SA92130085B1 - LOW SULFUR RUNNING PROCESSES - Google Patents

Abstract

There is disclosed a catalytic reforming method in which hydrocarbons are treated in a reactor system to produce an aromatics enriched product, said reactor system comprising: (a) a series of reactors (10,20,30), containing a catalyst bed comprising a sulfur sensitive zeolite reforming catalyst, and each being associated with (b) a respective furnace (11,21,31) each comprising a plurality of furnace tubes for heating hydrocarbons to an elevated temperature in the range of from 850 to 1025 F suitable for reforming, (c) a heat exchanger (12); and (d) a separator (13) for separating an aromatics enriched product from effluent gas; said method comprising passing hydrocarbons through said reactor system to contact the hydrocarbons with the reforming catalyst in said reactors and separating said aromatics enriched product from said effluent gas; wherein: (i) hydrocarbons are reformed in each of said reactors under low sulfur reforming conditions of less than 50ppb sulfur; and (ii) at least the furnace tubes of the reactor system are protected from carburization and metal dusting. Apparatus for carrying out the process is also described. <IMAGE>

Description

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Low sulfur sulfur reforming processes Full description BACKGROUND The present invention relates to improved catalytic reforming techniques; In particular the catalyst refinement of reduced sulfur and reduced water and in more detail relates to sulfur under sulfur conditions of the invention; Discover and control problems with catalytic reforming processes for reduced sulfur and catalytic reforming processes for low sulfur and water. © Catalytic reforming is well known in the oil industry and includes processing aromatics. ) the most important that is transformed during the hydrocarbon refinement process and includes the reactions of hydrocarbons hydrogen gow to aromatic compounds cyclohexanes to cyclohexanes from which alkyleyclopentanes are formed and the formation of aromatic compounds from cyclic alkylpentanes Vo from them and the formation of aromatic compounds from the hydrogen-hydrocarbon compounds by removing hydrogen from them and by forming rings. As hydrogen J acyclic hydrocarbons are non-cyclic from alkyl benzene compounds, dealkylation, and a number of other reactions occur such as alkyl removal, hydrogen cracking reactions, paraffins, and the formation of light gas alkylbenzenes methane compounds such as methane hydrocarbons that produce hydrocracking 0. It is important to reduce the cracking reactions of butane, propane, propane, ethane, and ethane with hydrogen as much as possible during refinement, because it reduces the results that approximate the resulting boiling points. It also reduces the amount of hydrogen and the boiling point of gasoline. Huge research has been devoted to octane and there is a demand for high-octane gasoline.

Ye. To develop incentive trimming and improved catalytic trimming processes. In order for the refinement process to succeed, the incentives should be well chosen, and the incentives should be effective in producing a high percentage of the products.

VY v, which contains high concentrations of liquid gasoline, which has a high boiling point in the boiling range of gasoline. Similarly, octane, which has an octane rating, aromatic hydrocarbons are light gaseous aromatic hydrocarbons. And to be hydrocarbons, there must be a low production of hydrocarbons needed to produce products of a certain quality to Fan incentives are good to reduce high temperatures as low as possible. Also, it is essential that the catalysts either have good stability so that the 0 properties of efficacy and selectivity can be retained over long periods of operation or be renewable enough to repeat without degrading performance. Catalytic reforming is also an important process for the chemical industry because of The existence of urgent demands for use in the manufacture of aromatic hydrocarbons products, insecticides, pesticides, synthetic fibers, and various chemical pesticides, such as synthetic fibers, synthetic rubber, plastics, plastics, detergents, adhesives, and adhesives. High gasoline, gasoline, pharmaceutical products, pharmaceutical products, synthetic rubbers, exchange resins, drying oils, drying oils, perfumes, perfumes, octane rating, and various other products well known to those savvy in the tech ion-exchange resins Industrial ionizers. At present, significant technical progress has emerged in catalytic reforming, including the use of catalysts or wide-pore alkali. These catalysts are characterized by the presence of alkali zeolite catalysts and are charged with one or more metals of the eighth group. It was found that the alkaline earth metal earthy is longer than those catalysts lin. This type of catalyst helps to select higher and lifetime previously used ones. 7. By discovering facultative catalysts with an acceptable live cycle; Successful commercial production of high zeolite seemed inevitable. However, it was later discovered, unfortunately, that these selective sulfur zeolite catalysts, containing a metal of the eighth group, are susceptible to sulfur poisoning. It was found that the face of 1 4497079 was strange; As per US Patent No. 1 in the hydrocarbon feedstock at sulfur levels this problem is effectively resolved if the sulfur is Yo 50 parts per billion; It is more preferred that it be less than 001 and preferably less than a low ofan

After identifying the sensitivity to sulfur associated with these new incentives, and specifically the necessary and acceptable levels for the sulfur process, cquifur, successful commercial production began on the horizon for these incentives, which faded with the emergence of another obstacle. It was found that some zeolite catalysts are wide in diameter and sensitive to the presence of water under the known reaction conditions. In particular, 0 was found to accelerate the rate of catalytic inhibition. It has been found that sensitivity to water is a serious handicap that may be difficult to combat effectively. Water is produced at the beginning of each cycle of the process when the catalyst is reduced with hydrogen. Likewise, the water produced during the process is corrupt when it leaks into the feed of the trimmer or when the feed becomes contaminated with a compound containing oxygen. Finally, additional techniques have been developed to protect Oh the incentives.

Once again, commercial production seemed feasible from a practical point of view by developing sulfur catalyst refinement systems and low water using zeolite catalysts with high selectability and wide diameter as a catalyst with long lifetimes. While sulfur and reduced water systems were effective at first; He discovered that it might be necessary to shut down the reactor system after only a few 1 weeks. The reactor system of one of the pilot stations repeatedly clogged after only short operating periods. It was found that these blockages are related to the accumulation of coking coal. Although the accumulation of coal between catalyst atoms is a common problem in hydrocarbon manufacturing processes, the extent of the blockage formation rate

The accumulation of coal on the surface of the catalyst atoms in this particular system exceeded any expectations.

° General description of the invention. One of the objectives of the invention is to provide a method for refining hydrocarbons under conditions of low sulfur, gylfur, to avoid the difficulties mentioned, Bilas, associated with low sulfur operations, such as the process for short periods. ° Another objective of the present invention is to provide a reactor system for the refinement of hydrocarbons under low ylfur conditions to allow the process for longer periods. And after analyzing and revealing in detail the phenomenon of blockage of the low sulfur reactor systems as a result of the accumulation of coal; is found; It contained atoms and droplets of a metal and the size of the droplets ranged within a few microns. I would think that there are serious Tan problems that have not been taken into account in traditional -0-refining techniques as the levels of eld sulfur in the process are significantly higher. and on the specified day; He discovered that there are problems that threaten effective operations and economic systems; And the integration of physical equipment and also discovered that these problems arose under low sulfur conditions and to an extent due to low water levels. Forty years ago, catalytic reforming reactor systems were made of ordinary mild steel - 00 (Da contains AY, Y0 chromium© and ZY molybdenum 140). over time; Experience has shown that systems can be successfully operated for twenty years without noticing a loss of physical robustness. The discovery of metal droplet atoms in blockages caused by coal buildup eventually led to an investigation of the physical properties of the reactor system. Surprisingly, (Glas) cases indicate symptoms of very serious physical decay in the entire reactor system, including the furnace tubes, piping, reactor walls, and other media such as catalysts. It contains iron “m” and metal screens in the reactors. In the end, he discovered that this problem is related to the excessive carbonization of steel, which leads to the brittleness of steel due to the injection of carbon into the metal. Thus, the possible catastrophic physical breakdown of the reactor system can be imagined. With traditional tempering techniques, carbonation was not a problem or significant and Yo was not expected to be present in contemporary systems of low sulfur and low water with the possibility of using conventional process equipment. It is apparent that the sulfur present in conventional systems effectively inhibits carbonation. YY).

+ In conventional processes, the sulfur process interferes in some way with the carbonization reaction. But in very low sulfur systems this inherent protection is no longer present. Figure 1a is a photographic micrograph of a mild steel inner tube section (ie the section subjected to the chemical process) in a commercial trimmer. The tube has been exposed to conventional tempering conditions for about 19 years. This image shows that the surface of the tube has not changed basically, with the structure of the tube remaining naturally unchanged after prolonged exposure to hydrocarbons at high temperatures (it is noted that the black part of the image is the background of the image only). Figure (1b) is a photographic micrograph of a coupon-shaped sample of 1 mild steel 00111 placed inside the sulfur reactor and reduced water in a pilot plant for 1 week only. The image shows the eroded surface of the sample (against the black background) in which fragmentation of the metal has occurred. The dark gray veins indicate the intermediate carbonation of steel 1H56; Which was carbonized and peeled to a depth of more than 1 mm. Of course, the problems associated with fa carbonation are only with the carbonization of the physical system. No carbonization of the steel walls leads to “metal dusting”, that is, the release of atoms and droplets of metal that are effective in the catalyst due to the corrosion of the metal. The reactive metal atoms provide additional sites for coal formation in the system. While catalytic inhibition due to coal build-up is a problem that generally has to be encountered in refinement, this is important to be andl leads to a new problem of blockages, exacerbating the existing problem to a large aa. And in fact 0 | It was found that moving active metal atoms and coal particles exacerbate the problem of coal accumulation throughout the system in general. In fact, the active metal atoms are catalysts for the formation of coal on them and particles accumulate at every place in the system, which leads to blockages and hot areas for exothermic methane removal reactions. As a result, an early blockage of the reactor system caused by coal occurs and cannot be controlled. This can lead to system shutdowns within weeks of startup. The use of the Yo process and reactor system of the present invention overcomes these problems. Therefore, the first distinctive aspect of the invention relates to a method for reforming hydrocarbons, which includes contacting hydrocarbons with a reforming catalyst, preferably a wide zeolitic catalyst, YY.

Large-pore zeolitic catalyst Contains an alkali or alkaline earth metal and is charged with one or more Group VIII metals in a Jolie system Has resistance to carbonization and metallisation which is an improvement over conventional reactor systems made of mild steel conditions Low sulfur even under low sulfur and water conditions; When refining, the flaking resulting from carbonation is less than 0.0 mm per year, preferably less than 0 # mm per year, and it is more preferable that the JH be less than 1 mm per year, and it is absolutely better that it be less than 1.1 mm per year. Avoidance of scaling to this extent will greatly reduce aeratorization and coal formation in the reactor system, allowing operation for extended periods of time. Another distinguishing aspect of the invention relates to a reactor system that includes means to provide 0 resistance against carbonation and metal fragmentation, which is an improvement over conventional systems made of mild steel in a method for reforming hydrocarbons using a reforming catalyst such as a wide pore zeolite catalyst, La Jarge-pore zeolitic catalyst in that is an alkali earth metal and charged with one or more metals of the eighth group under conditions of low sulfur guifur and the resistance to scaling is less than about ©,7? mm per year, preferably less than 0 # mm per year, and more preferably 1 to be less than 1 mm per year, and the absolute best is less than 11 mm per year. Thus, the present invention is based on discovery; Among other factors in low gylfur sulfur reforming systems and in sulfur and low water sulfur reclamation systems there are notable carbonization, fragmentation and coke problems. These problems are not found to a significant extent in traditional refining processes where there are higher levels of sulfur, quifur. The discovery led to the work of 00 | extensive development of solutions to these problems; These solutions are new to low sulfur refining processes; directed to the selection and identification of resistant materials in low sulfur rectification systems; Oriented towards methods for the effective exploitation and use of resistant materials with additives (other than sulfur) to reduce carbonization, metal fragmentation and coal build-up, various process modifications and things in common have been presented to effectively address the problems. Specifically, the discovery has led to the search for the identification and selection of resistant materials for tempering systems. Sulfur +: 16 N: low and preferable to reactor walls, furnace tubes and networks previously mentioned are not necessary in conventional tempering systems Jie alloys and stainless steel 1L

A ceramic and some chromized and chrome-aluminized materials and aluminum-coated materials, it was discovered that some other relevant materials that are placed in the form of plating or SUX .5 copper may be effective resistance. These materials include copper (xd) coating or coating; germanium, germanium, antimony, arsenic antimony, tin, tin, metallic compounds chromium, bismuth, lead, brass Yellow © or silicon silica resulting from the aforementioned metals, alloys and coatings based on silica similarly. In one of the preferred embodiments of the invention is a new resistant coating containing 0 tin. In addition the discovery led to the development of some additives; which are referred to herein primarily in terms of sulfur as anti-carbonation and char-build-up agents which are completely 0 sulfur free; These additives are compounds of sulfur tin that are needed. It is preferable that they be free of sulfur, organo-antimony compounds, organo-tin compounds, organic compounds, organo-bismuth compounds, organic bismuth compounds, and arsenic organic lead compounds. Low compuonds also led to the development of guifur. Also, problems associated with Vo sulfur refinement processes led to some unnecessary modifications and compounds in the process previously mentioned in conventional refinement processes. These include some temperature control techniques, the use of hydrogen between reactors, and more frequent catalyst regeneration processes; And the use of Tan hot hydrogen heating devices, phased tubes, the use of temperature stages, and the use of highly heated raw materials with higher tube diameters and/or tube velocities. 0 Brief explanation of the drawings Figure (1): A photographic micrograph A part of the inside of a steel furnace tube (i.e. the part that is subjected to the chemical process) in a mild steel tempering device, as mentioned previously. A commercial Le 06 that has been subjected to conventional tempering conditions for about approx. is a photographic micrograph. A sample in the form of a voucher of steel: (QV) and the form Yo and low water in sulfur placed inside the sulfur reactor y mild steel for only a week. VY experimental station for a period of:

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q An illustration of a reforming reactor system suitable for use in the present invention. : (Y) Figure Detailed Description Metallurgy terms used herein in this statement are given the common meanings as given in a publication of the American Metallurgical Society. For example, The Metals Handbook for types that do not have small quantities 1 are those carbon steels carbon steels (Jl) ° are limited from any alloying elements (other than those generally accepted amounts Of manganese and containing only a minor amount of any element (copper, copper, siticon, manganese copper, manganese, manganese, silicon, and carbon other than carbon is that type of mild steel And “soft steel” phosphorus, phosphorus, sulfur, and sulfur, which contains a maximum carbon equivalent to about 679 7. And carbonsteels, carbon steel Yo, which contains specific amounts of steel, is that alloy steel steels “alloy steel” and generally accepted amounts of manganese carbon alloying elements (other than carbon including phosphorus, sulfur, sulfur copper, silicon and manganese Known amounts of alloy steels Structural; added to make changes in the mechanical and chromium steel 7 01 physical and mechanical properties. The alloy steel will contain at least less than 0 or 7 # 01 multi-containing gree] is a type of stainless steel as the basic alloying element in the alloy. chromium chromium 7 01 to 11 is preferred and therefore the focus of the invention is generally to provide an improved method for tempering by using a tempering catalyst; In particular, a wide zeolitic catalyst, hydrocarbons, includes an alkali or alkaline earth metal and is charged with one metal or jarge-pore zeolitic catalyst Ye. Sulfur is one of the eighth group metals that are sensitive to sulfur: it is under low sulfur SiS conditions. This process should, of course, demonstrate better resistance to carbonization than conventional low sulfur techniques. sulfur for sulfur refinement One solution to the problem of the present invention is to provide a new zeolite reactor system that can incorporate one or more means using a catalyst. Refining as the aforementioned wide-pore zeolite catalyst, Yo sulfur, under sulfur conditions, which are sensitive to low sulfur.

1 Also used in this statement is at least one reactor system and “reactor system” means a reactor system (V) one tempering reactor and the corresponding furnace and piping system. The figure shows a typical trim suitable for the application of the present invention. It can include a group of reactors

GAS Each reactor contains a catalytic bed. The system includes (Tr), (701) and (01) trimming (OF), separating device (TY), (711) and (11) set of ovens © and from During the absolute research of the present invention it has been discovered that the problems associated with low refinement can be effectively addressed by selecting a suitable reactor system material sulfur sulfur during the process. Alloys such as mild chromium steel, typically tempered from mild steel, known for unremarkable rates of carbonization and fragmentation of the metal, for example, steel pipes of 0 years under Yo can age / Y,Y0 with a chromium ratio of m In it, furnaces made of these steels are not suitable under steel standard tempering conditions, as it was found that low-grade steels become brittle quickly as a result of carbonization within about one year only. Sulfur 7 1 Mo and molybdenum 7 7.50 by Cr, which contains chromium steel It was found that steel (Sid) mm per year. 1 carbonized and peeled to a depth of more than 1 Conditions of standard mineral practice known as low, for example, sulfur with resistance to charring and carbonization, and it is not necessary to resist sulfur refinement

Incoloy (A Yo) and (Incoloy 0 (A) as (Incoloy M nickel) Nickel-rich alloys other than Marcel and Haynes 230 (YV+) $inconel 600 (0) 0 371, 7116, 714 preferably 01 stainless steel baal A series of stainless steels are acceptable as materials for at least parts of the reactor system according to the present invention that come into contact with VEY and have been found to have resistance to carbonation. It is greater than the resistance of mild steel, hydrocarbons, nickel, and alloys rich in nickel, mild steel, such as those sold by the aluminum company. At first, I thought that the materials grafted with aluminum, Yo, would not provide alonized steel, what is called (alloy steel). Alon Corporation Required protection against carbonation in the reforming reactor system and the reforming process of the invention

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11 the present. It has since been discovered that applying thin layers of 1 aluminum or alumina to the surface of the metal from which the tempering reactor system is made, or simply using 0:260m1 alumina steel during installation, can provide surfaces with a degree of resistance. Sufficient for carbonization and metallurgy under conditions of low sulfur refinement, and such materials are relatively expensive. Although they are resistant to carbonization and metallurgy, they tend to crack and show significant decreases in fatigue strength. The base metal layer is exposed to cracks, which makes it vulnerable to carbonization and metal fragmentation

under low sulfur conditions. While aluminum-coated materials were used to prevent day Si in ethylene hydrocracking processes, these processes were conducted at temperatures >0 significantly higher than the annealing temperatures where carbonization is expected to occur. Carbonization and metallurgy were not among the problems of earlier refinements. Therefore, one of the other solutions to the problems of carbonization and fragmentation of the metal includes the use of thin layers of aluminum or alumina, at least part of the surfaces of Al lal Z that is the inside of the reactor system or Yu from that the use of materials coated with aluminum In fact, 1 metal surfaces that are particularly susceptible to carbonization and metallisation can be provided in the same way. These metallic surfaces include, but are not limited to, reactor walls, furnace tubes, and furnace lining. When placing the thin layer of 1 aluminum or alumina, it is preferable that this thin layer have Jian thermal expansion for the thermal expansion of the metal surface (such as mild steel) on which it is placed so that it can withstand shocks Thermal and YS cycles the repeated temperatures that occur during tempering.This prevents chipping or cracking which may expose the surface of the base metal to carbonization catalyzed by the hydrocarbon medium.In addition, the film must have a thermal conductivity equal to or greater than that of the conductivity.The metals used Appropriately in the construction of reforming reactor systems, the aluminum or alumina film in the reforming medium or in the oxidation medium associated with catalytic regeneration should not decompose, nor should it induce decomposition of hydrocarbons in the reactor system. VY

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Or alumina, suitable methods for placing thin layers of aluminum and preferred methods include Tam processes on metallic surfaces. Terrytown, Pa. Alon processing Inc. ° Basically, "colorization" is a high temperature diffusion process that alloys aluminum into the surface of the processed metal; Like mild steel of commercial quality. In the process, the metal (such as mild steel) is placed in a retort and surrounded by a mixture of mixed aluminum powders. The fam is sealed and placed in a control furnace under a suitable atmosphere. At a high temperature, the aluminum spreads to a depth After cooling the furnace, the bottom layer of the retort is taken and the excess powder is removed. Leveling operations, cutting excesses, flanks and other necessary secondary operations are carried out as appropriate. This process makes the metal that has been subjected to the "coloring" process resistant to carbonization and fragmentation It is also possible to apply thin layers of chromium or chromium oxide 1 on the metallic surfaces of the reactor system to make these surfaces resistant to carbonization and metallurgy under sulfuric conditions. Like the use of thin layers of alumina, aluminum, and aluminum-coated materials, metal surfaces coated with chromium or chromium oxide were not used to face the problems of du SY under conditions Low sulfur refinement. z on the burglary of chromium oxide or chromium oxide, and chromium Y can also be placed on metals subject to carbonization and metallurgy, such as the walls of the reactor or the walls of the furnace interior and furnace tubes. As any surface in the system may show signs of carbonization or metallisation under conditions of low chromium or chromium oxide, applying a thin layer of chromium gylfur sulfur to it is beneficial. Thinner sheets of chromium or chromium oxide, it is better to have a thermal expansion similar to the thermal expansion of the metal on which it will be placed. In addition, the thin layer of chromium or chromium oxide ps must be able to

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It can withstand thermal shocks and the frequent temperature cycles typical of chromium oxide or chromium oxide. This avoids cracking and cracking of the chromium film that would expose the lower metal surfaces to media that induce carbonization. Furthermore it; The foil must have a thermal conductivity equal to or greater than the thermal conductivity of the chromium oxide or chromium oxide layer of the materials appropriately used in reforming reactor © systems in order to maintain efficient heat transfer. Also, mild steel (particularly mild steel thinned to decomposition in chromium oxide or chromium oxide medium) should not be exposed to the chromium layer nor should it catalyze liad decomposition or in oxidation medium Hydrocarbons associated with regeneration in the reactor system. Ve hydrocarbons include appropriate methods for applying a thin layer of chromium or chromium oxide to surfaces such as mild steel using well-known deposition techniques. Preferred processes include powder and vapor diffusion processes similar to the "chromizing" process commercialized by Alloy Surfaces Inc. of Wilmington, Delaware. Essentially a vapor-diffusion process for coating the surface of the metal with chromium (similar to the coloration process described earlier).The process involves contacting the metal to be coated with chromium powder followed by a thermal diffusion step.This thus produces an alloy of chromium and the treated metal It makes the surface highly resistant to carbonization and leaching under conditions of low gujfur sulfur refinement. 0 In some areas of reactor systems local temperatures may become excessively high during pruning (eg from 87 µm to 77/7 ºC). In particular, this case occurs in the furnace tubes and in the catalyst layers, exothermic methane removal reactions inside the accumulated coal balls that are usually present, which leads to local hot zones. While it is preferable to use greet steels of the 70010 series over the use of mild steels and alloys rich in chromium Yo, the + Vo series shows an accumulation of coal and metal fragmentation at about a0 FA, and so on. The “01 stainless steel fall” series is useful in the present invention, but it is not the best. VY

And stainless steel types rich in chromium, such as £47 and 17?, are more resistant to carbonization than the 701 stainless steel series, as these types of steel are undesirable in terms of heat resistance properties ( as it may become brittle). Preferred resistance materials on the 001 series include stainless steel

oo For use in the present invention copper, tin, tin, arsenic, antimony, bismuth, chromium, brass 5 and common compounds of these metals and their alloys (such as alloys of copper, tin and tin Copper alloys, antimony, arsenides <3 (3M stannides, bismuthides, etc.). Steels and even nickel-rich alloys appear to contain

Ys These metals have a lower level of carbonation. In a preferred embodiment, these materials are available on sheets, plating, or coating (for example, oxide coatings), where it is not necessary to paint the surface that contacts the hydrocarbons only, which allows the use of traditional building materials such as mild steel, and among these materials Tin is particularly preferred as it reacts with the surface to provide a coating that has excellent resistance at higher temperatures; It resists peeling paint. Well thought of. Vo the containing layer can be a tenth of a micron thick to resist carbonation. Where practicable, it is preferable to place resistive materials in the form of a “paint-like formulation” (hereinafter referred to as “paint”) in the reactor system, such as mild steel and stainless steel [EY] that have the property Sufficient viscosity to provide a light coating of a measured and controlled thickness; best of all a highly reactive biodegradable coating Yo containing tin reduces to active tin and forms iron stannides and nickel at Heating in a reducing medium. It is best if the aforementioned paint contains at least four components (or equivalent in function): (1) a hydrogen-decomposing tin compound, (Y) a solvent system, and ( ) Tin metal fine fraction and (¢ ) Tin oxide as Yo reducing, absorbing, dispersing and binding agent. The coating should contain fine fraction solids to reduce stagnation to a minimum and should not contain Contains inactive materials that prevent active tin-N reaction with reactor system surfaces

: yo is a hydrogen octanoate compound, and as a tin and hydrogen-soluble compound in particular. Commercial formulations of this same compound are available. Tada tin octanoate will partially dry to a gum-like layer on a steel surface and this layer will not crack or separate. This property is necessary for the composition of any coating used in this field because it is likely that if the parts are hydrogen coated the coated material is stored for several months before hydrotreating © for parts before it should be 1 as well if it is hydrogen coated before assembly Hydrotreated tin octanoate is resistant to chipping during installation. As mentioned above, tin octanoate is commercially available. The compound is sold at a reasonable price and will gently decompose into an effective tin layer, forming at low temperatures hydrogen iron stannides iron stannides (ST) 716.7 up to 0 “N alone in the paint, as it is not sticky octanoate Tin octanoate should not be used sufficiently. Even when the solvent evaporates from it, the remaining liquid will drip and run on the coated surface. It will collect at the bottom of the tube. Sle Practically, if this compound is used to paint the horizontal furnace tube as an absorption, dispersing and bonding agent, it is tin oxide and tin oxide. organo- porous that can absorb an organometallic tin compound, tin, a compound that contains tin Vo and can be reduced to active tin and n in a reducing medium. In addition, the metallic tin compound can resist stagnation. Tan through a colloidal mill to produce fine tin oxide particles. Tin oxide treatment. It will provide the addition of tin oxide, and in contrast to the materials that increase the density of the paint, component (4) is chosen so that it becomes part of the formation, which is a thickening material that may leave gilica from the paint when it is reduced. It is not inert like silica 0 inactive surface coating after curing. Soft; That is, component (7) to ensure that the fin is finally added to the tin metal powder, capable of interacting with the surface intended to be coated at the lowest possible metallic tin temperature of 1 micron, even in a non-reducing atmosphere. Preferably, the size of the tin particles varies from tin to © microns, allowing excellent coverage of the surface to be coated with tin Yo. Non-reducing conditions occur during the drying of the coating and the welding of the tube joints. The presence of iN tin ensures that if a portion of the paint is not completely reduced it will be the desired metallic tin (5 8). It stannides to react and form the tin layer, and the solvent should be non-toxic and effective to make the paint sprayable and spreadable. if desired. Tin which decomposes, should evaporate rapidly and have solvent properties compatible with the tin compound is best of all while isopropyl alcohol and hydrogen isopropyl alcohol ° useful as necessary. Whereas, pentane and pentane hexane can be hexane organo-tin compound. It tends to precipitate organic tin compounds. Acetone Acetone "Ten-7710" with a ratio of tin. In one embodiment, tin paint can be used. “There is tin in it

Stannous octanoate in octanoic Ten-Cem cm isopropyl alcohol, tin oxide, tin metal powder, and isopropyl alcohol (acid) in several ways. For example, furnace tubes can be tin coated and tin can be applied tin of the reactor system for each tube separately as units.It is possible for a reactor system to contain a unit of furnace tubes (for example; about le gina faze of the present invention Gada etiquette a unit of furnace tubes) having Appropriate width, length and height (for example, ? meters in length and YE meters in height). Typically, each unit includes two upper return arches, 11.7 wide and 1.1 meters wide. The upper return arcs 1.7 are connected with two suitable diameters, preferably with a diameter of about 1.48 JU meters (Ae) of suitable length U, with four to ten tubes in the shape of a letter, so that the surface area changes The total intended to be painted in units (Saad) in length). Therefore it is 11577 sq.m. in one embodiment may amount to approximately Sled wide range; (ara 7) coating the units instead of the tubes individually may be useful in four aspects (V) coating the units instead of of individual tubes to avoid Cali coating with heat tin as the components of the units are usually heat treated at elevated temperatures Tas during production (7) that coating the units is often faster and less expensive than coating the tubes individually (7) coating should be The units are more efficient during production and (8) the coating of the units shall be of weld vo point coating. No

No, as the coating of the units may not be from the complete coating of the pipes, as if the pipes were painted individually. If the coating is not enough, the pipes can be coated individually. It is best to spray paint in the upper tubes and curves. Sufficient amount of paint should be applied to completely cover the upper return pipes and curves. After spraying the unit; It should be left to dry for about ;? 7 hours followed by exposing them to a slow stream of hot nitrogen (eg 16°C for a period of time; after that it is best to apply a second coat of paint and dry them in the manner described above. dag Apply the paint Leave the units on In a better way under slight nitrogen pressure without exposing it to temperatures exceeding about 71°C as the installation and also not exposing it to water except what it may be exposed to during the test with water.The effective iron-bearing coatings fron are also useful in the present invention. It is preferable that the iron-bearing paint contain various fin compounds to which iron has been added in amounts up to one-third of the ratio of iron to tin on a weight basis. For example, in the form of ferric oxide Fe,04 and the benefits should be provided by adding iron ron to the tin-containing paint, in particular: (1) facilitating the reaction of the paint to form iron stannides and thus behaves Plating in a fluid flow (7) dilutes the nickel concentration! in the stannides layer, thus providing better protection against char build-up and (7) the die should produce a coating that can 0 provide protection against char build-up of stannides 0e even if the underlying subsurface does not react well. Other means to prevent carbonization, charring, and metal fragmentation in the LSR system include the use of a metallic coating or lamination of the chromium-rich steels contained in the reactor system. These types of metal plating or plating may include tin, antimony, or bismuth, arsenic, and fin is particularly preferred. These coatings or sheets can be applied by methods including electroplating, vapor deposition, or soaking chromium-rich steel in a molten metal bath. VY

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It has been found that in nickel-containing sulfur-refining reactors, coal and metallurgy are particularly problematic. Coating steels with a layer of tin “n” thus creates a double layer of protection. And the chromium-rich nickel interior also resists carbonation, coal accumulation, and metal fragmentation, and produces chromium, and produces an outer layer rich in chromium tin, which also resists carbonization, coal accumulation, and metal fragmentation, and produces a fin tin layer, an outer layer of tin © steel that also resists carbonation buildup Coal and metal fragmentation. This occurs when the tin-plated steel is subjected to tempering temperatures typical of chromium, which is rich in chromium and iron stannides, to form iron sree sree; It interacts with steel a 145 up to leaving a layer of “see better” on the surface of nickel steel, and thus nickel is filtered out, and in some cases; It may be desirable to remove the chromium-rich steel Ve layer to expose the stainless steel (iron, nickel stannides JS) and chromium-tin steel to the steel layer. On fin stainless steel, for example; It was found that when a plating of tin m was placed and heated at about 149 m, a layer of 0 da jal stainless steel, chromium chrome 7117, containing about chromium in chromium, was produced. a steel Vo

EY grade stainless steel mainly compared to nickel stainless steel, it is desirable to change the chromium-rich steel and when applying a coating layer of steel iad, Hall the thickness of the metallic coating to achieve the desired resistance against carbonization and coal build-up And fragmentation of tin ales in chromium-rich steel This is done by adjusting the steel contamination time (Sa) of the resulting molten Yo. It may be from chromium-rich steel, and this will affect the thickness of the steel layer chromium-rich steel It is recommended to change the operating temperature or change the composition of the chromium-rich steel in the chromium-coated steel layer, thus controlling the concentration of the resulting chromium. With additional protection, the tin-plated tin gree It was also found that Yo steels can be protected from carbonization, metal disintegration and metal accumulation by a subsequent treatment process that includes applying a thin oxide coating with a thickness of a few Lag and this coating will be Cr,04 like chromium oxide and preferably Chrome oxide

VY

microns. This chromium oxide will protect steel types coated with aluminum and tin, such as (alonized steel) types, under conditions of low sulfur refinement. A layer of chromium oxide can be applied oxide by a variety of methods including: coating of chromium or dichromate followed by reduction and steam curing process CS par organo chromium or coating of chromium metal followed by oxidation of chromed steel The resultant chromium.The test of electroplating tin-coated steels that were subjected to low sulfur conditions for a long period of time showed that a layer of Ve chromium oxide was formed on the surface of the sulfur layer. Or under the stannides layer, the chromium oxide layer does not lead to the deterioration of the tin 1115 layer, but rather it seems to make steel more resistant to carbonization, metal accumulation and metal disintegration. Therefore (ga) put a layer of chromium oxide On types of steel [gree] coated with either tin or aluminum to produce types of steel that have greater resistance to carbonization and metal accumulation under Cagyl 0 low sulfur refinement. The following treatment process has special applications for treating steel types (gree) coated with tin or aluminum, which need to be replaced after prolonged exposure to low sulfur refinement conditions. It was also found that the aluminum-coated steel, such as the "alonized" steel, which is resistant to carbonization, under the current low gyifur sulfur refinement conditions, may become 0 more resistant by the following treatment with a tin coating, resulting in This steel is more resistant to carbonization since there is accumulated traces of carbonization resistance from both the aluminum coating and the tin coating. This post-treatment provides the additional benefit of treating A defects or cracks in the aluminum coating. In addition, such a subsequent treatment will result in lower costs since a thinner alumina coating can be applied to the surface of the Yo-Ten steel treated with Olay Gal. In addition, this next treatment will protect the lower steel layer, which is exposed when the aluminum-coated steel is bent, which may lead to cracking.

Ye in lal and exposing the steel to aluminum carbonization and the presence of cracks in the aluminum layer. Refining conditions. The treatment of the steel. Also, this next treatment process prevents the formation of charcoal on the surfaces of the steel that has been coated with steel. It also prevents the formation of coal that occurs under the cracks that appear on tin and non-tinned aluminum types of steel © on the face of tin that are tin-coated, alonized steel, and Clie. It has been found that sulfur is Only one that deposits black char on the uncoated side only under sulfur-refining conditions is a gentle char produced by low aluminum. Coal that forms on an aluminum-coated surface, and this coal is not able to cause acidic alumina cracking on acidic alumina sites coated with extra steel. Therefore, the application of a post-treatment by applying a tin coating to the Ye steel can provide an additional reduction of the problems of carbonization, coal build-up and aluminum aluminization in reactor systems operating under tempering conditions according to the invention. While we do not wish to be bound by any theory It is believed that the suitability of the various materials of the present invention can be selected and classified according to their responses to the carbonization media. for example; Iron is relatively unstable and carbonizes later and forms carbides, nickel carbides, nickel cobalt, cobalt Vo and niobium vanadium on which coal and crumbled metal residues are formed. While elements such as chromium, niobium, tantalum zirconium, tantalum molybdenum, molybdenum tungsten, and tungsten vanadium are stable, they have greater resistance to carbonization, coal buildup, and metal fragmentation. 3. Slay S zirconium does not form carbides or coal. These bismuth and antimony elements of tin, antimony, copper, copper, nickel, nickel and jron compounds can form stable compounds with several metals such as iron 70. Bismuthides, antimonides and antimonides at stannides under conditions of cultivation. Arsenic, arsenic, mercury G0 compounds of lead, compounds of lead 05, thallium, selenium, selenium, tellurium, tellurium, indium, germanium, and germanium are resistant. The last category of materials, Lad, is oxygen, oxygen, sulfur, sulfur, thallium, oxides platinum, platinum, gold, gold, copper, and silver. It includes metals such as silver, Yo, and these materials are resistant and do not form alumina carbides. And alumina silica is refractory like silica or it reacts with other metals in a carbonization medium under tempering conditions.

As previously mentioned, the selection of suitable metals that are resistant to carbonization and metallurgy and their use as coating materials for metal surfaces in the reactor system is one of the means to prevent problems of carbonization and metallurgy. Since carbonation and metal fragmentation may spread in a large number of minerals; Carburizing resistant materials may be expensive or alien to conventional materials (such as mild steel © used in the construction of reforming reactor systems. Therefore, it is desirable in the reactor system of the invention to use ceramic materials that do not form carbides under typical tempering conditions Thus they are not subject to carbonization for at least a portion of the metallic surfaces in the reactor system.For example, the least portion of the furnace tubes may be made of one or both of the ceramic materials.In selecting the ceramic materials for use in the present invention it is preferable that the ceramic materials have thermal conductivity Equal to or greater than the thermal conductivity commonly used in the construction of reforming reactor systems.In addition, the ceramic materials must have sufficient structural strength at the existing temperatures within the reforming reactor system.Also, the ceramic materials must be able to withstand thermal shocks and repeated temperature cycles that Occur during the operation of the reactor system When ceramic materials are used to build the inner surfaces of the furnace, the ceramic materials should have a thermal expansion equal to the thermal expansion of the outer metal surfaces with which the inner surface is in close contact. This avoids stress at the contact points during the temperature cycle when starting and stopping. Also, the ceramic surface must not be subject to dissolution in the hydrocarbon medium or in the oxidation medium that occurs during catalyst regeneration. The ceramic material chosen should not induce the decomposition of hydrocarbons in the reactor system. Suitable ceramic materials include silicon carbides, silicon oxides, silicon nitrides, and aluminum nitrides, where they are not limited to that. Among these, silicon carbides 11100 and silicon nitrides are particularly preferred for their demonstrated ability to provide complete lea to the reactor system under conditions of low gulfur refinement. Yo, and at least part of the metallic surfaces in the reactor system can be coated with silicon or g silica, and the metallic surfaces that can be coated include the reactor walls, furnace tubes, and the internal surfaces of the furnace, but are not limited to that, as VY signs appear. ‏

YY sulfur Carbonization and metal disintegration on any metallic surface in the reactor system under conditions of sulfur refinement on it. Silicon with electroplating silica or silica for coating metallic surfaces. Silicon can be placed in a vapor carrier gas. From the alkoxy silane and chemical vapor deposition of the alkoxy xylene compound, a thermal expansion is approximately equivalent to the expansion of silica or silicon. Also, it must withstand thermal shock and repeated temperature silicon cycle during tempering. This avoids cracking and cracking of the silicon wafer and exposure of the surface underneath to carbonization catalysed by the hydrocarbon medium. Also, silica or silica or silicon 1.0 and a thermal conductivity equal to or greater than silica The silica sheet Ve should have the thermal conductivity of metals traditionally used in reforming reactor systems for preservation in a silica or silica medium silicon for efficient heat transfer. The rectifying silicon wafer or in the oxidation medium associated with catalytic regeneration should not decompose nor should it decompose itself. Hydrocarbons Whereas, different regions of the reactor system of the invention (i.e. different regions in Vo 3 gall kiln) may be exposed to temperatures in a wide range, so the selection of materials can be coordinated so as to use those that provide better resistance to carbonization in those areas of the system that are exposed to higher temperatures. Effective in terms of coal accumulation and carbonization of ST are cobalt, cobalt nickel, nickel fron iron. 00 stainless steel Their unoxidized counterparts. for example; It was found that the stainless steel sample significantly; from the 7-series non-dled sample; 3 Roasted with air was more, and it is believed that this is due to the reduction of the oxidized steel again than the oxidized steel of the same type of steel is soft, and these metals are particularly effective in carbonizing nickel and / or nickel iron, which produces iron metals coal accumulation. Thus, it is desirable to avoid the use of these materials as much as possible during oxidative YO regeneration processes such as those typically used in catalytic reformation. Where it was found that stainless steel can provide resistance to build-up of air-roasted and tin-plated tin 01 series stainless steel

YY

YY

The stainless steel series Charcoal and carbonization are equivalent to the resistance offered by tinned and non-air-roasted stainless steel ingots. In addition; He will realize that oxidation will be a problem in systems where sensitivity is a minor issue and he uses sulfur, 16N, to suppress the activity of metallic surfaces. Sulfur levels 8 Any metal sulfides are formed on metallic surfaces after oxidation and reduction and then reduced to a soft metal. This metal will be very reactive to carbon build-up and carbonation. This is likely to cause serious mineral composition damage or large-scale coal build-up of the present invention. They can be used lik and other techniques can be used to address the problem in conjunction with appropriate material selection for the reactor system or they can be used alone. Among the techniques > Preferred additional; Addition of anti-sulfur agents against carbonation and build-up of coal during the refinement process. These agents can be added continuously during manufacturing and interact with those surfaces, or they can be placed as chydrocarbons from the reactor system that come into contact with the hydrocarbons. Pre-treatment of the reactor system . Z Vo and while we do not wish to be bound by any theory, it is believed that these agents interact with the surfaces of the Je lial system by decomposing and attacking the surface to form intermetallic compounds of iron and/or nickel such as stannides. Antimonides, bismuthides, plumbides, arsenides, etc., and intermetallic compounds that are resistant to carbonization, coal buildup, and metal fragmentation and can protect lower minerals.7 It is believed that intermetals are more stable than the metal sulphides used in 0 Systems in which hydrogen sulfide (HLS) is used to form oxides on the surface of the metal.These compounds are not reduced by hydrogen, such as metal sulfides, and as a result, they are less inclined than metal sulphides to disintegrate the system, so the continuous addition of a carbonation inhibitor can be reduced with minimal feeding.vo Non-sulfur anti-carbonation and char build-up agents include organometallic compounds such as ALS, organo-tin compounds, organo- bismuth compounds, and organo-arsenic compounds compuonds and VY compounds

Y ¢ organo-lead compounds include organo-lead compounds, tetrametheyl and appropriate tetraethyl lead compounds such as tetrabutyltin, organo-tin compounds, and organo-tin compounds are preferred. lead in particular, trimethyl tin hydride and tetrabutyl tin bismuth. Special organometallic compounds include bismuth neodecanoate ° copper naphthanate, chromium octate, chromium octate, neodecanoate palladium neodeconoat, and palladium manganese carboxylate. Manganese carboxylate 18 tetrabutyl germanium, tetrabutyl germanium silver neodeconoat, silver neodecanoate, triphenylantimony, tributylantimony, zirconium octate, triphnylarsine Ye mainly on the properties of Jeal lili The question of how and where these agents are added to a system depends on they can be added continuously or intermittently with the feed. Sad special process design. Since it is not preferable to add agents to the feed because it leads to accumulation in the primary parts of the reactor system . This may not provide adequate protection in other areas of the system. These agents are best provided in the form of coatings prior to installation, prior to initial commissioning (vo), or on site (ie in an existing system). This must be done correctly if it is added on site after the use of Jan organic tin compounds is believed to regenerate the catalyst. It is possible to apply micron-thick coatings of iron stannides, as coatings of organo-tin compounds are effective. The best method for coating agents is on the surface of a new or existing reactor or on the surface of a furnace tube 7 at hydrogen The organometallic compound in a medium of hydrogen Jad, new or existing, including tin, produces Sie at temperatures up to about 487 m. And for organic tin compounds with the metal surface, tin metal is active on the surface of the tube. At these temperatures the tin will react to form an oxide. The ideal temperatures at which the coating should be applied will depend on the particular organometallic Yo compound or on the mixture of compounds if alloys are used as desired. Excess batches of the organometallic coating agent can be fed into the tubes at a hydrogen flow rate

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Yo is high to carry the coating agent through the entire system in an aerosol form. Then the flow rate can be reduced to 0 to allow the metallic coating in aerosol form to coat and react with the furnace tube or from that the compound can be introduced as a vapor to decompose and react with the hot walls of the tube or reactor in the medium. Reductant. As previously mentioned, reforming reactor systems subject to carbonization and biodegradable fragmentation ° can be treated on those metal fins and coal build-ups by applying a biodegradable coating containing a tin compound to the areas most susceptible to carbonization. This method works particularly well in a temperature-controlled oven. Hot spots system Such control is not always available. If reactor "hot spots" appear; Especially in furnace tubes, where the organometallic compound may decompose and form 0 precipitates. Therefore, one aspect of the present invention is a process that avoids such deposits in reforming reactor systems where temperatures are not precisely controlled and high-temperature hot spots exist in the systems. Such a process involves preheating the entire reactor system to a temperature of From m with a hot stream of #176, preferably from 87 um to #7 2, preferably more than (a TY) 7995 m to Yo, and after preheating, a cooler gas stream is introduced at a temperature of hydrogen le It ranges from ? 00 7 m to 17 m and preferably from 1776 m to 17 m and is best at all at This stream contains an organometallic tin compound in the form of steam in a YAS system around the preheated reactor. This gas mixture can be introduced at the start of the stream and can decompose throughout the entire reactor system. Essentially, the modulator decomposes the colder organometallic gas as it travels as a wave through the reactor system. The colder organo-metallic tin compound decomposes on the hot surface by moving in the form of a wave metalic organo tin and covers it, and the organo-metallic tin vapor continues to treat the hot surfaces in the heart of the process from the reactor system. Therefore, the entire Yo .organo-metallic tin compound reactor system may have a uniform coating layer of the organo-metallic tin compound

Also, it may be desirable to perform several hot and cold temperature cycles to ensure that the entire reactor system has been coated with the organometallic tin compound. In the reforming reactor system of the present invention naphtha Lal) is refined to aromatic compounds. and naphtha Gaal feed) which is a light hydrocarbon, it is preferable 0 that its boiling point be within the range from about 17 °C to 77 °C; more than about 8 °C is preferred, and the naphtha Gail feed) contains hydrocarbons alpha hydrocarbons] or paraffinic and convert aliphatic compounds Wa od at least 0 to aromatic compounds in the reduction reaction zone. In the low sulfur sulfur system of the invention, it is preferable that the Ve feed contain at least 001 parts per billion (ppb) of sulfur, preferably more than at least 500 parts per billion (ppb) sulfur. Use a sulfur absorbent unit to remove slight excesses of sulfur. Preferred refinement conditions include a temperature of between 5a TYY #17C. Preferably between 4 5 um and 7 ** um. pressure between 0 and 100 atmospheric pressure and Yo preferably between 15 and Vor atmospheric pressure; A hydrogen cycling rate sufficient to produce a ratio of gram molecular weight of hydrogen hydrogen to hydrocarbon in the feed to the reaction zone between 11 and yo, preferably between 1 and 01, and a spatial fluid velocity per hour For the hydrocarbon feed stream over the trimming catalyst between 1.1 and 01 and more preferably Lomb Ye and to achieve the appropriate trimming temperatures; It is often necessary to heat the furnace tubes to high temperatures; These temperatures often range from 1107°C to 7°C; usually from 4 © Um to 197/7 AD; And most of the time from 87 um to 149 um. It was found, as mentioned above, that the problems of carbonization, coal accumulation, and metal fragmentation in low sulfur systems are related to very high local process temperatures; These problems, sala YO, are particularly in the system furnace tubes where particularly high temperatures prevail. and in traditional refining techniques where high levels of sulfur are present: 18N; The surface temperature of the furnace tube is up to 4 77 °C, which is normal. VY).

l However, no trace of excessive carbonization, coal buildup, or mineral fragmentation was observed. It was discovered in low sulfur systems that the carbonization, coal accumulation, bid and rapid metal fragmentation in steel types containing chromium and molybdenum increase temperatures to 01 C and stainless steel types. stainless steel temperatures are increased to 20 oY °. Therefore, the other distinguishing features of the invention are the decrease in the temperatures of the metal surfaces inside the furnace tubes, transmission lines and/or reactors of the tempering system below the aforementioned levels. For example, temperatures can be monitored using thermocouples distributed at several locations in the reactor system. And in case thermocouples can be attached to the surfaces of the external furnace tubes; Preferably at the hottest point of the bale (near the kiln outlet) and if necessary adjustments can be made in the operation of the process to maintain temperatures at desired levels. There are other techniques to reduce undesirable high temperatures at the system surfaces. For example, heat transfer zones can be used by means of resistance tubes (and are usually more expensive in vo) in the last stage Cun the higher temperatures are usually. In addition, very hot hydrogen can be added between the reactors in the reforming system. A large catalytic charge can also be used. The catalyst can be specified more regularly. In this case; It is best achieved using a bed-shifting process in which the catalyst is drawn from the last bed and regenerated and charged to the first bed. The carbonization and metal fragmentation can be reduced in the 7.0 low gylfur sulfur reforming reactor system of the present invention with the use of new equipment structures and other process conditions. for example; The reactor system can be built with tubes and/or phased heaters. Also, the heaters or tubes that are exposed to extreme temperature conditions in the reactor system can be made of materials that are more resistant to carbonization than in reforming reactor systems; Any items such as those described above. It is possible to continue making heaters or pipes that Yo has not been exposed to fan hot temperatures from conventional materials. By using such a phase system in a reactor system it is possible to reduce the overall system cost (since anti-carbonization materials are generally more expensive than conventional materials) while still being

Ya

It is possible to provide reactor system with sufficient resistance to carbonization and metallurgy under low tempering conditions. In addition, this should facilitate the retrofitting of existing gylfur sulfur reforming reactor systems to make them resistant to carbonization and metallurgy under low N!8:sulfur operating conditions since smaller reactor systems require replacement or modification with a staging design. Te 3a The reactor system can also be operated using at least two thermal zones; ° The temperature in one of them is the maximum, and the temperature in the other is at its lowest value. More heat than the upper one and a lower temperature than the lower one. And by low temperatures, it means the temperature at or close to it that the refinement operations are carried out, and it falls at a lower temperature than that at which the fragmentation of the metal begins, which causes Vs. When operating parts of the reactor system in different regions, the temperature must be reduced. metal in an amount equivalent to what it would be if the reactor system were at a temperature that induces the decomposition of the metal. Other benefits of such a system include improved heat transfer efficiencies; And the ability to reduce the size of the equipment due to the operation of parts of the system at higher temperatures. fragmentation of the metal without eliminating it completely. This cannot be avoided due to the temperature fluctuation that occurs from day to day during the operation of the reforming reactor system. Particularly the fluctuation that occurs during system start-up and shutdown, as well as temperature fluctuation during circulating and during heating of the process fluids in the reactor system. Minimal hydrogen heating (such as hydrogen Ale) using raw materials through the walls of the furnace. hydrocarbons is possible from the need to heat the hydrocarbons. Another process design approach includes providing a pre-existing reforming reactor system with wider tube diameters and/or or has greater tubular velocities to minimize exposure of the heating surfaces in the Yo hydrocarbons system Je lial)

VY

As previously mentioned, catalytic refinement is well known in the oil industry and involves processing naphtha fractions to improve the octane rating by producing aromatic compounds. The important hydrocarbon reactions that occur during the reformation process include the conversion of cyclohexanes to aromatic compounds by dehydrogenation, the conversion of alkylcyclopentanes to aromatic compounds by conformation, dehydrogenation, and the conversion of inorganic hydrocarbons Cyclic JY are cyclic aromatic compounds that have been dehydrogenated. A number of other reactions also occur, including dealkylation = (alkylbenzene compounds, formation of paraffins, and hydrocracking reactions that produce light gaseous hydrocarbons such as methane, ethane 01, propane, and butane butane Hydrocracking reactions should be reduced to a minimum during reforming because they reduce results whose boiling points are close to that of gasoline and also reduce hydrogen and so the term “refarming” in this statement refers to processing Hydrocarbon feed by using one or more reactions with transpiration of aromatic compounds in order to provide a product rich in aromatic compounds (i.e. the percentage of aromatic compounds produced is higher than the percentage of aromatic compounds in the feed).

While the present invention is directed towards catalytic refinement mainly, Taste will be generally used in the production of aromatic hydrocarbons from various hydrocarbon feedstocks under conditions of low sulfur refinement. While catalytic reforming typically converts naphtha compounds, other feedstocks can be similarly processed to provide a product rich in aromatic compounds. Thus, while converting naphtha is an embodiment of Slade, the present invention can Fa is for converting into various feedstocks such as paraffin hydrocarbons, 1-olefin hydrocarbons, acetylene hydrocarbons, cyclic paraffin hydrocarbons, cyclic olefin hydrocarbons dala, etc. Exclude saturated hydrocarbons from them, specifically saturated hydrocarbons, Yo, those in which there are from “to paraffin hydrocarbons.” Examples of paraffin hydrocarbons are n-heptane and two methyl pentane molecules such as p-hexane and methylpentane carbon, carbon atoms 0

. And methylhexane, dimethylpentane, and n-octane. Examples of acetylene hydrocarbons are those that contain from 1 to 10 carbon atoms, such as hexyne and heptane heptyne and octyne 0ctyne. Among the At paraffin hydrocarbons are hexanes, those in which from 1 to 10 © carbon atoms such as methyl cyclopentane and cyclohexane cyclohexane, methylcyclohexane, and dimethylcyclohexane. Typical examples of paraffin hydrocarbons are those that contain from 10 to 71 carbon atoms, such as methylcyclopentene. methyleyclopentene, cyclohexene, methylcyclohexene, and dimethylcyclohexene Ve. The present invention will be useful for etching under low sulfur conditions by using different types of etching catalysts. These catalysts include unlimited group VIII metals carried on refractory inorganic oxides such as platinum on alumina, platinum tin, PU/SN on alumina, platinum and rhenium, Pt/Re on alumina, and contain Vo Unlimited eighth group metals on zeolite such as platinum or platinum, tin M008, platinum and rhenium Pt/Re on zeolite such as zeolite type (1) and zeolite type (ZSM- 5) silicalite and beta, and the unlimited eighth group metals contain zeolites of type (1) zeolites, 1, alkaline and alkaline-earth alternating. It includes a better embodiment of the invention using a large-pore geolitic catalyst 0 comprising an alkali or alkaline earth metal charged with one or more of the Group VIII metals. It is best to use a catalyst in trimming a feed from (US) unbroken. The expression "large-pore zeolite" generally refers to a zeolite 6 having an effective pore diameter of between 1 and 11 angstroms. The preferred and useful wide-diameter crystalline zeolites of the present invention contain type (1) L zeolite | ©, (X) zeolite, zeolite (7) and faujasite These zeolites have apparent pore sizes equal to TC of THY angstroms. The best of all is zeolite type (1). YY).

1 of type (1) in the form of zeolite molecular weight ratios. The composition of the gramic zeolite can be expressed between the following oxides: (0.9-1.3) M,,0: AL,05(5.2-6.9) SiO, : Y 0 And “may be of any value 04” and symbolizes the valence of the cation to cation 04 and in the above formula it symbolizes perverted and mentions the property of (1) zeolite from zero to about 4. The x-rays of the zeolite are © The statement of which is incorporated into TY TYAS and the method of preparing it in detail in the US Patent No. of this specification for reference. The actual formula may differ without changing the crystalline structure.

Yoo to 001 to aluminum whose form is silicon The molecular ratio of silicon varies expressed as molecular ratios (Y) zeolite Y The chemical formula of zeolite can be written: gram between oxides in the form 0 (0.7-0) 1.1) Na, O : AL,03 : xSi0; : Y 0 is a value greater than ? and reaches about 1 and a value of » may reach about X. In the above formula, a model of X-rays deviating from the distinct powder that can ( Y) zeolite and for zeolite 8. More fully in (Y) zeolite it is used with the above formula for identification. A zeolite is described, the content of which is incorporated into this statement for reference. 700017 - US Patent No. 1 It is a crystalline zeolite molecular sieve that can be represented as (X) zeolite and zeolite with the formula: (0.7-1.1) My/nO: and molten: (2.0-3.0) SiO, : Y 0

Y In the above formula 14 stands for metal; Especially an alkali metal or an alkali earth metal and “is a valency of 14 and the crystalline zeolite. It may have a value of about +4 depending on the identity of 14 and the degree of hydration of the zeolite is 0. Its deflected X-ray model, its properties and method of preparation are similar to zeolite and zeolite. The content of which was incorporated in this statement to be YAAYY ££ more fulfilled in the US Patent No. Large-pore reference. It is preferable to have an alkali metal or an alkali earth metal in wide-pore zeolite or calcium strontium or Strontium barium and the alkali earth metal can be zeolite Yo zeolite and the alkali earth metal can be incorporated into the barium zeolite and preferably calcium over the alkaline earth metals barium by composition, impregnation or ion exchange. Barium is preferred

YY)

YY

The strong acid other than La Le si is less acidic than other acidic catalysts because it produces a less acidic catalyst. A portion of the alkali metal may be exchanged with the barium. This includes contacting zeolite 68 with a solution of zeolites known to ion exchange zeolites *“80. In this embodiment jon should contain an excess of 0 zeolite to © 77 by weight of zeolite 7 0.1 “h; better way ; Of the ps lll used in the invention, Jarge-pore zeolites are composed and the wide-pore zeolite catalysts ruthenium and rutium nickel are charged with one or more of the eighth group metals such as nickel, platinum, platinum, iridium and iridium paladium, palladium, rhodium, and rhodium, and these are platinum options, especially platinum iridium. The preferred eighth group is iridium 1, and that it is more stable under hydrogen, with regard to the formation of cyclic compounds dehydrogenated from the metals of the eighth group, hydrogen. The reaction conditions for the formation of dehydrogenated cyclic compounds in the catalyst are the same as the other platinum. If used, the preferred percentage of platinum weight

Joslin between, by large-pore zeolites, and group VIII metals are incorporated into large-pore zeolites, by synthesis, impregnation, or ion exchange in an aqueous solution of a suitable salt. And if desired, the process can be implemented simultaneously or in the form of zeolite, two metals of the eighth group, in a cascading zeolite. To be more clear, the following examples illustrate certain distinctive features of the invention. Where it should be realized that this invention is not limited in any way to the specific details > 0 mentioned thereof. /; inch in diameter A In these tests, copper tubes with a length of Yo series stainless steel were used as a reactor to study the carbonization of stainless steel wires and their transformation into brittle wires. Three wires of stainless steel wires TEV were inserted

YY

stainless steel 1072" each in tube; while keeping part of the tube with a length; inch at an equal temperature over its length of 177 m by means of a furnace. And keeping the system pressure at 4,? Y atmospheric pressure Hexane 86 was introduced into the reactor at a rate of YO µl/min or equivalent *0.0ml/h at a hydrogen flow rate of about ©"cm/?min (with © being the ratio of hydrogen to hydrocarbons hydrocarbons equal to (V:0) and the amount of methane in the resulting flow was measured to determine the ga 3 exothermic methane reactions. A successful experiment was conducted using essentially pure hexane containing less than 7 parts in a million sulfur, and it was found that the pipe had mia) with carbon after only three hours.This not only stopped the flow of hydrogen and hexane feeding, but also that the excess carbon ruptured The tube actually caused swelling in the reactor, and the ratio of methane in the resulting flow was approximately 0 to ZA before blockage. The experiment continued for 0© hours before it was stopped to check the wires.No increase in methane was observed during the experiment.It remained constant at about 17 wt. due to thermal cracking of Yo. There were no blockages resulting from the accumulation of sulfur. No carbonation was observed for steel wires. A similar experiment was conducted with only one furnace, adding 1 part per million sulfur (i.e. ten times lower than the previous experiment). This experiment resulted in slight methane formation or blockage after A hour. Examination of steel wire showed a small amount of surface carbon Ye, but there were no traces of carbon A. Another experiment was conducted except that 0001 ppm ela (percentage) 70) Hexane was added to the hexane as methanol.methanol, and no sulfur was added. The experiment lasted 1 hour, and no blockage occurred in the reactor. When the tube split, it was discovered that 0 Moa 7/5 of 1 Because a tube was filled with carbon, however, the accumulation of carbon was not as dangerous as what happened in the successful experiment, Yo. Example) (Y VY)

T tests were carried out to identify materials suitable for use in low sulfur reforming reactor systems; That is, materials that may exhibit better resistance to carbonization than mild steel traditionally used in low sulfur tempering techniques. In these tests a device including a Lindberg furnace used an aluminium©8 tube set to the nearest degree Celsius with the thermocouple placed on the outside of the tube in the hot zone. The furnace tube had an inner diameter of 5/8 inch. Several experiments were carried out at a used temperature of 7 69 °C using a thermocouple suspended in the heated area (about ¾ cm? inch) of the tube. The inner thermocouple measured temperatures from 0°C to 10°C with less stability than the outer thermocouple 0 > . Samples of all mild steel (170 0 carbon and chromium steel and 001 series stainless steel samples were tested at #17oC And 1271 m and 9 m for a period of YE an hour.The materials were exposed at a temperature of 47°C for a period of 960 hours under conditions of low sulfur gyifpr refinement.The different materials samples 1 were placed in an open boat inside the hot area of the furnace tube.The boats were 7 meters long. .4 cm 1 in. wide and 1.717 cm y/y in. and sits well within the hot zone of ¥ ¥ in. of the tube. Each boat is attached to a silica glass rod for positioning and lifting. Not used An internal thermocouple when the boats are placed inside the tube.Before operating the boot, S$, the tube is washed with nitrogen for a few minutes, and then, Ye, bubbles a commercial carbonated gas, Lie, consisting of a mixture of propane in hydrogen with a ratio of 79 propane in a 1 liter flask filled with toluene p «p:1e» at room temperature to draw about 71 toluene into the feed gas mixture. Gaseous flows were maintained from Yo to 1 cm/min at a pressure equivalent to atmospheric pressure inside the device. The temperature of the samples was raised to operating temperatures at a rate of 144 degrees per minute.

Yo and after exposing the materials to the carbonated gas for the desired period at the desired temperature; The device is extinguished by a stream of air that is projected onto the outer surface of the tube. When the apparatus is sufficiently cold, the boat is lifted for examination and analysis. nitrogen The hydrocarbon gas is displaced with nitrogen. Before starting operation, the test materials are cut to the appropriate size and shape ready for visual examination. After each pre-treatment such as cleaning or roasting, the samples are weighed. Most samples weigh 0 mg. Typically, each of the experiments was conducted with three to five samples in boat 701 less than ? In each experiment 1 stainless steel series. A sample of stainless steel was placed in the experiments as an internal standard sample. After completing each of the experiments, the condition of the boat and each of the materials was carefully observed. The boat was also photographed. Each material is then weighed to determine changes keeping any 0 epoxy coke deposits with the appropriate substrate. Then, the samples were mounted in epoxy resin with grinding and polishing to prepare them and for analysis using a scanning electron microscope and descriptive resin analysis to determine the responses of coal accumulation, metal fragmentation and carbonization for each of the materials. It is necessary that the residence time of the carbonization gas used in these tests be higher than Experimental Cag pall duration of stay in a typical commercial process was significantly reduced. Thus V0 is believed to be more severe than experimental conditions in commercial operations. Some materials that fail (in terms of durability) in these tests can be relied upon for commercial production. Nevertheless, the test provides a reliable indicator in terms of the relative resistances of the materials towards coal build-up, carbonization and metal fragmentation. The results are shown in the table below: YL The percentage increase in weight as a result. atomizing composition carbon carbon accumulation hr YE (Ye hard A © steel carbon steel hard 1 Cras SY,Yo

Ni Nickel 0010©: Chrome 08 Minor None vot

AR

Viv Slight N/A 08 Chromium 0010: Nickel Ni 0 dro. Watch Carbon steel ¢ 1 Severe 0 Chromium 0 As Severe 1 Yet N/A 1 viv No There is 0p 0 h carbon steel oY ¢ steel severe CrasSY,Yo 1 severe Yet ° nil 1 viv nil GH er + :117 + and 1 for TT weight Of course the results are above They are qualitative results and depend on the shape of the surface. That is, the microscopic surface roughness of the metals. The percentage indicates the weight gain due to the accumulation of char on the self-catalytic surface oo. Example (7) The same techniques as le were used to heat a wide variety of materials at 49°C for 36 hours. The results are shown in the table below. Each group represents a side-by-side comparison in a single boat under identical conditions. Table Ve (1) Percentage increase in weight as a result of metal Composition Carbon accumulation Group I inconel ov inconel 001 severe 0 chromium © nickel Ni 41 3 oxide (7) 71 mild oxide — 1 ?new ¢ no 08 chromium 0 0 nickel Ni vv group II

Ni Nickel 0 Cres Sho EVER ¢. inconel 001 Ni inconel 0 ©: Slight ©? Chrome A YY.

Ni nickel (TY Cr as SY) moderate 1 incoloy A+ + incoloy slight traces of 1 pm, third group

Ni Nickel 4 Cres SYY Moderate < 10 incoloy Incoloy 6m

Ni Nickel 4 Cros SYY Slight ¥ Haynes 071 Haynes -— Slight Traces v Alcuized Tinted Y EV Slight Traces B < 1 B Group IV

Ni nickel 0 (pure) 10% intense Ni nickel Cu copper 0 (pure) zero none Cu copper --- tin “5” (molten) zero none —- Zero None Tin can Tin can (Tin 0] + carbon steel (c steel, 11, 0 +, 11 (by weight) Z 0 + CiHg 75 (VY) Roasted in air for 2 hours at a temperature of 1000C To produce a thin layer of oxide. (Y) (4) Example Additional materials were tested using the techniques described in Example (7) again (unless otherwise indicated). € 57 series and stainless steel stainless steel Stainless steel samples were placed in a sample boat and tested in real time in the carbonization device at a temperature of VV series stainless steel facall 7 m over a period of two weeks. Another change. On the other hand, large quantities of Cus 447 series stainless steel Ve

YY

Ya

A hole with a depth of VEY series stainless steel formed from charcoal on the surface of stainless steel, 11 cm from which coal and metal fragmentation emerged. I electroplated 11 tin with carbon steel. The coating on the samples is equivalent to chromium, chromium, copper, silver and silver. An hour of carbonization tests at a temperature of 44 C did not form any VT cm coal. And after 00017 0, charcoal is formed on the chromium-coated grilles on the tin and chrome-coated grilles, but in places where the paint peels off. The grids of copper and silver, on which no coating was applied, and which were subjected to the carbon steel test conditions at the same time with the coated grids, showed severe carbonization with charcoal and fragmentation of the metal. All o£ were painted. stainless steel series Samples of Yo stainless steel mesh were tested and these samples were tested with chromium or chromium tin a sample either with 47 series tin in a carbonization test at a temperature of 597 C. The stainless steel samples were exposed to rust for a period of weeks. At the end of each week, the samples were cooled to room temperature for fin observation and documentation using imaging. Then it is heated to 097 °C. The tin-plated grille was also free of charcoal except for some areas chromium free of charcoal and the Vo chrome-plated grille. 447 series stainless steel, one of which is not 7V6 (in which nickel is 001 inconel). tin coated and the other tin coated The tin coated sample crumbled but not to the level of the uncoated sample © (2) Example Exothermic during methane The following experiments were carried out to study the reaction of reduced methane formation. Formation and burning of coal balls during refinement under conditions of sulfur methane. Tin “Ren” was tested as an additive to reduce the refining of methane. In reactor systems for the refinement of low “6N” sulfur, deposits of coal containing molten Yo were found during refinement when fron molten It is believed that the formation of iron fron on iron particles at temperatures between 87 um and 91 ºC is due to the extreme exothermic reactions that occurred during

YY)

Politeness. It is believed that the only way to generate these temperatures is through the formation of highly exothermic methane. The high temperatures are particularly surprising since the modulation is generally endothermic in nature and tends to actually cool the reactor system. The high temperatures are generated inside the isolated coal balls, fas, by the diffusion of hydrogen within the catalytic fron iron remnants, which stimulate the formation of methane from coke and hydrogen. In this experiment, steel wool was used. wool to study the formation of methane in a very small experimental station. Casing an all stainless steel tube of diameter 170 cm (7.70 in) with 1.04 g of steel wool and baked at 0°C 275°C. Hexane and hydrogen were passed over fron iron, and the outgoing current was analyzed in terms of feeding components and results. The steel wool was pre-treated in hydrogen for 10 hours before the introduction of hexane, then hexane was introduced into the reactor at a rate of YO μl/min with hydrogen at a rate of about 1cm/cm. ?the minute. At the beginning, methane formation was low, and it continued to increase as the experiment continued1. In the end, it reached 0.76, then injected 1.1 cm of ctetrabutyl tin into the purified feed stream before it reached iron. Methane formation decreased to about 7 and continued at level 7 for ? hours. The experimental data are summarized in the following table. A 7.9.1 ¢,00 1 1 digit Y,AY £,YY 1 AR Term AR

AY, YY £,0. £.80 Yi, vy added tetrabutyl tin 1 1 AA 7 ALLY Caracalla 7 £,Y¢ Y,41 AA,77 Col 01,¢ Y,VyY M L AA 1 p. 9 Aggregates and Aquarium Lac AA,” and from the above results it can be seen that adding tin to steel wool stops the acceleration of methane formation and reduces methane levels Example (6) © Additional tests were carried out using steel wool coated with Gas with tetrabutyl tin, specifically “as in Example (©); three JS injections were injected, of which consisting of 0.1 cm tetrabutyl tin dissolved in 1 cm hexane in stainless steel tube 5101855 175 cm (Y,Y0 inch) containing 1.009 grams of steel wool, and the solution was carried over the steel wool in a hydrogen stream of 0 at a temperature of 487 °C. Then Adal hydrocarbons Ba day die 18 m Jaa introduced a flow of hydrocarbons equal to Yo μl/min and a flow rate of hydrogen equivalent to about Yo cm/min. Then he analyzed the outgoing gas in terms of the presence of methane and remained at level 7) for a period of YE an hour. After YE 1 hour no hydrogen© or feed could be detected at the outlet of the tube. The internal pressure rose to 7004 atmospheres. when slitting the reactor tube; It was found that the coal had completely blocked the pipe. Thus, it can be seen that the organo-tin compounds can prevent the carbonization of Ummu steel wool under tempering conditions. no

1 (7) Example To investigate the effect of carbonation conditions on (1) another experiment was conducted, such as the successful experiment in the example, which was tinned “n” by steaming in a stainless steel tube, stainless steel wires, and the only difference from the experiment The most successful is the use of a gold-plated reactor flow rate of 001 ml per minute higher than equivalent to hydrogen + hydrogen and at the incision of methane for hours without blockage or formation of methane A The experiment continued for a period of time and appeared Only one black stripe, carbon on the tube and checked it. No clogging or carbon streaks were noticed on the wire. It is believed that this defect is due to the coating method. Carbon of carbon stainless faa ll can protect stainless steel tin and these show Experience is that tin is carbonized in a manner similar to carbonation. Unlike sulfur: 8[n], it is not required to inject it in a continuous steel Ve form into the feed to keep the sulfur continuous in the feed. While sulfur should be injected into the system at a level Sufficient to maintain hydrogen sulfide partial pressure of hydrogen sulfide from the feedstock will result in the initiation of sulfur and any desulfurization as surface sulfide on steel 10 hours after the reactor system. This usually occurs during sulfur carbonization after sulfur stripping sulfur stop Yo The invention is described in terms of preferred applications It should be recognized that Lai obvious changes and modifications can be made for those skilled in the art. For example, silica, zirconium, and niobium can be coated in the reactor system with niobium (tee) parts of steel, although these techniques may be chromium or tungsten, tungsten ceramic, and porcelain. Implementation or use or it is costly to the extent that it is impossible to implement. Or it is possible to reduce the fan hard 0 to the reaction temperature. hydrocarbons Using heat exchangers to heat the hydrocarbons using tubes of hydrocarbons Or it is possible to reduce the exposure of heating surfaces to hydrocarbons whose diameters are wider or by using higher tube velocities. Principally there are changes and modifications which may be made to the preferred embodiments above to be apparent to those skilled in the art and which may be deemed to fall within the scope of the invention as defined in the following claims. Yo

Claims (1)

Protection Elements -1 | 1 A method for the catalytic reforming of hydrocarbons using a zeolite reforming catalyst Y with large pores that includes 138 ajkali or alkali earth 3 and is loaded with one or more metals of the eighth group “Group VIII metals 3 includes the following steps: © 0) supplying a feed stream of naphtha containing the hydrocarbons to be 1 refined and a percentage of sulfur JSulfur of 100 parts per billion; (Y) 7 Introduce said feed stream containing low percentage:16 sulfur into System A a reforming reactor comprising at least one furnace to heat said feed stream to 1 tempering temperatures and at least one reforming reactor; In the aforementioned reactor system, 01 of the aforementioned feed stream comes into contact with a surface part that contains tin and has a resistance to carbonization and leaching 1 greater than that of mild steel under conditions of low sulfur; B (0) Contacting the hydrocarbons present in the feed stream of low Vy sulfur with the aforementioned refinement catalyst in the aforementioned reactor system to form aromatic compounds .aromatics Vi 1 "- a method for ameliorating hydrocarbons according to claim (1) in which the aforementioned surface part containing tin has a greater resistance to carbonization than that of ajuminized steel under sulfur conditions sulfur and reduced water. Conditions of sulfur and low water. hydrocarbons of stainless steel faall series .001 L 1 #- A method for reforming the Bs hydrocarbons of claimant (1); wherein the sud ahd fin-containing portion of the reactor system in contact with the hydrocarbons comprises an alloy that does not contain nickel nickel in essence. 1-1 method for reforming the Tg hydrocarbons of claim (1); wherein the surface Y portion of said surface consisting of tin comprises a portion of a furnace tube in reactor system 7 that comes into contact with the hydrocarbons. 1-1 a method for reforming hydrocarbons of claim (1); Cua Part 7 of said surface consisting of tin on part of the reactor wall in the reactor system is in contact with hydrocarbons 1 “- a method for reforming hydrocarbons 5 of protection (1); where Part Y comprises said surface containing tin “n” over Cu-Sn alloy (tin and copper .(copper ¥ 1 4- A method for refining hydrocarbons according to claim (1); wherein part Y provides the said surface containing tin by applying a metallic coating; cade paint Y or any other coating consisting of tin on a material with a basic composition.-1-01 Method for tempering hydrocarbons of claim (1); wherein the Y portion is said surface containing tin Ylad tin in maintaining its resistance to carbonation after ¥ oxidation.-11-1 A method according to claim (V) to refine hydrocarbons to form aromatics comprising the contact of hydrocarbons with a zeolite catalyst for A zeolitic catalyst 5 with large pores in low sulfur conditions during the addition of a sulfur-free agent resistant to carbonization and at least one coal build-up to provide the O reactor system with improved resistance to carbonization and metal leaching. VY 1 method for reforming hydrocarbons according to claim (11) comprising coating the said tubes with an anti-carbonation and anti-coke agent selected from class 1 consisting of 'organo-tin compounds' antimony compounds organo- 43 pac antimony compounds ¢ argano-bismuth compounds lS ye © organic arsenic organo-arsenic compounds and organic lead compounds .organo-lead compounds 1 . 1 46 method for reforming Ga hydrocarbons for protection squeezing) 1 comprising the introduction of the said low sulfur feed stream Y into a reforming reactor system of which at least the Y part is made of chromium-rich steel 1 chromium treated with metallic paint containing ¢ .tin 10 1 the method according to claim (1) where the tin plating is applied by electroplating Y; vapor deposition; or impregnation in a bath of molten tin 1 - A method for refining the hydrocarbons Gg hydrocarbons of the protection element (1 where Y at least part of the Je lid system is preheated) by a stream of hydrogen gas Heat Y to a temperature of From about (Ve) a TIAL (@) to 1171°C S110 : exposes said preheated reactor system portion to a coolant stream of about EE has a temperature from about (GE) AY EE to 77.7 °C (GA) contains 1 hydrogen and an organo-metallic tin for .compound AY \ method (as of protection element ) 0” ( 1 where the reactor system part is preheated and exposed to the 1 refrigerant stream again, VA) method for reforming the hydrocarbons of element Protection Cun (1) Part 7 furnish said surface containing tin by applying a paint on a composition Y base material, wherein said paint is a biodegradable reactive paint consisting of tin applied Ge ca lo Refining reactor system exposed to hydrocarbons ° at elevated temperatures under low gulfur sulfur conditions. It forms a tin complex with said part of the rectification reactor system which is placed upon it after heating it in a reducing medium. 1 In a method for refining the hydrocarbons (la hydrocarbons) of protection element (A) 1 where the ¥ of the aforementioned paint contains (1) a tin compound that is hydrolyzable with (Y) ¢hydrogen ¥ Solvent system 0 tin metal divided as EXE ¢ tin oxide .tin oxide -71 1 method for refining hydrocarbons according to the protection element (Yo) where the tin compound has a “compound” The aforementioned hydrogen-degradable n is 7 tin octanoate 1 7- A method for refining hydrocarbons according to the protection element (VA) where it includes £7 Y The said paint is on tin metal finely divided with a pore size ranging from about 1 to ¾ micron. 1 0 77- A method for refining hydrocarbons of claim (VA) wherein ¥ said paint comprises a solvent system consisting of at least one component selected from 1 ¢ isopropyl alcohol hexane and pentane 1 ?- A method for refining hydrocarbons according to the protection element (VA) where the said paint includes tin oxide: 1-Yo 1 method for refining hydrocarbons according to the protection element (VA) Wherein said biodegradable reactive paint Y consisting of tin fin contains no reactant other than 1 which prevents the reaction of the tin reactant with the part of the reforming reactor system to which the paint is intended to be applied. -Y1 1 method for reforming hydrocarbons of claim 1 A) ( wherein Y comprises the application and reduction of the biodegradable reactive paint consisting of tin Ain 1 77 - method for reforming hydrocarbons Gy nydrocarbons For protection element (V1) where 0 is applied to the aforementioned biodegradable reactive paint that contains tin “n” by spraying. The said surface formed from tin by applying paint to a composite ¥ base material; said paint includes: (1) a compound containing one or more tin; and (Y) 8 an iron compound One or more ron compounds where the ratio len) is vay 1 by weight. YY a 1?7- A method for refining the hydrocarbons Gy hydrocarbons of the protectant (YA) where the Y iron compound is Fe,05. 1,000 a method for refining hydrocarbons according to claim (YA) wherein said Material Y is supplied in the form of a primer compound coating; So that the aforementioned basic composite material is mild steel or 48 JY stainless steel 1 1?- The Ty method of claim (1) includes supplying a feed stream consisting of hydrocarbon Y and sulfur at a rate of less than about 0 ppb. 1 7 ??- A method for reforming hydrocarbons using a reforming catalyst that includes a zeolite of type Y zeolite I 1. For the formation of aromatic compounds caromatics The mentioned method includes ¥ supplying a hydrocarbon feed stream sulfur hydrocarbon reduced by ¢ reducing the sulfur content of the hydrocarbons stream to less than about 0 ppb; and contacting said reduced sulfur 1 hydrocarbon feed stream with said rectification catalyst in a reactor system Where the hydrocarbons (a = hydrocarbons) come into contact with a part of a steel surface that contains at least one component on A from the group consisting of tin, germanium and antimony cantimony q. Yo for mild steel 1) 7?- A method for reforming the hydrocarbons Gay pydrocarbons of the protection element (YY) where the aforementioned deny Y is the reforming catalyst with platinum. 1 ??- A method for refining the G85 hydrocarbons of the claim (YY) whereby the flow of Y hydrocarbons through at least one furnace having a metallic surface containing YY Why 3 on tin coming into contact with hydrocarbons and forming part of the said reactor ¢ system. Yo 1 method for the refinement of hydrocarbons in accordance with claim (77); The effluent hydrocarbons contain gulfur sulfur at a rate of less than about OR 1 ppb. YT 1 method for reforming hydrocarbons according to claim Cua (YO) The mentioned rectification catalyst comprises a platinum-laden zeolite of type 1, L zeolite STV 1 method for reforming hydrocarbons For the formation of aromatic compounds Y 5 using a reforming catalyst comprising a large-porous zeolite; ¥ said method comprises the flow of hydrocarbons consisting of sulfur ¢ of less than about 0© ppm through a reforming reactor system of which at least part© is heated to the sulfur temperature and has a steel surface steel plated 1 with tin in contact with hydrocarbons ¢hydrocarbons and the surface of said part 7 of the reactor system has an improved resistance to carbonization and leaching that is greater than that of mild steel A and contact with hydrocarbons flowing with said reforming catalyst At refinement temperatures to convert at least part of the aforementioned hydrocarbons A into aromatic compounds. 1 78- The Ey method of the claimant (TV) in which the aforementioned etching catalyst includes a zeolite of stretchable Y L zeolite L steel There is a method of providing the aforementioned surface by coating the steel (FV) of the element of protection, Way -749 1, with a substance containing tin “n” and heating the coated surface in a reducing atmosphere to make a part on Y steel JY gall of less than tin “n interact with 11th £4 1 0 40- Gay method for claimant (TR) wherein said refinement catalyst comprises platinum carried on zeolite L a. 41 1 - Tag method of protection Cum (TV) Said reactor system shall consist of at least one furnace at Y containing steel tubes through which said hydrocarbons 1 flow said to be heated to the tempering temperature; So that the inner surfaces of the mentioned ¢ tubes are coated with a tin-containing material and heated in a hydrogen atmosphere to provide ° improved resistance to carbonization and metal leaching. 01 7?;- Gy method of claim (8) wherein said rectification catalyst comprises platinum Y carried on a type L zeolite. (67 Gay method of claim (£1) wherein said reactor system comprises at least one L reactor consisting of a catalyst for reforming and having a tinned steel wall portion y to provide y improved resistance to carbonization and leaching. 01 44- Gay method of claim (£7) wherein said refinement catalyst comprises platinum Y carried on a zeolite L a. 1 - A method for catalytic reforming of hydrocarbons using a zeolite reforming catalyst with large pores Y for the production of aromatic compounds. sulfur hydrocarbon stream to less than about 506 parts per 2 billion; 1 (vii) supply a reforming reactor system with improved resistance to carbonization and leaching where said system 7 comprises at least one furnace consisting of a single current contact furnace tube assembly YY Ow A feed said low 16Nh sulfur hydrocarbon and heat said feed stream 1 to catalytic tempering temperatures; where at least part of said furnace tubes 1 have a resistance to carbonization and leaching as great as at least comparable to that of EY series 1 stainless steel?; And VY the aforementioned reactor dead hydrocarbons come into contact with the catalyst for refinement .aromatics mentioned for the production of aromatic compounds V¢ 1 51 method for the refinement of hydrocarbons la hydrocarbons of the (to) element, where the aforementioned reforming reactor system includes steel surfaces, at least part of which has been initially coated 1 with aluminum aluminum or tin 1 Gy -47 tin for protection (£7) Method for pre-tinning steel surfaces aluminum Y by an annealing process. tin for protection (£7) Method for pre-tinting steel surfaces Gay 8 ?- 1 7 by electroplating process 1 45- A method for refining the Gay hydrocarbons of protection (47) whereby at least Y part of the steel surfaces of said reactor system are initially coated With a coating that includes aluminum, then a 406 treatment process is carried out that includes applying a metallic coating ¢ containing Hin aluminum according to the element of protection (£9 L, where the first coating method includes aluminum 1 06 XY by Germanization process. 1) A method for tagging the tag hydrocarbons of the protection element 5) where the AR is coated ¢aluminum (at least 2) of the metallic flakes in the reactor system with a Y-diaphragm or made of “chromium oxide” or “chromium oxide” chromium alumina “chromium v” or “chromium aluminum” Covered with aluminium (ag 07 1 for the element of protection) 1 0 where the method of producing the chromium film includes “chromium oxide” Y chromium oxide aluminum or alumina or calumina or the covering material 7 with aluminum or chromium using a high temperature diffusion process. 1 07 pursuant to Claim 1m wherein includes the method of coating at least part of the metal Y surfaces of the reactor system with a film of alumina Wa sll or aluminum sll or made of ¥ aluminized material. aluminum Gay - 54 1 of claim (0) comprising the method of coating at least part of the metal surfaces Y of the reactor system with a film of chromium, chromium oxide, or v made of chromium-coated material .chromium 1©5- A method for reforming hydrocarbons according to the element of protection (£0) where the reactor system is made at least partially from a ceramic material in contact with the hydrocarbons. 1 7- Tidy method for claim (00) where the ceramic material is at least one component of the group consisting of silicon carbides 1: “00:” and 7 silicon oxide compounds Compounds of silicon nitride esilicon nitrides and compounds of aluminum ¢ nitride aluminum nitrides 1 7 2 - A method for reforming hydrocarbons of claim (©) where Y uses heaters and/or staging tubes in said reactor system or System 1 is heated using superheated raw materials; or use pipes of large diameters; or use tubes 11th oY higher flow velocity; or separate thermal zones or compounds terminated to an effective range o to provide a resistance such that brittleness is less than © , Y mm/year. 1-0A method of sulfurization according to the element of protection (0£) where the said reactor system includes a part made of mild steel and during sulfurization Gad sulfur conditions with a Y ratio of less than 100 parts per Billion The temperatures of the parts of the reactor system made of JY 58 ¢ mild mild steel do not exceed N 501 (104 F). 1 4- Method for smelting according to the element of protection (£0) Cua The said reactor system includes an X part made of stainless steel fall during smelting under conditions including a sulfur content of less than 1 0 © ppb; temperatures of ¢ parts of the reactor system made of all stainless steel are not greater than 5F (sr 001.14)° 1 6 according to claim (oq) includes the method of adjusting the temperature of said metallic surface 1 | Using a thermocouple. 11-1 A method for reforming pydrocarbons of claim (£0) where said reactor system Y comprises at least one reforming reactor 6 and where at least part of the reactor system in contact with hydrocarbons is a choose from ¢ group OSH copper copper tin carsenic FH) din antimony ¢ antimony ° germanium <germanium copper ¢brass sisal lead bismuth 1 chrome cchromium and its alloys. TY 1 is a method for reforming hydrocarbons according to claim (TY) in which at least Y portion of the reactor system in contact with the hydrocarbons is antimonide or germanide ila formed from a compound of antimony \ARoy a] ¢ has a melting point less than that of antimony or of a germanide compound having a melting point of 2 less than that of germanium. 01 7.11- A method for reforming hydrocarbons according to the claim element (VF) where at least 7 part of the reactor system in contact with the hydrocarbons is 1 antimonide or germanide Formed from antimony sulfide ¢ or germanium. 1 ©1- A method for refining hydrocarbons 5 of protection element (VV) where at least part 7 of the reactor system in contact with hydrocarbons is coated with paint containing ¥ containing chromium or electroplated with chromium before politeness. (0 11) A method for rectifying G5 hydrocarbons of protection (10) where at least the Y part of the reactor system in contact with hydrocarbons is coated with a paint containing ¥ containing chromium salt before recharging. 1- 17- A method for reforming the 68g hydrocarbons of protection (1) wherein the Y portion of the reactor system in contact with the hydrocarbons is a metallic coating; for a shell or coating of a material selected from the group consisting of copper 'copper tin 'tin ¢ arsenic 'arsenic antimony 'antimony germanium ;yellow sense' 'brass ¢ lead aba) © bismuth chromium its alloys and alloys ; and where 1 polishes metallic paint; The aforementioned coating or coating by contacting the material with a metal of (metal oxide metal oxide and/or another metallic compound chosen from group A consisting of copper copper tin arsenic FH) tin antimony < antimony germanium ¢germanium 9 brass 5+ lead lead bismuth and chromium .chromium 1 18- a method for refining the hydrocarbons Ty hydrocarbons of the protection element (TV) where Cig 0%: Y metallic paint; Said coating or coating by adding a fine powder of metal 1 metal oxide and/or other metal compound reacted under reducing conditions. 1 18 methods for reforming hydrocarbons according to claim 1 0 include Y placing the material in the form of a metal halide at elevated temperatures. 1 70- A method for refining the hydrocarbons Gy hydrocarbons of the protection element (19) where the Y material is tin “n” and placed in the form of a metal halide shal. 11No- A method for reforming hydrocarbons according to claim (1) where the material is placed on a base composite material using chemical vapor deposition. VY) A method for reforming hydrocarbons according to claim (VV) wherein the base component Y is a surface pre-carbonated in a reforming reactor system. YY 1 method for reforming hydrocarbons to claim (£0) comprising: 7 Provide a protective anti-carburizing and anti-corrosion layer to a steel part in said Y-reactor system by means of 00) applying a metallic coating; metal sheathing or metallic coating Al is effective in forming a protective anti-carburizing layer on the steel part; to obtain an effective thickness of separating ° The steel part is free from hydrocarbons during operation while avoiding any 1 > large liquid metal embrittlement; and (b) the formation of a protective layer attached to the steel part through a carbide-rich intermediate bonding layer VE 1 method according to Claim 7 0 Cua sulfur levels not exceeding about Yo ppb. Vo 1 method according to the claim (VT) which includes the method of applying a metallic coating; casing or OO 7 is another coating consisting of tin on a surface in the reactor system. . It includes a method of applying a tin-based paint of (Vo) of claim 7-1 VY 1 method of claim (V7) wherein said tin-based paint of Claim Y comprises a tin compound tin hydrolysis fable 'hydrogen solvent system; Finely divided tin metal v and gin oxide are effective as a spongy/dispersing/binding agent. Jdron, where the paint contains iron (VT) method according to the protection element -YA 1 1 4- Td method, for the protection element (VA) where the paint contains a ratio of tin n to ¥ iron 01 Omron and .1 Gay 0 1 for the element of protection (VT) incorporating a metallic coating method; A shell or other Y-coating consisting of tin and a stainless steel portion of the reactor system 7 treated to form a protective layer of pickel-rich stannide comprising intrusive ¢ impurities of carbide bonded to the steel portion by Intermediate bonding layer of stainless steel nickel-depleted pickel and rich in carbide 6 includes 1 extraneous impurities of stannide 1 1 method for the refinement of the Ga hydrocarbons of the protectant (to) where it includes Said furnace tubes having great resistance to carburizing and metallisation of a similar amount on at least Y Si of stainless steel series 7 ¢ Y on pala 334 1 in the form of metallic coating; casing; paint or other coating to a composite base material.AY 1 of claim (AY) comprising a method of coating a part of the reactor system with a VY film ¥ From aluminum 'alumina chromium' or chromium oxide <oxide 1 or make a material coated with aluminum or chromium . AY 1 for the protective element) Cua “(A 1) includes the method of coating the said part of the reactor ¥ system with a silica or silicon AS 1 film according to the protection element (AY) where the said reactor system includes steel surfaces 1 where At least part of the steel surfaces in the reactor system are first coated with aluminum or tin, then a thin coating of chromium oxide is applied. .chromium oxide ¢ AO 1 method according to claim (AY) wherein said pipes having a carbonization resistance Y greater than that of stainless steel fall of series 7 ¢ A shall have a sala mounted v A pre-carburized core has been treated to provide such resistance. tin Where said substance is Tin (AY) Method 1885 of claim AT 1 1 - Method of claim Cua (AY) Said substance is effective in maintaining Y its resistance to carbonization after oxidation . JAA 1 method of Claim 0 (AY) wherein said pipe having a carbonization resistance XY greater than the TAC of Series 9 stainless steel includes ? on a coating of reductant 01 over a base composite material; Said reducing substance is supplied by exposing it to a reducing medium at the reaction site. 1 4- Method of claim Cua (AA) The reducing medium comprises hydrogen .hydrogen Y VY ov, where the method includes placing the material to be reduced on (AA) of the protective element Gay - 1 form of paint. The aforementioned Y (yal Cua (£0) tubes are made A method for catalytic refinement according to Claim 951-1 has a resistance of steel of series No 7 or of stainless steel faall of 7 stainless faall of stainless steel Stal Jay on Silas for carburizing and chamfering of the metal Large by Y series 497 ?. steel ¢ for the element of protection (£0) where the furnace tubes mentioned Tay are made by a method of catalytic tempering 7-1 and where their surface parts that are intended to come into contact with the feed stream are treated steel of steel Y heated so as to provide improved resistance to carbonization and metallurgy using a method comprising the application of a metallic coating; a coat of paint or coating on the said surfaces. which includes the method of applying a biodegradable reactive paint consisting of (AY) of the protective element ld, 7 -1 on a steel part of the reforming reactor system; this paint is reduced to tin of tin 7 with said steel part of the iron stannide system reacting to form tin stannide Y The reforming reactor when heated under reducing conditions. A method of catalytic reforming according to element of protection (£0) where said catalyst is 4-1 A. zeolite L on a stretchable zeolite J gana platinum A catalyst of platinum Y A method for tempering according to the element of protection (£0) where at least part of the furnace tubes 40 1 is made of the aforementioned nickel in contact with Feed stream of non-nickel alloy 7 intrinsic. 1 of protection (£0) where at least part of the Tay reactor wall has a method of tempering -45 01 oA In the reactor system in contact with the feed stream, the carbonization resistance is as large as 7 for at least 1 series stainless steel. 1 97- Method for refinement 85) of protection element (£0) Cun At least part of the reactor system l in contact with the feed stream shall be a material chosen from the group consisting of 3: tin copper © din arsenic arsenic antimony 2007 brass cbrass lead ¢bismuth <2 $a» ¢lead t chromium cchromium its alloy compounds and alloys. 1 4- A method of annealing according to claim (AV) where the said material is a material that does not choose from its alloys or alloys. 1 4- A method of tempering according to the element of protection (AY) in which the said material is effective in maintaining its resistance to carbonization after oxidation. -0 1 method for the Tay refinement of the protective element (AY) whereby at least part of said Y reactor system shall be made of chromium steel having a metallic coating comprising ¥ tin cin Antimony < antimony is bismuth or .arsenic arsenic -011-1 Curing method according to Claim (£0) Cua At least part of the reactor system ¥ shall be made of ¥ steel SY, first coated with aluminum or tin, then a thin coating of 1 oxide shall be applied Chrome.chromium oxide steel At least part of Cus (£0) steel for protection element Gay is coated with a 0" -1 trimming method and then the aforementioned reactor system is first aluminum-coated with aluminum ¥ tin after-treatment Includes an applicator of metallic paint containing tin 7 0" 1 trimming method according to the element of protection (£0) whereby at least part of the reactor system is heated ‎VY 04 Y preheated by a stream of hydrogen gas triturated to a temperature of about 1 a VAAL (750°F) to 1171°C (1104) and then subjected to said Grae heated reactor system portion to a refrigerant stream of about 1°C Its temperature ranges from about 4 °C (GE) to daily (GA) SEY on hydrogen 1 and an organo-metallic tin compound 1 4 - Gig method for element Protection (£0) Cua Parts of the reactor system are made of mild steel Y and other parts of the Je lid system are made of stainless steel 3 and where; during annealing under conditions containing sulfur at a ratio of less than 50 parts per gpl (the temperatures of reactor system parts made of mild steel ° shall not exceed #001 or 50 F) and the temperatures of reactor system parts made of 1 shall not exceed of stainless steel at 51.87 (Yi Y0) ao = ( 1 - A method for reforming hydrocarbons comprising contacting hydrocarbons Y with a large-pore zeolite catalyst including An alkali or alkali earth metal and loaded with one or more Group VII metals in a reactor system with improved resistance to carbonization and metal fragmentation in sulfur conditions “it is low” and the resistance mentioned during refinement is such that 1 Brittleness is less than about 0.0 Y mm/year; And at least part of the metallic surfaces in the v reactor system in contact with hydrocarbons is coated with a thin film of silica or silicon A (silicon VY).