable at elevated temperatures and in the presence of water with the formation of hydrochloric acid, an effective amount of an agent comprising at least one nadobny complex metal salt and a complexing reagent on the basis of organic acids, with the specified agent is injected into the specified hydrocarbon stream, when the stream has a temperature below which there is a substantial hydrolysis of the specified chloride-containing compounds.

2. The method according to claim 1, wherein the hydrocarbon stream is selected from the group that includes crude oil, shale oil and kerosene.

3. The method according to claim 2, in which the hydrocarbon stream includes crude oil.

4. The method according to claim 2, in which the hydrocarbon stream includes shale oil.

5. The method according to claim 2, in which the hydrocarbon stream includes kerosene.

6. The method according to claim 1, wherein processing the Gent is added to the hydrocarbon stream at a temperature below approximately 400° F.

7. The method according to claim 6, in which after adding a processing agent to the hydrocarbon stream is subjected to temperatures in the range from 600 to 750°F.

8. The method according to claim 1, in which the chloride compound includes a metal chloride.

9. The method according to claim 8, in which the chloride compound comprises a chloride of alkali or alkaline earth metal.

10. The method according to claim 1, wherein the metal salt is a salt of magnesium.

11. The method according to claim 10, in which the complex is a stable oil, colloidal dispersion.

12. The method according to claim 11, in which the complex forms a colloidal dispersion in the hydrocarbon stream.

13. The method according to claim 10, in which the metal salt is an oxide or magnesium carbonate.

14. The method according to claim 10, in which the complexing agent based on organic acid is a carboxylic acid, sulfuric acid or phosphoric acid.

15. The method according to claim 10, in which the agent is a complex of magnesium salts and complexing reagent magnesium salts of organic acids.

16. The method according to claim 1, wherein the hydrocarbon stream contains naphthenic acid.

Priority points and features:

29.04.2002 according to claims 1, 2-16;

21.02.2003 on the basis of claim 1 "when the specified agent is injected into the specified hydrocarbon stream, when the stream has a temperature of below to the Torah is significant hydrolysis of the specified chloride-containing compounds".



 

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