MXPA97008014A - Method for the supply, in steam phase, of anti-cranks for heating - Google Patents

Abstract

The present invention relates to a method for preventing the incrustation and formation of coke on the sections that are at high temperatures, of equipment for processing hydrocarbons, which come into contact with a hydrocarbon fluid. The method comprises adding to a carrier, before the carrier comes into contact with the sections at high temperatures of the equipment, an effective amount of an antiscaling agent in its vapor phase, selected from the group consisting of tri-tertiary butylphenol phosphate esters and compounds having the formula I: wherein Q is Z or R with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms, and only one or two occurrences of R may be alkyl, Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 may be alkyl and "n" is a whole number from 1 to 9, and mixtures of the same

Description

FIELD AND BORROWER OF THE I NVENC ION The present invention relates to a method for reducing fouling on the surfaces of the equipment used in the treatment at high temperatures, of petroleum fluids, which comprises treating the refinery equipment, which works at high temperatures, or the petroleum fluid. which is being processed in refinery equipment, at high temperatures, with at least about 5 parts per million phosphate ester of tri-t-butylphenol or a compound having the formula I: I wherein Q is Z, or R, with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms and in the most preferred form of 1 to 4 carbon atoms, and only one of the two occurrences of R can REF .: 025953 be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R, and only one of the two occurrences of each of R2 or R3 can be alkyl, and "n" is an integer from 1 to 9, preferably from 1 to 5, and in the most preferred form, "n" is an integer from 1 to 3. In an especially preferred embodiment of the invention, "n" is 1, and R, R2 and R3 represent hydrogen.

INTRODUCTION This invention relates to a method for the treatment of refinery equipment at high temperatures or fractions of petroleum processed at high temperatures, in that equipment, to minimize the formation of scale and coke in the equipment. The term "oil fractions" encompasses crude oil, crude oil residues such as residues from a vacuum operation, and other petroleum fractions such as diesel, which are heated in the presence or absence of hydrogen, in a manner to obtain thermo-fractionation products, with a lower boiling point, or to improve the handling of the material thus treated. Likewise, the additives of this invention can be successfully used to reduce the coke scale, in the pyrolysis or thermofraction furnaces, used for the manufacture of ethylene from various petroleum, gaseous and liquid fluids. The additives of this invention are the phosphate ester of tri-t-butylphenol or the phosphate esters of monoalkyl and dialkyl, aryl, alkaryl, cycloalkyl, alkenyl, and aralkyl. The phenol phosphate esters of this invention can be monomeric or can be oligomeric, such as where "n" in the above formula is an integer greater than about 1. In the treatment, at high temperatures, of crude oil or its fractions, and the like, the incrustation occurs in the furnace coils, in the transfer lines, and in the exchangers, due to the coqui fication and the deposition of polymers. The fouling problem is a major operational difficulty experienced when ethylene plants are put to work, and in processes where heavy grades of oil are treated, to reduce their molecular weight or to improve their handling characteristics, including, but not limited to, viscosity reducers, fluid or delayed coke operations, integrating hydrotreaters / hydrodes, and other processes. Depending on the rate of deposition, the operation, periodically, of all furnaces used to heat-fraction petroleum fluids, including ethylene plants, viscosity reducers, and the like, must be stopped for cleaning. The term "fluid", as used herein, is intended to include the term "feed". In addition to the periodic cleaning program, stoppages are sometimes required in the operation of the equipment, due to sudden increases in pressure or temperatures, which result from the formation of deposits on the coils of the furnace and in the exchangers of the transfer lines. Cleaning operations are expensive, both from the point of view of time, as well as from the point of view of work, and they are typically carried out, either mechanically, or by a steam / air bursting step. In the mechanical cleaning operation, which is also referred to as "addition of pig iron for raising the temperature", the deposits are subjected to the action of a brush or scraped, or otherwise mechanically removed from the surface of the equipment that is in contact with the fluids and the reaction products. The cleaning method, which is referred to as "breakage by temperature variation", is one in which the temperature of the heater tubes rises and falls several times. Due to the difference in the shrinkage and expansion coefficients, the material of the pipe and the coke deposits, the coke deposits are broken, allowing them to detach from the pipes, the breaking process by temperature variation, it could be followed by a step in which a stream of air, steam or a mixture of them is blown through the equipment. During this step, the equipment is maintained at temperatures typically ranging from about 500 ° C to about 600 ° C. Typically, steam is injected first. The steam reacts with the coke deposits, burning the vapors and converting them into carbon oxides. After hours of steam treatment, most of the coke has normally been burned. To eliminate the remaining coke, air is added gradually to the steam. Various additives have been used to try to minimize the formation of scale in the processing, at high temperatures, of fractions of crude oil. Suggested materials include the monoalkyl and dialkyl phosphate, aryl, alkaryl, cycloalkyl, alkenyl, and aralkyl esters, such as those exemplified in U.S. Patent No. 4,105,540. Other materials that have been used include the phosphate or acid phosphate esters of alkyl, in combination with thiodipropionates, such as those exemplified in U.S. Patent No. 4,226,700, and the monophosphate and diphosphate esters, and the phosphate esters, described in U.S. Patent Nos. 4,024,048, 4,024,049, 4,024,050 and 4,024,051. Although these phosphate materials, in general, have been used successfully in some plants, the use of these materials has proved unsatisfactory, leading to the presence of corrosion in units that have been treated with these materials. It is speculated that, although they are effective as anti-scalants, the phosphite esters and the monophosphate and diphosphate esters suggested by the prior art are hydrolyzed at high temperatures, producing acid products of corrosion. In the related, co-pending application, serial No. 08 / 427,915, filed April 26, 1995, the use of certain t-butylphenol phosphate esters as anti-scalants is described. It is also discovered, in that application, that the compounds have the formula I: wherein Q is Z, or R, with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group, having 1 to 7 carbon atoms and most preferably from 1 to 4 carbon atoms, and only one of two of the occurrences of R may be alkyl; Z is represented by formula II: p wherein R2 and R3 are the same as R and only one of the two occurrences of each of R2 or R can be alkyl, and "n" is an integer from 1 to 9, preferably from 1 to 5, and in the More preferably, "n" is an integer from 1 to 3, they are good anti-fouling agents. In an especially preferred embodiment of the invention, "n" is 1, and R, R2 and R3 represent hydrogen. Phosphate esters act as passivators under certain injection conditions. Once the metal surfaces of the hydrocarbon process equipment are free of deposits, the antifreeze is introduced to the equipment as a vapor and mixed with a stream of air, steam, inert gas such as nitrogen, hydrocarbon gases. , or a mixture thereof. If the anti-fouling agent has a high stability to oxidation, hydrolytic stability, and is present in the stream in the form of a diluted vapor, the antifoulant decomposes or degrades at high temperatures, in a specific way, when it is put in Contact with the metal surface of the tube. The fragments of the decomposition form a film that has coke-removing characteristics (in the form of a passivating film). The antiscalant is generally injected as a mixture with air stream, steam, inert gas such as nitrogen, hydrocarbon gases, or a mixture thereof. The injection of the antifouling can be continued with the introduction of the hydrocarbon fluid. In addition, the injection of the anti-fouling agent can be started and maintained during the injection of the hydrocarbon fluid, without first having to first passivate the surfaces of the equipment that comes into contact with the hydrocarbon fluid. Therefore, an object of this invention is to provide the technique, a method for preventing and inhibiting the formation of scale, on the surfaces that are in contact with the hydrocarbon fluids defined herein as liquid, gaseous hydrocarbons, or mixtures thereof. A further objective of this invention is to provide the art with a method for inhibiting fouling in the processing, at high temperatures, of hydrocarbon fluids, especially crude oil fractions. Yet another objective of this invention is to provide the art with a method for preventing scale fouling in the high temperature section of the oil processing equipment, including viscosity reducers, delayed coke former, kiln preheater for ethylene, and the like, using an effective amount of tri-t-butylphenol phosphate esters or compounds having the formula: Q i wherein Q is Z, or R, with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group, having 1 to 7 carbon atoms and most preferably from 1 to 4 carbon atoms, and only one or two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R, and only one of the two occurrences of each of R2 or R3 can be alkyl, and "n" is an integer from 1 to 9, preferably from 1 to 5, and in the most preferred form, "n" is an integer from 1 to 3. In an especially preferred embodiment of the invention, "n" is 1, and R, R2 and R3 represent hydrogen.

BRIEF DESCRIPTION OF THE INVENTION This invention is therefore directed to a method for preventing fouling and formation of coke, in the sections at high temperatures, of the equipment for the processing of hydrocarbons, which are in contact with a hydrocarbon fluid, which comprises adding to the hydrocarbon fluid, before it makes contact with the sections at high temperatures, of the equipment for the processing of hydrocarbons, an effective amount of tri-t-butyl phenol phosphate ester or a compound having the formula I: Q Q wherein Q is Z, or R, with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group, having 1 to 7 carbon atoms and most preferably from 1 to 4 carbon atoms, and only one or two occurrences of R can be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one or two occurrences of each of R2 or R3 may be alkyl, and "n" is an integer from 1 to 9, preferably from 1 to 5, and in the form more preferably, "n" is an integer from 1 to 3. In an especially preferred embodiment of the invention, "n" is 1, and R, R2 and R3 represent hydrogen.

DESCRIPTION OF THE PREFERRED MODALITIES This invention is therefore directed to a method for preventing fouling and formation of coke, in the sections at high temperatures, of the equipment for the processing of hydrocarbons, which are in contact with a hydrocarbon fluid, which comprises adding to the hydrocarbon fluid, before it makes contact with the sections at high temperatures, of the equipment for the processing of hydrocarbons, an effective amount of tri-butyl phenol phosphate ester or a compound having the formula I: wherein Q is Z, or R, with the proviso that two occurrences of Q are Z, R is hydrogen, or a straight or branched chain alkyl group, having 1 to 7 carbon atoms and most preferably from 1 to 4 carbon atoms, and only one or two occurrences of R can be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one or two occurrences of each of R2 or R3 may be alkyl, and "n" is an integer from 1 to 9, preferably from 1 to 5, and in the form more preferably, "n" is an integer from 1 to 3. In an especially preferred embodiment of the invention, "n" is 1, and R, R2 and R3 represent hydrogen.

THE INVENTION Compounds that fall within the formula, as described above in the present invention, are commercially available. Among the available materials is a product designated as LDP-301, from FMC Corporation. It is believed that this product, by the use of chemical analysis, is a compound having Formula III with a small amount of structure IV. m IV It is established that the LDP-301, by its manufacture, is useful as a base fluid resistant to fire or an additive that prevents wear, highly stable. LDP-301 is also recommended for use as an additive in base fluids of carboxylic esters. It is established that the LDP-301 has the following physical properties, which are presented in Table I below: TABLE I The tri-t-butylphenol phosphate esters, used in the process of this invention, are materials that are commercially available. In the practice of this invention, it is preferred to use a material sold by FMC Corporation under the tradename Durad "620 B. Table II lists physical properties of this material, provided by the manufacturer.

TABLE II Although the phosphate ester, trimers, t-butyl and unsubstituted materials are exemplified in the related application, serial No. 08 / 427,915, filed April 26, 1995, which is incorporated subsequently by reference, in this specification, it has now been demonstrated that other compounds such as cyclophosphazine (X-1P, from Dow Chemical Company), and other oligomeric phosphate ester materials, such as those described in Formula I of the present application, also they have a higher activity as antifouling materials, for refineries, by injection in vapor phase. One embodiment of the invention is a method for preventing fouling and formation of coke, in the sections at high temperatures, of the equipment for the processing of hydrocarbons, which come into contact with a hydrocarbon fluid. The method comprises adding to a carrier, typically a stream of air, steam, or a mixture thereof, before the carrier comes in contact with the high-temperature sections of the equipment for processing hydrocarbons, a effective amount of an antiscaling agent in its vapor phase, selected from the group consisting of tris-tertiary butylphenol phosphate esters and compounds having the formula I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q are Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms , and only one of two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9, and mixtures thereof. The high temperature section of the equipment for the processing of hydrocarbons must be operated at a temperature of at least 240 ° C to vaporize the antifreeze before the antifreeze makes contact with the surfaces of the process equipment. The equipment for the processing of hydrocarbons, which benefits from this invention, is selected from the group consisting of: viscosity reducers; delayed coke formers; preheater; ovens; transfer lines; exchangers; catalytic fluid disintegrators; hydrotreators; hydrodisintegrators; and furnace coils, specifically, but not limited to those units in front of catalytic units (examples of catalytic units are the catalytic fluid disintegrators (FCC) and the hydrodisintegrators). Another embodiment of the present invention is a method for preventing the incrustation and formation of coke on the surfaces of the sections at high temperatures, of the equipment for the processing of hydrocarbons, which comes into contact with a hydrocarbon fluid. The processing equipment and / or the carrier must be operated at a temperature of at least about 240 ° C. The method comprises adding an effective amount of an antimicrobial in its vapor phase, selected from the group consisting of tris-tertiary butylphenol phosphate esters and compounds of the following formula I, to a carrier stream, before it makes contact with the equipment used for the processing of hydrocarbons: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q are Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms , and only one of two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9, and mixtures thereof. The antifreeze is added to the equipment for the processing of hydrocarbons, in a carrier selected from the group consisting of: steam; air; hydrocarbon gases; inert gases, such as nitrogen; and mixtures thereof. The stream of the carrier, which contains the antifouling, can be added to a hydrocarbon fluid before it makes contact with the sections at high temperatures, of the equipment for the processing of hydrocarbons, it can be injected into the high-temperature sections of the equipment to the processing of hydrocarbons when a hydrocarbon fluid is not being processed or can be injected into the sections at high temperatures, of the equipment for the processing of hydrocarbons, both before and during the processing of a hydrocarbon fluid. The addition of the anti-fouling agent, in the presence or absence of the hydrocarbon fluid, can be injected into the sections at high temperatures, of the equipment for the processing of hydrocarbons, on a continuous base or on an intermittent basis. The processing equipment that can benefit from the present invention includes viscosity reducers; delayed coke formers; preheater; ovens; transfer lines; exchangers; catalytic fluid disintegrators; hydrotreators; hydrodisintegrators; and furnace coils, specifically, but not limited to those units in front of catalytic units (including fluid catalytic disintegrators and hydrodisintegrators). The antifreeze can be added to the carrier currentof air, steam, or mixtures thereof, before the introduction of the carrier to an ethylene furnace or to a viscosity reducer. Another embodiment of the invention is a method for inhibiting the formation of coke on the surfaces of sections at high temperatures, of equipment for the processing of hydrocarbons that is in contact with the hydrocarbon fluid, which comprises: a. descoquif icar the equipment for the processing of hydrocarbons; b. before subjecting a hydrocarbon fluid to process, add to the process equipment, an antiscaling agent in its vapor phase, selected from the group consisting of: 1. tri-tertiary butylphenol phosphate esters; 2. compounds having the formula I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms , and only one of two occurrences of R may be alkyl; Z is represented by formula II: p wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and, 3. mixtures thereof; c. form a thin layer of coke on the surfaces of the process equipment; and then, d. feed the hydrocarbon fluid to the process equipment.

The addition of the antifouling can 'Discontinue during the processing of the hydrocarbon fluid, or it may be discontinued before the processing of the hydrocarbon fluid. The anti-fouling agent can be added intermittently, before processing the hydrocarbon fluid, or continuously, before processing the hydrocarbon fluid. The antifouling can also be added intermittently during the processing of the hydrocarbon fluid, or continuously during the processing of the hydrocarbon fluid. The hydrocarbon fluid typically contains at least one fraction selected from the group consisting of: ethane; propane; butane; naphtha; kerosene; diesel oil; and, residue. The antifreeze is added to the process equipment, in a carrier selected from the group consisting of: steam; air; hydrocarbon gases; inert gases; and, mixtures thereof. The antiscaling agent is preferably added in a range from about 0.0005% to less than about 10% based on the% volume or% mol, of the carrier stream, before the hydrocarbon fluid processing, most preferably in a range from about 0.001% to less than about 10% based on the volume% mass flow of the hydrocarbon fluid, during the processing of the hydrocarbon fluid, and most preferably in a range from about 0.005% to less than about 10% based on the% volume or mol% of the carrier gas, during the previous passivation, and from approximately 5 to approximately 2,000 parts per million (ppm) based on the mass of the hydrocarbon stream, during maintenance dosing.

It is important, as discussed above, that during the addition of the antifouling, the process equipment is maintained at a temperature of at least about 240 ° C. The process equipment is operated or operated, typically, between the temperatures of about 200 ° C and about 1,200 ° C. Another embodiment of the invention is a method for inhibiting the formation of coke on the surfaces of the sections at high temperatures, of the equipment for the processing of hydrocarbons, which are in contact with the hydrocarbon fluid, which comprises: a. processing a hydrocarbon fluid, in the presence of an antifoulant, in its vapor phase, selected from the group consisting of: 1. tertiary butylphenol phosphate esters; 2. compounds having the formula I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms, and only one of two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and, 3. mixtures thereof; and, b. forming a thin layer of coke on the surfaces of the process equipment, whereby the surfaces of the process equipment are inhibited against the formation of additional coke, during the processing of a hydrocarbon fluid.

The antifouling can be added intermittently, during the processing of the hydrocarbon fluid, or continuously, during the processing of the hydrocarbon fluid. The hydrocarbon fluid may contain at least one fraction selected from the group consisting of: ethane; propane; butane; naphtha; kerosene; diesel oil; and, residue. The antifouling can be added in a range from about 5 to about 2,000 ppm, based on the mass flow of the hydrocarbon fluid, during the processing of hydrocarbon fluid. During the addition of the antifoulant, the process equipment must be maintained at a temperature of at least about 240 ° C. Another embodiment of the present invention is a method for increasing the duration of the run or maneuver in the equipment for the processing of hydrocarbons, used to process a hydrocarbon fluid, which comprises: a. decoding the process equipment; b. before subjecting a hydrocarbon fluid to process, add to the process equipment an antiscaling agent in its vapor phase, selected from the group of: 1. tri-tertiary butylphenol phosphate esters; 2. compounds having the formula I: I wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched decadal alkyl group, having from 1 to 7 carbon atoms, and only one of two occurrences of R may be alkyl; Z is represented by formula II wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and?, n "is an integer from 1 to 9, and, 3. mixtures thereof; c) form a thin layer of coke on the surfaces of the process equipment, which are in contact with the hydrocarbon fluid, and then, d) feed the hydrocarbon fluid to the process equipment, whereby the surfaces of the process equipment they are inhibited against the formation of additional coke during the processing of the hydrocarbon fluid, thereby increasing the duration of the run or maneuver in the process equipment Another embodiment of the present invention is a method for increasing the yield of the product, of the processing of a hydrocarbon fluid, through the equipment for the processing of hydrocarbons, which includes: a) decooking the process equipment, b) before submitting a hydrocarbon fluid to the process, adding an anti-chemical in its vapor phase, selected from the group of: 1. tri-tertiary butyl phenol phosphate esters; 2. compounds having the formula I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms , and only one of two occurrences of R may be alkyl; Z is represented by formula II: O wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and, 3. mixtures thereof; c. forming a thin layer of coke on the surfaces of the process equipment, which are in contact with the hydrocarbon fluid; and then, d. feeding the hydrocarbon fluid to the process equipment, whereby the surfaces of the process equipment are inhibited against the formation of additional coke during the processing of the hydrocarbon fluid, thereby increasing the yield of the hydrocarbon fluid processing product , through the process team. In the process of this invention, the antifouling materials, represented by Formula I and the description of the phosphate ester of tri-t-butyl phenol, are generally added to a fraction of the petroleum which will be subjected to a high temperature process operation, in an amount to provide from about 5 ppm to about 2,000 ppm of active, preferably from about 5 ppm to about 1,000 ppm active, most preferably from about 5 ppm to about 500 ppm active, and in most preferred form from about 5 ppm to about 100 ppm of anti-foulant active, or mixtures thereof, as represented in Formula I or the tri-t-butylphenol phosphate ester as added to the hydrocarbon stream, prior to introduction from the stream to the process area at high temperatures, from the equipment for the processing of hydrocarbons, in d The current will be subjected to relatively severe conditions that can lead to the formation of polymers or coke. The additives of this invention are generally soluble in the hydrocarbon fluid to which they are applied, and to make their application easier, they can be diluted with common solvents such as kerosene, heavy aromatic naphtha, or the like, before their introduction to the system. . Surprisingly, the material acts as an antiscaling agent in the processing of petroleum fractions, at high temperatures, to which they are added.

What is meant by the term processed at high temperatures, is that they are temperatures that vary from a temperature as low as approximately 100 ° C, the boiling point of water, to approximately 1,000 ° C or higher. Generally the additive of this invention is added to the hydrocarbon fluids which will be subjected to temperatures of up to about 330 ° C (about 626 ° F) at atmospheric pressure, which is the approximate temperature at which thermo-fractionation starts. As stated at the beginning, the antifouling process of this invention can be applied to a wide variety of process operations, which are carried out at high temperatures. Among the operations of the oil processing to which the present invention may find applicability, are those operations wherein high molecular weight materials are thermocracked to produce low molecular weight materials or to lower their viscosity. These operations include hydrotreating, hydrodisintegration, coke formation, viscosity reduction, steam disintegration, reformation, and the like. The materials can also be used in the feed materials, which go to the pyrolysis or thermo-disintegration furnaces, for the manufacture of ethylene, and the like. Additives can be added to delayed coke formers, preheater, furnace, refinery pipeline, equipment top line, and other sections where hydrocarbon fluids are subjected to process, high temperature or heated to high temperatures. The additives can also be added to the effluent of hydrocarbon fluids, which leaves the operations described above. Also, the operating units that could benefit from the treatment with the present invention are furnaces that are associated with atmospheric and vacuum distillation towers, and other units that heat the crude oil before processing. It is believed that the addition of the claimed materials, tri-t-butyl phenol phosphate ester, of the compound represented by Formulas I and II, to the equipment for the processing of hydrocarbons, during the cleaning steps when the equipment is out of line or stopped (the hydrocarbon stream feed has been stopped) or the hydrocarbon stream or effluent from a process section at high temperatures, is particularly beneficial since it is believed that sections at high temperatures destabilize certain components in the fluids of hydrocarbons thus treated, and that the additive of this invention acts to prevent the formation of coke and scale, on the sections of the equipment that are in contact with the hydrocarbon fluids, hot, as they leave the heated sections. The present invention, characteristically, can be advantageously carried out in practice with any crude petroleum material, such as one selected from the group consisting of crude oils and reduced crude oils. Typically, the phosphate ester materials of this invention are added to a crude petroleum material, at a lower level from about 5 ppm based on the total weight, to about 2,000 ppm based on the total weight, as the upper limit . It should be noted that the upper limit will be limited by economic aspects, and not by the effect of the additive, and quantities greater than approximately 2,000 ppm of the additive may be added. Preferably, the total amount of the additive of this invention, added during the cleaning step or to the hydrocarbon fluid material, ranges from about 5 to about 2,000 ppm (on the same basis). In the processing of crude oils, the heating times can vary enormously, as those skilled in the oil refining technique will readily appreciate, but generally they are in the range from approximately a few seconds to several hours, although longer and shorter times can be involved. As used herein, the term "crude oil" may be considered to refer to materials used as initial fluids for a crude oil refining operation, such as a petroleum having a composition that is substantially found in nature, and that that composition has not been altered appreciably by the use of distillation or pyrolysis. Examples of crude oils include many materials, such as crude oil from a refinery's battery limits (for example, crude oil as it exists in storage containers, which precede refining), degassed crude oils (for example, a crude oil that has been depleted at temperatures that are typically above the range of from about 75 ° F (23.9 ° C) to about 125 ° F (51.7 ° C), to remove low boiling point hydrocarbons, such as lower alkanes and other low-boiling volatiles), crude sand impregnated with pitch (for example, a product obtained from a destructive distillation of a tar sand), condensed crude (for example, a crude oil obtained by the condensation of the final products). heavy, from a natural gas well), bituminous shale oil (for example, crude oil obtained from a natural gas well), shale oil bit uminous (for example, crude oil obtained from oil shale by destructive distillation, followed by hydrogenation), raw, untreated oils (for example, a crude oil that has undergone a process whereby the content of mineral salts present in an initial crude oil, it is typically reduced to a salt content of not more than 5 pounds per 1,000 barrels, although the amount of salt remaining in the desalted crude oil can vary widely such that those experienced in petroleum technology sometimes they overlap the intervals they mention, so that it is not well defined. The initial crude oil fluids, preferred in the present invention, include the oil from battery limits, degassed crude oil, and de-fired crude oil. Similarly, it can be considered that, as used herein, the term "reduced crude oil" refers to an initial crude oil, which has been subjected to distillation at temperatures that are generally above those used for producing a degassed crude oil, using temperatures as those indicated above, such as a residual crude oil (usually a liquid) that has not been substantially altered except as a result of heating and removal of material therefrom by distillation of the product of pyrolysis. Examples of reduced crude oil include a wide variety of materials as will be readily appreciated by those skilled in the art, such as crude petroleum residues (eg, a product resulting after gas oils boiling in the range of about 400 ° F ( 204.4 ° C) to approximately 575 ° F (301.7 ° C), have been removed from a crude oil by fractional distillation), atmospheric residues (for example, a product that results from the fractional distillation of a crude oil in a tubular heater and which boils above a temperature that is in the range from about 350 ° F (176.7 ° C) to about 650 ° F (343.3 ° C), viscous tars (for example, a product resulting from a fractional distillation of a atmospheric residue in vacuum equipment and boiling above a temperature that is in the range of approximately 1,000 ° F (537.8 ° C) to approximately 1,500 ° F (815.6 ° C), at pressures from about 1 psig (0.070307 Kg / cm) to about 5 psig (0.35 kg / cm). Viscous tars can be considered to include coke-forming fluids. The reduced crude oils, preferred herein, include crude oil residues, atmospheric debris and viscous tars. The processing of crude oil materials, in a refinery, is a relatively well developed technique. Characteristically and usually, the processing of crude oil comprises a series of successive steps. These steps, characteristic and preferably, are as follows: A. heating a crude oil in at least one heat exchanger, to a temperature typically in the range of from about 100 ° F to about 200 ° F, B. desalify crude oil, typically and preferably, through the secondary steps of (1) turbulently mixing the crude oil which has preferably been preheated first, as indicated above and as is typical, with an amount from about 3 to about 8 parts by weight of water per 100 parts by weight of the crude oil, to form a water-in-oil emulsion, (2) break that emulsion through the use of chemical agents, media electric, or some combination thereof, and (3) Separate the resulting aqueous phase from the oil phase resulting crude, C. Additional heating of the resulting crude oil, in at least one subsequent desalter exchanger, up to a temperature that is Typically in the range from about 200 ° F to about 500 ° F, D. further heating, in an additional manner, the resulting crude oil, in a furnace, to a temperature that is typically in the range of from about 500 ° F to about 700 ° F, 10 E. charging the crude oil so heated, to an atmospheric distillation equipment, where that crude oil is distilled, in a fractional way, Progressively, at temperatures typically in the range of from about 300 ° F to about 650 ° F, under pressures that would typically be from pressures that include atmospheric pressure up to approximately 50 p.s. i. a and collect the distillates until an atmospheric residue results which boils over a The temperature typically lies in the range from about 300 ° F to about 650 ° F, F. heating the atmospheric residue in a vacuum oven, to a temperature typically in the range of from about 650 ° F to about 800 ° F, while maintaining a pressure below atmospheric, typically from about 5 to about 14 ps i. a, 15 G. Charge the atmospheric residue, thus heated, to a vacuum distillation equipment, where that atmospheric residue is distilled progressively by fractional distillation, at a temperature typically in the range of from about 800 ° F to about 1100 ° F, under a pressure that typically ranges from about 1 to about 5 p.s. i. and collecting the distillates until a viscous tar results which typically boils in the range from about 1000 ° F to about 1500 ° F at a pressure below atmospheric typically ranging from about 1 to about 5 p.s. i. a, and H. progressively heating the viscous tar in an area that is at temperatures that typically range from about 860 ° F to about 900 ° F, at pressures that typically range from about 50 to about 350 psi, for a time ranging from about 1. second until approximately 1/2 hour.

In the case of step (H), the heating can occur either in a zone of a coke former or in a thermofraction zone. In the case of a zone of a coke former, the heating is pyrolytic, and the distillates are brought together, until a final solid residue which is a coke is obtained. In the case of a thermo-fractionation zone, the process involved is called "viscosity reduction" and the distillates are brought together without changing the fluid nature of the initial viscous tar (as is the case with coke formation). the residence times of the charged material (initially viscous tar) in a zone of the coke former typically lengthen for periods of time greater than about 10 seconds, and the common coking times vary from about 45 minutes to about 4 hours. the residence times of the initial tar, in a viscosity reducing operation, in a thermofraction zone, typically they are less than about 10 seconds, at most. In the steps of processing crude oil, described above, a coke-forming furnace can follow step (G) and precede step (H) in such a way that after step (G) the following sequence of process steps occurs, after step (G) in place of step (H): (H) heating the viscous tar in an oven, to a temperature in the range from about 538 ° C to about 816 ° C (from about 100 ° F) to about 1500 ° F) at a pressure close to atmospheric, and passing the tar thus heated, to a zone of abrupt expansion, at temperatures typically ranging from about 860 ° F to about 900 ° F, at pressures that typically vary from approximately 50 to approximately 350 psig That zone of abrupt expansion can be either an area of a coke former or a viscosity reduction zone, as indicated above. If it is a zone of coke former, the residence time in these areas is prolonged and pyrolysis occurs. If it is a zone of viscosity reduction, the residence time is short and thermocracking occurs, giving rise to naphtha and diesel as light products and producing a residue that is less viscous than the filler material. These process steps, crude oil and reduced crude oil, as indicated, are well known in the petroleum refining art and do not constitute as such part of the present invention. Those skilled in the art will appreciate that many variations, etc., can be used in any hydrocarbon processing operation, involving for example, additional steps, substitute steps, recycling loops, and the like. The above summary is merely representative but characteristic of the sequence of steps typically found in a refinery when processing crude oil. Oil processing is discussed in certain reference works such as Nelson's entitled Pe trol eum Refinery Engineering, see, for example, chapter 7, pp. 248-260; chapter 8, pp. 265-268; chapter 17, pp. 547-554; and, chapter 19, pp. 678-693. All these processing steps of crude oil characteristically cause incrustation of the equipment used for processing hydrocarbons, in the absence of an additive or the like, as those skilled in the art will appreciate well. The fouling deposits appear to occur, more frequently, at temperatures ranging from about 93 ° C to about 982 ° C (about 200 ° F and about 1800 ° F) or even higher such as, for example, in certain ethylene furnaces . The types of equipment affected more frequently include heat exchange surfaces, such as those indicated above. The encrusting deposits as such are typically and principally polymerization products and in characteristic form are black. some are initially sticky masses that turn into coke-like masses at elevated temperatures. The inorganic portions of these deposits frequently contain components such as silica, iron oxides, sulfur oxides, iron sulphides, calcium oxide, magnesium oxide, inorganic chloride salts, sodium oxide, alumina, sodium sulfate, oxides of cr, cr salts, and the like. These deposits are not easily solubilized by common organic solvents and these deposits can be distinguished from corrosion and mud formation, which sometimes occur in the final products. Antioxidants, stabilizing chemicals, and the like, conventional, are relatively, and characteristically, ineffective as anti-inflammatory. During a distillation or pyrolysis carried out with a crude petroleum material containing material of Formula (1) and / or (2), this additive material does not characteristically creep into the vapors emitted, but remains nonetheless, in the residue involved. (reduced crude oil). In that reduced material, of course, physical and chemical changes may occur, during a distillation or pyrolysis operation, given, but it is now speculated (and in the present it is not intended to find a theory for this) that the by-products, products of degradation, and the like, are not appreciably carried away by a vapor phase current removed during a distillation or pyrolysis operation of a reduced crude oil.

The following procedures are presented to describe preferred embodiments as well as preferred utilities of the invention and are not intended to limit same unless stated in the appended claims. One method in which the claimed materials could be applied is that of heating heaters wherein the hydrocarbon fluid (hydrocarbon feed) is heated to a minimum temperature of about 240 ° C within the thermal units. That equipment includes, but is not limited to, oil heaters, vacuum heaters, viscosity reduction heaters, and retard coke formers. The fluid is heated in the heater section of the equipment, to a pre-selected temperature. In the case of a delayed coke-forming heater, the heater load is heated such that thermofraction occurs in the reactor located at a later site (which is also referred to as a cylindrical tank for coke). However, a certain amount of heat fractionation is carried out in the heater and this leads to the undesired formation of deposits (coqui fication) the light products leave the cylindrical tank for coke, through the line of the upper part, of the former of coke, and are loaded as recycled, back to the bottom of the fractionator. There they are combined with the non-recycled material and are reloaded to the heater. As coke is formed in the heater, the coke acts as an insulator, thereby decreasing the heat transfer process with the equipment. As a result, the equipment must be heated more intensively to maintain the outlet temperature in the heater. However, the equipment has a critical operating temperature, from approximately 1250 ° F to approximately 1350 ° F, above which the equipment can not operate safely. At that time the operation of the equipment must be maintained and one or more of the cleaning methods described above carried out. A maneuver in refinery equipment that works at high temperatures, between cleaning procedures, lasts between 6 days to 4 years, and the average of that maneuver is approximately one year. In the refinery equipment that works at high temperatures, a passivation step can be carried out which involves treating the surface of the equipment that typically comes into contact with the hydrocarbon fluid, when the equipment is disconnected or out of operation, when the hydrocarbon fluid is not being processed. The refinery equipment can be passivated using the following procedure. The temperature of the heater must be maintained at a temperature sufficient to maintain the temperature of a hollow injection shaft located at a point before the heater inlet, at least at a temperature of 240 ° C. The hollow shaft needs to be positioned such that it can be maintained at a temperature of at least about 240 ° C due to the radiant heat of the heater or through some other mechanism. To maintain the temperature of the tubular structure at least at about 240 ° C, the heater, including the tubes at that location, should typically be maintained at least about 300 more preferably at about 400 ° C. The air flow, defined as the air flow necessary to move the hydrocarbon fluid, and other materials, through the tubes, should also preferably be kept heated to a temperature of at least about 200 ° C, before it enters the air. heater or before it makes contact with treatment materials such as the antifouling agents of the present invention. A typical flow of air is approximately 2000 feet / hour. The temperature of the air flow is extremely important if the condensation of the treatment materials has to be avoided. Once the air flow and temperatures stabilize, the pressure that is in the system will be approximately 40 pounds. The treatment materials, in this case, the claimed anti-foulants, are injected through the tubular structure at a concentration below about 10 volume percent (% mol). The antifouling is evaporated in the hollow shaft. As the vaporized antifouling reacts with the surface of the refining equipment, a film of coke scavenger material is formed on the surfaces of the refinery equipment. A more detailed description of the mechanism is present in the article "formation of solid films from the vapor phase, on surfaces that are at high temperatures" by James Makki and Earl Graham and published in the Journal of the Society of Tribologists and Lubrication Engineers, vol.47, 3, 199-206, incorporated herein by reference. The antifouling is fed to the heater at a rate of about 1.9 liters / day (0.5 gallons / day) to about 5.7 liters / day (3 gallons / day), more preferably from 1.9 liters / day (0.5 gallons / day to about 2 gallons / day), and most preferably from 3.0 liters / day (0.8 gallons / day) to about 4.5 liters / day (1.2 gallons / day), for a time from about 5 minutes to about 30 minutes, in a form more preferably from about 5 minutes to about 20 minutes, and most preferably from about 5 minutes to about 15 minutes. Longer periods of time such as 3 days or more may be employed depending on a wide variety of factors including the type of cleaning process, the process for hydrocarbons used, the type of equipment involved, and the condition under which the hydrocarbon process will be carried out. The feed flow rate of the antifouling can then be increased 'gradually so as not to interfere with the flow of air through the equipment or otherwise subject shock waves to the system. The feed rate is increased from about 1 gallon / day to about 2 gallons / day, more preferably from about 1.2 gallons / day to about 1.9 gallons / day, and most preferably from about 1.4 gallons / day to about 1.8 gallons / day. The feed rate, increased, for the antifouling, to the heater, should be maintained for at least a time ranging from about 30 minutes to about 1 hour, more preferably for a time of at least about 2 hours to about 3 hours , most preferably from about 4 hours to about 5 hours. As discussed above, longer periods of time such as up to 3 days or longer may be employed, depending on a variety of factors including the type of process, the cleaning, the hydrocarbon process to be employed, the type of the equipment being treated, the condition under which the hydrocarbon process will be carried out. More than one tubular injection structure can be used in this procedure. Multiple tubular injection structures promote a more uniform treatment of the equipment surface. An additional tubular structure could be placed at a later site, of the convection section, of the refinery equipment, such as in the tubes to absorb shocks; the tubes that connect the convection section with the radiant section. The heater must be maintained at a temperature sufficient to maintain the temperature of a tubular injection structure located at a site posterior to the inlet of the heater, at a temperature of at least about 240 ° C. The tubular structure needs to be positioned such that it can be maintained at a temperature of at least about 240 ° C by the radiant heat of the heater or through some other mechanism. To maintain the temperature of the tubular structure at a value of about 240 ° C, the heater, including the tubes at that location, should typically be maintained at a temperature of at least about 300 ° C, more preferably at about 400 ° C. . The air flow, defined as the air flow necessary to move the fluid of hydrocarbons and other materials, through the tubes, should also be maintained at a temperature of about 240 ° C, or preferably heated to at least that temperature, before of entering the heater or before it makes contact with the heating materials such as the antifouling agents of the present invention. The typical flow of air is approximately 2,000 feet / hour. The temperature of the air flow is extremely important if the condensation of the treatment materials should be avoided. Once the air flow and temperatures are stabilized, the pressure in the system will be approximately 40 pounds. The treatment materials, in this case, the claimed anti-foulants, are injected through the tubular structure at a concentration below about 10 volume percent (% mol). The antifouling is vaporized in the hollow shaft. As the vaporized antifouling reacts with the surface of the refining equipment, a film of coke scavenger material is formed on the surfaces of the refinery equipment. The antifoulant is fed to the heater at a rate of about 0.5 gallons / day to about 3 gallons / day, more preferably from 0.5 gallons / day to about 2 gallons / day, and most preferably from 0.8 gallons / day to about 1.2 gallons / day, for a time from about 5 minutes to about 30 minutes, more preferably from about 5 minutes to about 20 minutes, and most preferably from about 5 minutes to about 15 minutes. The feed flow rate of the antiscaling agent can then be increased gradually so that it does not interfere with the flow of air through the equipment or otherwise subject the system to shock waves. The feed rate is increased from about 1 gallon / day to about 2 gallons / day, more preferably from about 1.2 gallons / day to about 1.9 gallons / day, and most preferably from about 1.4 gallons / day to about 1.8 gallons / day. The feed rate, increased, for the antifouling, to the heater, should be maintained for at least a time ranging from about 30 minutes to about 1 hour, more preferably for a time of at least about 2 hours to about 3 hours , most preferably from about 4 hours to about 5 hours. Another location of a tubular injection structure, at the end of the radiant section. Using the "burn-in with inverted flow", where air is forced through the outlet of the radiant section. Using this procedure, the radiant section is coated more intensively with the film resulting from the reaction of the vaporized antifoulant and the surfaces of the refinery equipment. In addition, a continuous treatment of the antifouling can be used, wherein the antifoulant is injected with the hydrocarbon fluid. As described above, the heater must be maintained at a temperature sufficient to maintain the temperature of a tubular injection structure located at a site posterior to the heater inlet, at a temperature of at least about 240 C. The tubular structure needs to be positioned in such a way that it can be maintained at a temperature of at least about 240 ° C by the radiant heat of the heater or through some other mechanism. In order to maintain the temperature of the tubular structure at least at about 240 ° C, the heater, including the tubes at that site, typically should be maintained at a temperature of at least about 300 C, more preferably at a temperature of about 400 C. The air flow, defined as the flow necessary to move the flow of hydrocarbons and other materials, through the tubes, should also be maintained at a temperature of at least about 240 ° C, or preferably should be heated up to that temperature. temperature, before the heater enters or before it makes contact with the treatment materials such as the antifouling agents of the present invention. The typical flow of air is approximately 2000 ft3 / hour. The temperature of the air flow is extremely important and the condensation of the treatment materials must be avoided. The hydrocarbon fluid feed begins. Once the airflow, hydrocarbon fluid feed and temperatures are stabilized, the pressure in the system will be approximately 40 pounds. The antiscalant is injected through the tubular structure at a concentration below about 10 volume percent (% mol). The antifouling is evaporated in the tubular structure. As the vaporized antifouling reacts with the surface of the refinery equipment, it forms a film of coke scavenger material on the surfaces of the refinery equipment. The antifoulant is fed into the heater at a rate from about 1 gallon / day to about 100 gallons / day more preferably from 4.0 gallons / day to about 7.0 gallons / day, and most preferably from 4.5 gallons / day to approximately 6.5 gallons / day. The feed rate of the antifouling is maintained at least for a time from about 1 day to about 3 years, more preferably for a time at least from about 1 day to about 180 days, and most preferably from about 1 day to about 120 days. Longer or shorter times may be used, depending on a wide variety of factors including the type of procedure to be used in the processing of hydrocarbons, the type of equipment involved, the duration of the maneuver or run , and the conditions under which the process is carried out. The antifouling vapor found in the hydrocarbon fluid would supply the coating formed during the previous passivation process or create a coating as the antifouling vapor reacts with the surfaces of the refinery equipment. However, this continuous treatment process can not be used in catalytic fractionators for fluids, hydrotreaters, hydrodisintegrators, or any other refinery equipment that contains a catalyst bed at a site subsequent to the unit consisting of the heater. Another application of the claimed antiscaling agents includes injecting one or more of the claimed antiscaling agents during an in-line roughing process. Line grinding is one in which one or more lines (duct) of the heater are put out of operation and treated with steam and / or condensate to remove the coke deposits in the line, while the hydrocarbon fluid continues to process. through the other heater lines. After the coke debris has been removed, the temperature of the heater must be maintained at a sufficient value to maintain the temperature of a tubular injection structure located at a site posterior to the heater inlet, at a temperature of about 240 ° C. . The tubular structure needs to be positioned in such a way that it can be maintained at a temperature of at least about 240 ° C by the radiant heat of the heater or through another mechanism. To maintain the temperature of the tubular structure, at least about 240 ° C, the heater, including the tubes at that site, should typically be maintained at at least about 300 ° C, more preferably at about 400 ° C. Obviously at the temperatures at which the slag process is carried out, to which the proper vaporization of one or more claimed anti-foulants which are being injected into the line that is not functioning should not matter. Many of the commercially available anti-foulants are hydrolyzed in the vapor, vapor / air, or air, at the roughing or slag temperatures, causing additional problems without inhibiting or preventing coke deposits. The claimed anti-foulants are much more stable under the severe scouring conditions, and should be able to minimize at least the deposition of coke in the refinery equipment. The air flow, defined as the air flow necessary to move the hydrocarbon fluid, and other materials, through the tubes, should also preferably be kept heated to a temperature of at least about 240 ° C, before it enters the air. heater or before it makes contact with treatment materials such as the antifouling agents of the present invention. A typical flow of air is approximately 2000 feet / hour. The temperature of the air flow is extremely important if the condensation of the treatment materials has to be avoided. Once the air flow and temperatures are stabilized, the pressure in the system will be approximately 40 pounds. The treatment materials, in this case, the claimed anti-foulants, are injected through the tubular structure at a concentration below about 10 volume percent (% mol). The antifouling is evaporated in the hollow shaft. As the vaporized antifouling reacts with the surface of the refining equipment, a film of coke removing material is formed on the surfaces of the refinery equipment. The antifoulant is fed to the heater at a rate of about 0.5 gallons / day to about 3 gallons / day, more preferably from 0.5 gallons / day to about 2 gallons / day, and most preferably from 0.8 gallons / day to about 1.2 gallons / day, for a time from about 5 minutes to about 30 minutes, more preferably from about 5 minutes to about 20 minutes, and most preferably from about 5 minutes to about 15 minutes. Dosages and treatment times will vary markedly depending on a variety of factors including the type of process used, the type of equipment being treated, and the conditions under which the process is carried out. The feed flow rate of the antiscaling agent can then be increased gradually so that it does not interfere with the flow of air through the equipment or otherwise subject the system to shock waves. The feed rate is increased from about 1 gallon / day to about 2 gallons / day, more preferably from about 1.2 gallons / day to about 1.9 gallons / day, and most preferably from about 1.4 gallons / day to about 1.8 gallons / day. The feed rate, increased, for the antifouling, to the heater, should be maintained for at least a time ranging from about 30 minutes to about 1 hour, more preferably for a time of at least about 2 hours to about 3 hours , most preferably from about 4 hours to about 5 hours. Changes can be made in the composition, operation and arrangement of the method of the present invention, described, without departing from the concept and scope of the invention as defined in the following claims.

Claims (34)

1. A method to prevent the incrustation and formation of coke on the sections that are at high temperatures, of equipment for the processing of hydrocarbons, which are in contact with a hydrocarbon fluid, characterized in that it comprises adding to the fluid of 10 hydrocarbons, before it makes contact with the sections that are at high temperatures, of that equipment for the processing of hydrocarbons, an effective amount of 15 an antiscaling agent in its vapor phase, selected from the group consisting of tris-tertiary butylphenol phosphate esters and compounds having the formula I: Wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms; carbon, and only one of two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9, and mixtures thereof.

2. The method according to claim 1, characterized in that the high-temperature section of the equipment for processing hydrocarbons is at a temperature of at least about 240 ° C.

3. The method according to claim 1, characterized in that the antiscaling agent is added to a stream selected from the group 10 consisting of: air; steam; and mixtures thereof, before the addition of the antiscaling agent, to the hydrocarbon fluid, in an amount of about 5 parts per million 15 up to about 2,000 parts per million, based on the mass of the hydrocarbon fluid.

4. The method of compliance with Claim 1, characterized in that the equipment for the processing of hydrocarbons is selected from the group consisting of: viscosity reducers; coke formers 25 delayed; preheater; ovens; transfer lines; exchangers; catalytic thermo-disintegrators for fluids; hydrotreators; hydrodisintegrators; and furnace coils.

5. The method according to claim 1, characterized in that "n" is an integer of 1 to 10

6. The method according to claim 5, characterized in that each occurrence of R, R2 and R3 15 is hydrogen.

7. The method according to claim 1, characterized in that the sections at high The temperature of the equipment for processing hydrocarbons is in contact with a hydrocarbon fluid at a temperature of at least 240 ° C, characterized in that 25 comprises adding an effective amount of an antifoulant, in its vapor phase, to a carrier stream, before it makes contact with the equipment for processing hydrocarbons.

8. The method according to claim 7, characterized in that the antiscaling agent is added 10 to the process equipment, in a carrier stream, selected from the group consisting of: a. steam; b. air; 15 c. hydrocarbon gases; d. inert gases; and e. mixtures thereof.

9. The method of compliance with 20 claim 7, characterized in that from about 0.0005% by volume to about 10% by volume is added, based on the volume of the current to the 25 which is added the antiscaling agent.

10. The method according to claim 7, characterized in that "n" is an integer from 1 to 5.

11. The method according to claim 10, characterized in that each occurrence of R, R2 and R3 is hydrogen. 12. The method according to claim 10, characterized in that R is hydrogen or an alkyl group containing 1 to 4 carbon atoms.

Carbon, and at least one of the occurrences of R is alkyl.

13. The method according to claim 7, characterized in that the antiscaling agent is added to the carrier stream, before its introduction into an ethylene furnace or before introduction to a viscosity reducer.

14. A method for inhibiting the formation of coke on the surfaces of the sections at high temperatures, of the equipment for the processing of hydrocarbons, which is in contact with the hydrocarbon fluid, the method is characterized or comprises: 10 a. de-coking the equipment for the processing of hydrocarbons; b. before the processing of a hydrocarbon fluid, add an antifouling in its phase to the process equipment 15 steam, selected from the group consisting of: 1. tri-tertiary butyl phenol phosphate esters; 2. compounds that have the formula 20 I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group, having from 1 to 7 carbon atoms , and only one of two occurrences of R may be alkyl; Z is represented by formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9, and 3. mixtures thereof. c. form a thin layer of coke on the surfaces of the process equipment; and then, feed the hydrocarbon fluid, to the process equipment.

15. The method according to claim 14, characterized in that the addition of the antiscaling agent is discontinuous during the processing of the hydrocarbon fluid.

16. The method according to claim 14, characterized in that the addition of the antiscaling agent is discontinuous prior to the processing of the hydrocarbon fluid.

17. The method according to claim 14, characterized in that the antifouling is added intermittently, before the processing of the hydrocarbon fluid.

18. The method according to claim 14, characterized in that the antiscaling agent is added continuously before processing the hydrocarbon fluid.

19. The method according to claim 14, characterized in that the antiscaling agent is added intermittently during the processing of the hydrocarbon fluid.

20. The method of compliance with 10 claim 14, characterized in that the antifouling is continuously added during the processing of the hydrocarbon fluid.

21. The method according to claim 14, characterized in that the hydrocarbon fluid contains at least one fraction selected from a group consisting of 20 of : to . ethane; b. propane; c. butane; 25 d. naphtha; e. kerosene; f. diesel oil; and g. residue

22. The method according to claim 14, characterized in that the antifoulant is added to the process equipment in a carrier current selected from the group that 10 consists of: a. steam; b. air; c. hydrocarbon gases; d. inert gases; and 15 e. mixtures of them

23. The method according to claim 14, characterized in that the antiscaling agent is added in 20 a range from about 0.0005% by volume to about 10% by volume, based on the volumetric flow of the carrier, before the processing of the hydrocarbon fluid.

24. The method according to claim 14, characterized in that the antiscaling agent is added in a range from about 5 ppm to about 2,000 ppm, based on the mass flow of the hydrocarbon fluid, during the processing of the hydrocarbon fluid.

25. The method according to claim 14, characterized in that during the addition of the antifoulant, the process equipment is maintained at a temperature of at least about 240 ° C.

26. The method according to claim 14, characterized in that during the addition of the antifoulant, the process equipment is maintained at a temperature ranging from about 200 ° C to about 1200 ° C.

27. a method for inhibiting the formation of coke on the surfaces of sections at high temperatures, of equipment for the processing of hydrocarbons, which are in contact with hydrocarbon fluid. The method is characterized in that it comprises: a. process a hydrocarbon fluid in the presence of an antiscalant in its vapor phase, selected from the group consisting of: 1. esters butylphenol-triterium phosphate; 2. compounds that have Formula I: wherein Q is selected from the group consisting of: Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms, and only one or two occurrences of R may be alkyl; Z is represented by Formula II wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and 3. mixtures thereof; and b. forming a thin layer of coke on the surfaces of the process equipment, whereby the surfaces of the process equipment are inhibited against the formation of additional coke during the processing of a hydrocarbon fluid.

28. The method according to claim 27, characterized in that the antiscaling agent is added intermittently during the processing of hydrocarbon fluid.

29. The method according to claim 27, characterized in that the antiscaling agent is continuously added during the processing of the hydrocarbon fluid.

30. The method according to claim 27, characterized in that the hydrocarbon fluid contains at least one fraction selected from the group consisting of: to ethane; propane; c butane; naphtha; e kerosene; f gas oil; g residue.

31. The method according to claim 27, characterized in that the antifoulant is added in a range from about 5 ppm to about 2000 ppm, based on the mass flow of the hydrocarbon fluid, during the processing of the hydrocarbon fluid.

32. The method according to claim 27, characterized in that during the addition of the anti-crusher, the process equipment is maintained at a temperature of at least 240 ° C.

33. A method for increasing the duration of operation or run of the equipment for the processing of hydrocarbons, used to process a hydrocarbon fluid, characterized in that it comprises: a. decoding the process equipment; b. before processing a hydrocarbon fluid, add to the process equipment an antiscaling agent in its vapor phase, selected from the group consisting of: 1. tri-tertiary butyl phenol phosphate esters; 2. compounds that have Formula I: Q Q Q Q I wherein Q is selected from the group consisting of Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms, and only one or two occurrences of R may be alkyl; Z is represented by Formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and 3. mixtures thereof; c. forming a thin layer of coke on the surface of the process equipment that is in contact with the hydrocarbon fluid; and then, d. feeding the hydrocarbon fluid to the process equipment, whereby the surfaces of the process equipment are inhibited against the formation of additional coke during the processing of the hydrocarbon fluid, thereby increasing the duration of operation of the process equipment

34. A method to increase the yield of products, of the processing of a hydrocarbon fluid, through the processing equipment for hydrocarbons, characterized in that it comprises: to. decooking the process equipment; b. before processing a hydrocarbon fluid, add to the process equipment an antiscaling agent in its vapor phase, selected from the group consisting of: 1. tri-tertiary butyl phenol phosphate esters; 2. compounds that have Formula I: Q Q where Q is selected from the group consisting of Z and R, wherein two occurrences of Q and Z, and wherein R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms, and only one or two occurrences of R may be alkyl; Z is represented by Formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and R3 can be alkyl, and "n" is an integer from 1 to 9; and 3. mixtures thereof; c. form a thin layer of coke on the surfaces of the process equipment that is in contact with the hydrocarbon fluid; and then d. feeding the hydrocarbon fluid to the process equipment, whereby the surfaces of the process equipment are inhibited against the formation of additional coke during the processing of the hydrocarbon fluid, which increases the product yield, the fluid processing of 10 hydrocarbons, through the process equipment. fifteen twenty SUMMARY OF THE INVENTION The present invention relates to a method for preventing the incrustation and formation of coke on the sections that are at high temperatures, of equipment for processing hydrocarbons, which come into contact with a hydrocarbon fluid. The method comprises adding to a carrier, before the carrier comes into contact with the sections at high temperatures of the equipment, an effective amount of an antiscaling agent in its vapor phase, selected from the group consisting of tris-tertiary butylphenol phosphate esters and compounds that have Formula I: Q Q i wherein Q is Z or R with the proviso that two occurrences of are Z, R is hydrogen, or a straight or branched chain alkyl group having from 1 to 7 carbon atoms, and only one or two occurrences of R can be rent Z is represented by Formula II: wherein R2 and R3 are the same as R and only one of two occurrences of each of R2 and 3 can be alkyl and n "is an integer from 1 to 9, and mixtures thereof.