SA05260058B1 - Low sulfur refinement processes - Google Patents

Abstract

Abstract: The invention discloses a method for reforming hydrocarbons comprising contacting hydrocarbons with a catalyst in a reactor system having improved resistance to carbonization and metallising under low sulfur conditions.

Description

v low sulfur sulfur refinement processes Full Description Background of the Invention This application is a partial application of Application No. 17170088, which was filed in the Kingdom of Saudi Arabia on 9/17/4; 1H corresponding to 497/4/5 A.D. sulfur The present invention relates to improved techniques for catalytic refinement, especially under conditions of sulfur and low water, and in particular the invention relates to; detects and controls problems with reduced sulfur catalytic refinement processes and low sulfur and low water catalytic refinement processes. Catalytic reforming is well known in the oil industry and includes octane processing to improve the octane rating of naphtha fractions (oil) ) the most important ones that are transformed during hydrocarbon reactions and include aromatics of hydrocarbon reactions to aromatic compounds by removing cyclohexanes from the cyclohexanes and forming aromatic compounds from alkylcyclic hydrogen compounds and forming Hydrogen aromatic compounds that are formed by the dehydrogenation of acyclic hydrocarbons from non-cyclic hydrocarbons and by the formation of rings. A number of other reactions also take place, such as the removal of alkyl hydrogen and the formation of compounds of paraffins alkylbenzenes from the alkyl benzene compounds dealkylation 0 that produces hydrocracking hydrocarbons and hydrogen cracking reactions paraffins butane propane propane ethane and ethane methane Light gaseous hydrocarbons such as methane and it is important to reduce the hydrocracking reactions as much as possible during refinement because they are butane and reduce gasoline and reduce the results whose boiling points are close to the boiling point of gasoline. resulting. And because there is a demand for hydrogen gasoline, the amount of hydrogen

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Considerable research has been devoted to the development of incentive discipline and improved incentive discipline 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 ALD products that have a boiling point similar to that of gasoline and contain high concentrations of aromatic hydrocarbons that have a boiling point Octane is high. Likewise, there should be a low production of light gaseous hydrocarbons. And that the incentives have good effectiveness in reducing the very high temperatures required to produce products of a certain quality to the lowest possible extent. It is also essential that the catalysts either have good stability so that their efficacy and selectivity properties can be maintained over long periods of operation or that they are AS of retreading sufficiently to replicate this without compromising performance. Catalytic refinement Lind is an important process for the chemical industry due to the increasing demand for aromatic hydrocarbons for use in the manufacture of various chemical products such as synthetic fibers, insecticides, adhesives, detergents, and detergents. Plastics, synthetic rubbers, pharmaceutical products, gasoline with a high octane rating, perfumes, drying oils, jon-exchange resins, and various other well-known products. faa for those savvy in the industry.

An important technical advance in catalytic reforming has now emerged, involving the use of wide-pore zeolite catalysts. These catalysts are characterized by the presence of alkali, alkaline earth metal, and are charged with one or more of the eight group metals. It was found that this type of incentive helps to choose in a higher way and Goda lives longer than those incentives used previously.

¢ By discovering optional incentives with an acceptable live cycle; Successful commercial production of Tl seemed inevitable. However, it was discovered later, unfortunately; These highly selective, wide-pore zeolite catalysts containing a metal of the eighth group are strangely susceptible to sulfur poisoning. As in US Patent No. 0459715717 and at the end; It was found that this problem would be effectively addressed if the sulfur in the hydrocarbon feedstock was at low levels, preferably less than 100 ppb; It is most desirable that it be less than 90 ppb to achieve an acceptable level of incentive stability and effectiveness. And after identifying the sensitivity to sulfur associated with these new incentives, and specifically the necessary and acceptable levels for the sulfur process: “18H; Successful commercial production of these stimuli began to appear, which faded with the appearance of another hurdle. It was found that some zeolite catalysts are wide in diameter and very sensitive to the presence of water under the known reaction conditions. In particular, water has been found to accelerate the rate of motivational 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 (hydrogen yo). Likewise, the water produced during the process, Tans, when it leaks into the trimmer feed or when the feed becomes contaminated with a compound containing oxygen. Finally, additional techniques have been developed. To protect incentives. Once again, commercial production seemed to be feasible from a practical point of view by developing sulfur catalyst refinement systems and low water using zeolite catalysts with a high capacity of 0 > selection and a wide diameter 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 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 coal (coking), and although the accumulation of coal between catalyst atoms is a common problem in hydrocarbon manufacturing processes, the extent of the rate of ve blockage by the accumulation of coal on the surface of catalyst atoms in this particular system has exceeded any expectations.

General description of the invention One of the objectives of the invention is to provide a method for refining hydrocarbons that induces low sulfur conditions to avoid the aforementioned difficulties 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 sulfur conditions to allow the process for longer periods. After analyzing and revealing in detail the phenomenon of blockage of low sulfur reactor systems as a result of coal accumulation; aang that it contained atoms and droplets of a metal and the size of the droplets ranged from 0 to within a few microns. I may think that there are serious problems Tan that are not taken into account in traditional refining techniques as the levels of sulfur and water in the Jef process are clearly high. Specifically; He discovered that there are problems that threaten effective operations and economic systems; Physical equipment integration and Load discovered that these problems arose under conditions of low sulfur and to some extent due to low water levels. For forty years ago, catalytic reforming reactor systems were made of mild steel (slag ging) on 77,725 chromium © and 721 molybdenum (Mo). With the passage of “Bl,” experience showed that the systems could be operated successfully for twenty years. Without noticing a loss of physical strength.The discovery of metal droplet atoms in the blockages caused by the accumulation of coal eventually led to the investigation of the physical properties of the reactor system.It is surprising that cases of 0 symptoms of very serious physical decomposition were discovered in the entire reactor system, including the pipes Furnace tube, piping, reactor walls, and other media J Catalysts containing iron 08 and metal screens in reactors.In the end, it was discovered that this problem is related to excessive carbonization of steel. Which leads to the brittleness of steel due to the injection of carbon into the metal.The extent of the potential catastrophic physical collapse of the reactor system can be imagined.

With traditional refinement techniques, carbonation was not a problem or significant and was not expected to be present in contemporary systems of low sulfur and low water with the possibility of using traditional process equipment. It is apparent that the sulfur present in conventional systems effectively inhibits carbonation. 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. Brief Explanation of Drawings Figure 1a is a photographic micrograph of a section of the inside of a mild steel furnace tube (ie, the part subjected to the chemical process) in a commercial trimmer. 0 The tube has been subjected to conventional tempering conditions for approximately 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 mild steel that was placed inside the sulfur reactor and reduced water in an experimental station for only 11 weeks. 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 carburization of steel 5881, which was carburized and flaked to a depth exceeding 1 mm. Detailed Description 7 Of course, the problems associated with fag carbonation are only physical system carbonization. The carbonization of the steel walls leads to "metal fragmentation", i.e. the release of effective metal atoms and droplets in the catalyst due to the corrosion of the metal. The reactive metal atoms provide additional sites for coal formation in the system. And while inhibition of the stimulus arising from the accumulation of coal is a problem that must be encountered in general in refinement, this important ye source for the formation of coal leads to a new problem of blockages, which exacerbates the existing problem to the extent

big. In fact, it was found that moving active metal atoms and coal particles exacerbate the problem of coal accumulation through the system in general. In fact, the active metal atoms are a catalyst for the formation of coal on them, and particles accumulate in every place of the system, which leads to blockages and hot areas arise from exothermic methane removal reactions. coal and cannot be controlled, which can lead to system shutdowns within weeks of start-up. The use of the process and reactor system of the present invention overcomes these problems. Therefore, the first characteristic aspect of the invention relates to a method for reforming hydrocarbons, which includes contacting hydrocarbons with a reforming catalyst, preferably 01 large-pore zeolitic catalyst 260106 containing alkali metal or alkaline earth and charged with one or more of Group VIII metals in a reactor system that has resistance to carbonation and metal fragmentation, which is an improvement over conventional reactor systems made of mild steel in low sulfur conditions (Jag) in conditions of low sulfur and water; And when trimming, the flaking resulting from carbonation is less than 0.0 mm per year, preferably less than 0.9 mm 1 per year, and it is more preferable that it be less than 1 mm per year. 1.1 mm per year. Avoiding scaling to this extent will greatly reduce soll fragmentation and coking in the reactor system allowing operation for extended periods of time. Another distinguishing aspect of the invention relates to a reactor system that incorporates means to provide resistance against carbonation and metal fragmentation, which is an improvement over conventional systems made of mild steel7 in a method for reforming hydrocarbons using a reforming catalyst such as a large-pore zeolitic catalyst. zeolitic catalyst including an alkaline earth metal and charged with one or more metals of the eighth group under low sulfur conditions and the scale resistance is less than about Yio mm per year and preferably less than V0 mm per year and preferably more It should be less than 1 mm per year, and it is best that it be less than 0.1 Yo mm per year.

A

Thus, the present invention is based on discovery; Among other factors, in low sulfur rectification systems and in low sulfur and water rectification systems there are notable carbonization, fragmentation and coke problems. And that these problems do not exist to a significant extent in the traditional refinement processes, where there are higher levels of sulfur, and the discovery led to intensive work and the 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 of exploiting and using resistant materials effectively with additives (other than sulfur) to reduce carbonization, fragmentation and coal build-up, various process modifications and things in common which have been presented to confront the problems effectively. Resistant to low sulfur reforming systems, preferably reactor walls, furnace tubes and grids mentioned Gi is not necessary in conventional reforming systems such as alloys, stainless steel, aluminium-0, chromized and some ceramic materials Also, it has been discovered that some other relevant materials which are applied 0 in the form of lamination, coating, coating, etc., may be effective resistance. These materials include copper, tin, arsenic arsenic and antimony germanium-28, brass, lead-0, bismuth, chromium, and metallic compounds resulting between the said metals, alloys and coatings with a silica or silicon basis similarly.In one of the preferred embodiments of the invention © - available A new resistant coating containing tin (din). In addition, the discovery led to the development of some additives; which are herein referred to as anti-carbonation and anti-charcoal agents which are sulfur-free primarily out of necessity; It is preferable that they be completely free of sulfur. These additives are considered to be organic tin compounds, organo-antimony compounds q, organo-bismuth compounds, organic arsenic compounds, and organo-lead compounds. Alia organic and low organo-arsenic compuonds led to the development of sulfur. Also, problems associated with sulfur-refining processes led to some unnecessary modifications and compounds in the process previously mentioned in traditional refining processes. These technologies include some temperature control techniques and the use of °

Very hot OS between reactors and regeneration processes for more hydrogen catalyst, use of phased heaters and tubes, use of temperature stages, use of superheated raw materials with higher tube diameters and/or tube velocities. Brief explanation of the drawings are Photographic micrograph of part of the inside of a furnace tube from : (Ih) Fig. 0 (i.e., the part subjected to the chemical process) in soft mild steel IY as Lie 19 commercial tempering apparatus that has been subjected to conventional tempering conditions for approx. ,

Jala reported on a photographic micrograph of a coupon-shaped sample from Boke (Fig. 1b). 11: He and water, sulfur cog SH, were placed inside a mild steel reactor of low Vo for a week only. ) Figure Detailed Description Metallurgy terms used herein in this statement are given the common meanings as stated by the American Metallurgical Society. For example, The Metals Handbook at vy. They are those types that do not contain small quantities, for example, carbon steels; Carbon steels are limited from any alloying elements (other than those generally accepted amounts of manganese and contain only a minor amount of copper, silicon, manganese, manganese, manganese, silicon carbon, other than carbon AT, is an element that is mild steel, phosphorus, sulfur, and sulfur, copper Yo.

0

This type of carbon steel is carbonsteels that contain carbon at a maximum percentage of about 76 72. And “alloy steels” are those steels that contain specific amounts of alloying elements (except for carbon and amounts Generally accepted manganese, silicon, copper, copper, sulfur, and phosphorus ° are among the known amounts of structural alloy steels; added to effect changes in mechanical and physical properties. Alloy steels will contain less than 10 7 chromium and stainless steel is a type of multiple steel types containing at least 7 01 or preferably 11 to 7 chromium chromium as a basic alloying element

in the ingot.

01 The focus of the invention is therefore generally to provide an improved method for reforming hydrocarbons 5 using a reducing catalyst; In particular, a large-pore zeolitic catalyst that includes an alkali or alkaline earth metal and is charged with one or more of the group VIII metals that are sensitive to sulfur under low sulfur conditions. This process must of course demonstrate better resistance to carbonization than conventional techniques

ve to refine low sulfur.

One of the solutions to the problem on which the present invention focuses is to provide a new reactor system that can include one or more means by using a reforming catalyst such as the aforementioned wide-pore sulfur-sensitive zeolite under low sulfur conditions.

The expression 'reactor system' as used herein means at least one reforming reactor and the corresponding furnace device and piping system. Figure (Y) shows a typical reactor system suitable for the application of the present invention. It can include A set of reforming reactors (01), (01) and (Yr) each reactor contains a catalyst layer. The system also includes a set of furnaces (11), (YY) and (TY) and a separator (VY).

1

And through absolute research with the present invention it was discovered that the problems associated with refinement

Low sulfur can be effectively counteracted by selecting a suitable reactor system material for contact with hydrocarbons during operations. Refining reactor systems are typically made of mild steel or alloy steels such as chrome steel.

chromium steel 0 is known for its imperceptible rates of carbonization and metal volatilization. For example, in the article, furnace tubes made of steel with a percentage of chromium Cr 7.785 7 # can last

Lele Yo under standard culture conditions. It was found that these types of steel are not suitable

under low sulfur conditions. It becomes brittle quickly as a result of carbonation, within about a year

only one. Sled found that steel contains 7.80 Cr chromium and molybdenum.

1 16 00 / carbonized and crusted to a depth of more than 1 mm per year.

In addition, the materials are considered under the conditions of the standard metallurgical practice known as resistance to charring and carbonization, and it is not necessary to resist sulfur refining of low sulfur three nickel-rich alloys such as (Incoloy 5, Incoloy 800 (A+), Incoloy (AYe, Incoloy 825). and (inconel 0 (Nee) and (Marcel and Haynes 230 (Y¥ +

10. Not acceptable because it shows excessive accumulation of coal and fragmentation of the metal. The Yoo stainless steel faa ll series preferably 14 and 31 FY Vg VEY are acceptable as materials for at least parts of the reactor system according to the present invention that come into contact with hydrocarbons and have been found to have a resistance to carbonation greater than that of

Mild steel and nickel-rich alloys

7 At first, I thought that aluminum inlaid materials such as those sold by Alon Corporation or what is called (alloy steel) 21001260 would not provide the required protection against carbonization in the reforming reactor system and the tempering process of the invention current. It has since been discovered that applying thin layers of aluminum or alumina to the surface of the metal from which the reactor system is made, or simply using

vo aluminized steel (UE alonized steel) composition can provide sufficiently resistant surfaces

VY

The low and that such materials are expensive sulfur for carburizing and metallising under conditions of sulfur refinement relatively although they are resistant to carbonization and metallisation, but they tend to crack and show decreases in stress resistance. The base metal layer is exposed to cracks, which makes it vulnerable to carbonization and fragmentation of the metal under sulfur-refining conditions °. While aluminum-coated materials were used to prevent carbonization in the cracking of ethylene with water vapor, these processes have been conducted at temperatures 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 GAY solution to the problems of carbonization and alumina includes the use of thin layers of ys aluminum or alumina at least part of the surfaces of the Nl that are the interior of the reactor system or alternatively the use of materials coated with alumina aluminum In fact, metal surfaces that are particularly susceptible to carbonization and metallurgy can be provided in the same way. These metallic surfaces include the reactor walls, furnace tubes and furnace lining where no Vo is applied and when the thin layer of aluminum or alumina is elongated. It is better for this thin layer to have thermal expansion Bilas for the thermal expansion of the metal surface (such as mild steel) placed on it so that it can withstand thermal shocks and repeated temperature cycles that occur during sharpening. This prevents cracking or cracking of the thin layer that may The surface of the base metal is exposed to carbonization catalysed by the hydrocarbon medium.Y- In addition, the film must have a thermal conductivity equal to or greater than that of the conductivity. or alumina in the reforming medium or in the oxidation medium associated with the regeneration of the catalyst and should not induce decomposition of the hydrocarbons in the reactor system.

VY

Or alumina include suitable methods for placing thin layers of aluminum Preferred methods include Jaa processes on metallic surfaces Well-known deposition techniques Commercially marketed alumina from Alonizing Powder and vapor diffusion such as the “coloring” process Terrytown, Pennsylvania. Process The metal (such as mild steel) is placed in a retort and surrounded by a mixture of mixed aluminum powders. The retort is blocked by Tus and placed in a controlled furnace under a suitable atmosphere. At a high temperature, aluminum spreads to a great depth in the process. The treated metal which 0 > results in an ingot. After the furnace is cooled, the bottom layer of the retort is taken and the excess powder is removed. The operations of leveling, trimming excesses, flakes 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 the metal crumbles Under conditions of low sulfur refinement according to the invention. Thin layers of chromium or chromium oxide ve can also be applied to the metal surfaces of the reactor system to make these surfaces resistant to carbonization and metallisation under conditions of low sulfur refinement. As with 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 carbonization problems under conditions of low sulfur refinement. 7 It is also possible to place chromium or chromium oxide on the surfaces of metals subject to carbonization and metallurgy Jie reactor walls or furnace interior walls and furnace tubes. As any surface in the system may show signs of carbonization or fragmentation of Sl under low sulfur conditions a thin layer of chromium or chromium oxide may be beneficial.

0 chromium oxide or chromium oxide When the thin layer of chromium is placed, it is preferable that it have a thermal expansion similar to the thermal expansion of the metal on which it will be placed. In addition, the thin layer must be of Chromium is able to withstand thermal shocks and the repeated temperature cycles chromium oxide or chromium oxide used during tempering. This avoids cracking and cracking of the chromium 0 thin film which may expose the lower metal surfaces to carbon inducing media. The thin chromium layer must have a thermal conductivity equal to or greater than the thermal conductivity of the materials used in order to maintain adequate mild steel in reforming reactor systems (particularly mild steel or chromium oxide) effective heat transfer Also, the chromium 0 film should not undergo decomposition in the reducing medium or in the oxidation medium associated with the regeneration of chromium oxide in the reactor system, nor should it catalyze the decomposition of ala hydrocarbons or chromium oxide, including Appropriate methods for applying a thin layer of chromium using mild steel deposition techniques on surfaces such as chromium oxide mild steel are well known. Preferred processes include powder and vapor diffusion processes similar to the “ve coating” process commercialized by Alloy Services Alloy surfaces Inc) "chromizing" a SIL in Wilmington, Delaware. The 'chroming' process is primarily a vapor phase diffusion process for Gara Wg (Tha) process coating (similar to the anodizing process described chromium The surface of the metal is chromium, followed by a thermal diffusion step. chromium Contacting the metal intended to be coated with chromium powder - v. And the treated metal and make the surface resistant to chromium carbonization, and this results in an alloy of low chromium. Sulfur and fragmentation of the metal to a large extent under conditions of sulfur refinement, and in some areas of the reactor systems, the local temperatures may become excessively high during Al-Tahdib (eg from 487 CE to 177 CE). In particular, this methane exothermic state occurs in the furnace tubes and in the catalyst layers, in methane removal reactions.

Vo within the accumulated coal balls that are usually present, which leads to local hot areas. While mild in the series is preferred over the use of mild steel types: steel, the use of steel types shows an accumulation of coal and the fragmentation of metal in Yoo. The series chromium and alloys rich in chromium in 001 stainless steel faall resistance JY sill is about 78 m. Thus, it is useful to use the series of the present invention, but it is not the best at all.

And stainless steels rich in chromium, such as £87 and EY, are more resistant to carbonization than the Cua 00 series stainless steel. These steels are undesirable in terms of heat resistance properties ( as it may become brittle). The preferred resisting materials on the 0 ye stainless steel series for use in the present invention include copper, tin, arsenic, antimony, bismuth, chromium, and brass. And the common compounds of these metals and their alloys (such as copper alloys, tin, copper alloys, copper, antimony, stannides, arsenides, bismuthides <a sa 3 5 arsenides, etc.). Steels and even nickel-rich alloys containing these metals show a lower level of carbonization. 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 touches hydrocarbons only, which allows the use of traditional building materials such as mild steel, and among these materials, tin is preferred. tin in particular Cua reacts with the surface to provide a coating that has excellent resistance at temperatures (lel © | and resists flaking of the paint. It is also believed that the containing layer could be a tenth of a thickness

Micronized to resist carbonation. Where practical, it is preferable to place resistive materials in the form of a 'paint-like formulation' (hereinafter referred to as Lag) in the reactor system, such as mild steel and stainless steel. Sufficient viscosity to provide a light vo coating with a measured and controlled thickness; Best of all, the paint is highly biodegradable 0591

To the reaction and contains tin, tin is reduced to active tin and forms iron stannides and nickel stannides and nickel upon heating in a reducing medium. The best of all is that the aforementioned paint contains four components At least 0 (or equivalent in function): (1) a hydrogenated tin compound, (7) a solvent system, (*) a metal tin fragmented, and (£) tin oxide as a reducing, absorbing, dispersing and binding agent. The coating should contain finely divided solids to reduce stagnation to a minimum and should not contain inactive materials that prevent effective tin interaction with the surfaces of the reactor system .

ve, and as a tin compound that is soluble in hydrogen, the tin octanoate compound is Tada tin octanoate in particular. Commercial formulations of this same compound are available and Tiga will dry to a gum-like layer on a steel surface that will not crack or separate. This property is necessary for the installation of any paint used in this field because it is likely that the coated material will be stored for several months before the hydrogen treatment as well if

1 The parts were painted before assembling with hydrogen. Also, if the parts were cauled before, they should be resistant to etching 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 that forms iron iron stannides in hydrogen at temperatures as low as (Se)ATV.

7 Tin octanate should not be used alone in paint as it is not viscous enough. Even when the solvent evaporates, the remaining liquid will drip and run down the coated surface. In practice, if this compound is used to coat the tube of the horizontal furnace, De, it will collect at the bottom of the tube.

Tin oxide as an absorbent, dispersing and binding agent is a porous 8-containing vo compound that can adsorb an organometallic tin compound

VY

It can be reduced to active tin 8 in a reducing medium. Organo-metallic tin compound via a colloid mill to produce fine tin oxide particles. In addition, tin oxide can be processed into a very resistant dry-touch tin oxide paint that resists rapid stagnation. The addition of tin oxide will provide flow. In contrast to the materials that increase the density of the coating, the component (;) is chosen so that the preform, which is a silica condensing material such as silica, becomes part of the coating when it is reduced. And it is not Te a ineffective surface coating may be left after curing. To ensure that (YF) is smooth; That is, the tin component, and finally, tin metal powder is added to the reaction with the surface intended to be painted at the lowest temperature 108 metallic tin possible, even in a non-reducing atmosphere. Preferably, the tin particle size ranges from 00 to 0

Ain micron to © micron allowing excellent coverage of the surface to be tinned Non-reducing conditions can occur during coating drying and tube welds and joints.

Lalas not to reduce part of the paint ala that in metallic tin and ensures the presence of the desired tin metal. The stannides to react and form the tin layer tin will be tin metal and the solvent should be non-toxic and effective to make the paint sprayable And spread when yo tin desire. It should evaporate quickly and have solvent properties compatible with a tin compound that is better than isopropyl alcohol which hydrolyzes.”©90:08. And isopropyl alcohol is useful as necessary. Pentane and pentane are hexane release, while hexane can be as acetone-26 tends to precipitate organic tin compounds. organo-tin compound Y- 7718 has 0 tin by tin In one embodiment tin plating may be used

Stannous octanoate in Ten-Cem cm" 5 tin, tin metal powder, and isopropyl alcohol 3ST. (octanoic acid .isopropyl alcohol

A Tin can be applied in a number of ways. For example, the furnace tubes of the reactor system can be coated individually as units. It is possible that the system of the refinement reactor according to the present invention contains le sia Tare of furnace tube units (for example; about TE furnace tube units) having an appropriate width, length and height (iad)? Yoh Jud and ?, 1 meter wide and 17.7 meters high). Typically, each unit includes two upper return arches of two suitable diameters, preferably about 1.7 meters in diameter. The two upper return apses are connected by four to ten U-shaped tubes of suitable length (for example, 1.8 meters long). Therefore, the total surface area to be painted in the units can vary within a wide range; Od may in one embodiment be about YOYY 0 square metres. And coating the units instead of the tubes individually may be fade in four aspects (1) Painting the units instead of individual tubes avoids damage to the tin coating by heat, as the components of the units are usually treated with heat at high temperatures Tas during production (Y) that coating units is often faster and less expensive than coating individual tubes (©) coating units should be more efficient during production and (;) coating units should be more efficient than welding point coating. That the coating of the units may not be completely coating the tubes as if the tubes are coated individually.If the coating is not enough, the GS can be coated.The tubes can be coated individually.7 It is better to spray the paint in the tubes and the upper curves.Sufficient amount should be applied of paint to cover the upper return pipes and curves Lol and after spraying the unit it should be left to dry for about VE hours followed by exposure to a slow stream of hot nitrogen (eg 16C for 4 hrs). Therefore, it is better to apply a second coat of paint and dry it in the manner described above, nitrogen.After applying the paint, the units are better left under nitrogen pressure ve

Yad)

Slight without exposing it to temperatures exceeding about 97 °C, such as Lady Sl, not exposing it to water, except as it may be exposed to it during the water test.

And the effective iron-bearing paint, Lad sada iron, in the present invention. It is preferable that the iron-bearing paint contain various tin compounds to which iron has been added

lias 0 is up to a third of the iron ron to tin ratio on a weight basis.

It could be adding cron for example. As ferric oxide, 88,0. The benefits should be available by adding iron 000 to the tin-containing paint, in particular: (1) facilitating the reaction of the paint to form iron stannides and thus the paint behaves as a fluid flowing (1) dilution of the nickel concentration in

| The layer of tin 82001085 thus provides better protection against coal build-up and (©) should

It results in a coating that can provide protection against char build-up of iron stannides even if the underlying substrate does not react well.

Other means of preventing carbonization, charring, and metal fragmentation in a low sulfur reactor system include the use of a metallic coating or plating of chromium-rich steels.

chromium Vo contained in the reactor system. It may include metallic coatings or laminations

These are tin, antimony, bismuth, or arsenic, and tin 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.

7 It has been found that in low sulfur reforming reactors where AnSh, coal build-up and metal fragmentation are particularly problematic, coating of nickel-containing and chromium-rich steels with a layer of tin Thus creating a double layer of protection. It produces an inner chromium-rich layer that also resists carbonation, coal build-up, and metal fragmentation, and produces an outer tin layer that also resists carbonation, coal build-up, and calcification fragmentation.

vo tin outer layer also resists carbonization, charring, and metallurgy. This happens when

Y. Tin-plated 8N for tempering temperatures chromium rich in chromium steel The steel is exposed to M; It reacts with steel E to form typical iron steroids (TER) with a temperature of up to 1H. Thus, nickel E1H is better filtered from the surface of nickel M1, nickel stannides, and in some cases; The chromium-rich steel may leave a layer of steel, iron, iron and nickel stannides. It is desirable to remove the 0-chromium-rich chromium layer to expose the stainless steel layer. steel faall on stainless steel tin for example; It was found that when plating Jad tin at 40°C and heated at about 49°C, a layer of stainless steel anal and nickel-free chromium chromium 7117 containing about chromium rich in chromium steel was produced. 40 grade stainless steel mainly compared to nickel 01 stainless steel, it is desirable to chromium rich in chromium steel Wl and when applying a coating layer of changing the thickness of the metallic coating to achieve the desired resistance against carbonization, coal build-up and metal fragmentation In a chromium-rich steel bath, for example, this can be done by adjusting the molten steel contamination time. The resulting tin may be chromium-rich steel, and this will affect the thickness of the steel layer Vo Chromium-rich steel It is desirable to change the operating temperature or change the composition of the rich steel in the plated chromium steel layer and thus control the resulting chromium concentration. steel It was also found that additional types of steel can be protected from carbonization, metal fragmentation and metal build-up by a subsequent treatment process that includes applying an oxide coating, and this coating will be thin. with a thickness of .Cr,05 as thin chromium oxide; This chromium oxide protects steel types, chromium oxide, with a thickness of a few microns. And the placement of chromium oxide (alonized steel) types (Jie tin steel) and aluminum ila steel will result in reduced sulfur conditions that induce sulfur refinement.

The chromium oxide layer can be applied in a variety of ways, including: a coating of chromium or cla SU binary followed by a reduction and steam treatment with an organo chromium compound or a layer of chromium metal followed by oxidation The resulting chromium-coated steel. A test of electroplated tin-coated steels, which Cag dal exposed to low sulfur refinement for a long period of time, showed that a layer of chromium oxide was formed on the surface of the tin layer or under the tin layer. The chromium oxide layer deteriorates the stannides layer and even seems to make steel more resistant to carbonization, metal build-up, and metallurgy. Accordingly, applying a layer of chromium oxide on steels coated with either tin or aluminum leads to the production of steels with greater resistance An SU and an accumulation of ll Under conditions of low sulfur refinement 0, the following treatment process has special applications for treating steel types that are coated with tin “n” or aluminum, which need to be replaced after long exposure to low sulfur conditions. Veo also found that steel coated with aluminium, Jie aluminum, "alonized" steel, which is resistant to carbonization under the conditions of current low sulfur sulfur refinement, may become more resistant by subsequent 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 repairing any 00 defects or cracks in the aluminum coating. In addition, this next treatment (Jia) will result in lower costs since the thinner alumina coating (Sey) is applied to the surface of the steel which will be treated with a tin coating. In addition, this next treatment will protect the steel layer. steel, which is exposed when the aluminum-coated steel is bent, which may lead to cracks in the aluminum layer and expose the steel AY to the carbonization that occurs in ve tempering conditions.

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Also, this next treatment process prevents the formation of coal on the surfaces of steel, which is the formation of coal that occurs under the cracks that appear on AIS steels, and prevents tin and non-tinned aluminum from being coated with aluminum It was found that samples of alonized steel that were coated with tin on one face only lead black on the uncoated side only under conditions of low sulfur refinement. And the coal that forms on an aluminum coated surface is a gentle coal produced by cracking on acidic alumina sites, and this coal is not able to cause additional sedimentation. Accordingly, the application of a post-treatment by applying a tin coating to aluminum steel can provide an additional reduction of the problems of carbonization, coal build-up and metal fragmentation 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 different materials of the present invention can be selected and rated Ga for their responses to the carbonization media. For example, iron 8, cobalt, nickel, and carbides are relatively unstable, which later get refined, and coal and crumbled metal residues are formed on it. While Jia elements chromium, niobium Vo, vanadium, molybdenum pil gall 5 tungsten, tantalum, and zirconium form stable carbides that have greater resistance to carbonization, coal build-up, and metal fragmentation. The elements tin, antimony, and bismuth do not form carbides or coal. These compounds can form stable compounds with several metals such as iron, nickel and copper under refinement conditions. stannides, antimonides 0, bismuchides 5, compounds of lead, mercury, arsenic, germanium, indium, tellurium, selenium, thallium, and sulfur sulfur and oxygen are La resistive. The last category of materials includes metals such as silver, copper, copper, gold, platinum, and refractory oxides such as silica, silica, alumina, and these

The material is resistant and does not form carbides; Or react with other metals in a carbonization medium under denaturing conditions. As mentioned by Gla, 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; Carbide-resistant materials may be expensive or alien to traditional materials (such as mild steel (mild stezl) used in building 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, and so on. They are not susceptible to carbonization for at least part of the metallic surfaces in the 0 reactor system. For example (JO) the least part of the furnace tubes may be made either or both of ceramic materials. In selecting ceramic materials for use in the present invention it is preferable that Ceramic materials have a 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 1 at the existing temperatures within the reforming reactor system.Lady The ceramic materials must be capable of 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 equivalent to the thermal expansion of the outer surfaces with which the inner surface is in close contact. This avoids stress at the contact points during the #0 temperature cycle when starting and stopping. Lads 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 1600L, silicon oxides Yo 5 11100, silicon nitrides and aluminum nitrides.

Yt and nitrides of silicon carbides, and among these, silicon carbides 0 where it is not limited to silicon 85 111600 are particularly preferred due to their ability to provide complete protection for the system of low sulfur reactor under sulfur-reducing conditions. It is possible to coat at least part of the metallic surfaces in the reactor system with a layer of, and the metallic surfaces that can be coated include the reactor walls, silica or silica, the furnace tubes, and the internal surfaces of the furnace, as they are not limited to that, as they show signs of Carbonization and metal fragmentation on any metallic surface in the reactor system under conditions of sulfur refinement on it. Silicon Gohl can be used with electroplating silica silicon to paint metal surfaces. Silicon 0 can be used as a vapor carrier gas. From the alkoxy silane and chemical vapor deposition of the alkoxy xylene compound, a thermal expansion is approximately equivalent to silica or silicon. Also, it must withstand thermal shock and repeated temperature cycle during trimming. This avoids chip cracking and exposure of the surface underneath to carbonization that is stimulated by the esilica, Vo silicon, or hydrocarbon silica medium. The silica sheet must also have a thermal conductivity close to or greater than the thermal conductivity of metals conventionally used in reforming reactor systems to maintain efficient heat transfer. The silicon wafer should not decompose in the reforming medium or in the oxidation medium associated with the regeneration of the catalyst as well as the silica or the silicon itself. With the invention (i.e. different areas in the furnace) may be exposed to temperatures in a wide range, the selection of materials can be coordinated so that materials that provide better resistance to carbonization are used in those areas of the system that are exposed to higher temperatures.

With regard to the selection of materials, it was discovered that the surfaces of oxidized group VIII metals such as (and carbonation of (andl) are more effective in terms of the accumulation of cobalt, cobalt, nickel, nickel, iron, faa Wags, and their non-oxidized counterparts. for example; It was found that the air-roasted steel sample was more effective; Significantly; from VEY series non-oxidizing stainless steel of the same type as A98 steel. It is believed that this is due to the reduction of the steel dello soft and these metals are active in the form of nickel and / or nickel iron oxidized again, which produces iron metals, especially in the carbonization and accumulation of coal. Thus, it is desirable to avoid the use of these materials as much as possible during oxidative regeneration processes such as those typically used in catalytic reformation. Where it was found that air-roasted and tinned tin 010 series stainless steel stainless steel can provide resistance to carbon build-up and carbonization equivalent to the resistance shown by non-air-roasted tin-0 stainless steels. Yoo stainless steel chain Add to that; He will realize that oxidation will be a problem in systems where sulfur effectiveness is a minor issue and sulfur uses the catalyst's sensitivity to sulfur on such sulfur metallic surfaces. At any time when the sulfur levels in the systems become insufficient, any metal sulphides are formed on the metallic surfaces after oxidation and reduction ae and then reduced to a soft metal. This metal will be very reactive to carbon build-up and carbonation. It is widespread and dangerous in the composition of minerals or to the accumulation of Tal that is likely to cause damage of the present invention. Lids and other techniques to address the problem can be used in conjunction with appropriate material selection for the reactor system or they can be used alone. STL and ASH coal accumulation are among the preferred auxiliary techniques; Addition of anti-sulfur agents © Refining Process. These agents can be added continuously during manufacturing and act on the reaction, or the hydrocarbons can be added to those surfaces of the reactor system that come into contact with the hydrocarbons prior to the reactor system. These agents interact with the surfaces of the system and/or the reactor nickel by decomposition and attack the surface to form intermetallic compounds of iron xe va bismuthides, antimonides, antimonides, stannides such as cnickel tins, etc. Resistant intermetallic compounds, carsenides, arsenides, plumbides, and lead for carbonization, coal build-up, and metal fragmentation, and can protect lower minerals. 9 to form oxides on the surface of the metal. As a result, metal sulfides such as hydrogen metal sulfides do not reduce these compounds with hydrogen, as they are less inclined than metal sulfides to fade the system. Therefore, the continuous addition of the carbonation inhibitor with the feed can be reduced to a minimum. Non-sulfur agents against carbonation and coal build-up include organometallic compounds and organo-tin compounds such as organo-arsenic compounds and organo-bismuth compounds, including organo-lead compounds. Compounds and organic lead compounds alah and tetramethyl tetrathyl suitable organo-lead compounds such as organo-tin compounds preferably organic tin compounds ctetrametheyl lead as trimethyl tin hydride and trimethyl tin hydride Especially tetrabutyl tin Vo. Special organic phosphatases include neodecanoate, chromium octate, bismuth neodecanoate, tiodecanoate, manganese carboxylate, manganese carboxylate, copper naphthanate, and tetrabutyl silver neodeconoat, palladium neodeconoat, palladium Y, tributylantimony, tetrabutyl germanium, zirconium lactate, triphnylarsine dn8, and triphenylantimony zirconium octate dependent The question of how and where these factors are added to the reactor system depends primarily on the specifics of the particular process design. For example, it can be added continuously or intermittently with feeding. vo

winding as 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, or on site (ie in an existing system). This must be done correctly if it is added at 0 location after the stimulus renewal. Very thin coatings can be applied. As it is believed using organo-tin compounds, micron-thick coatings of iron stannides are effective. The best method for coating agents on the surface of a new or existing reactor or on the surface of a new or existing tube furnace involves the decomposition of the organometallic compound in a medium of hydrogen at 0 temperatures up to about 487 °C. For organic tin compounds, for example, active tin and metalloids are produced on the surface of the tube. vey At these temperatures, tin will react with the surface of the metal to form an oxide on it. The ideal temperatures at which the coating should be applied will depend on the particular organometallic compound or mixture of compounds if alloys are used as desired. Excess batches of the organometallic coating agent may be fed into the tubes at a high hydrogen flow rate to carry the coating agent through the entire system in an aerosol form. Sa then reduced the flow rate to allow the metallic coating in aerosol form to coat and react with the furnace tube or reactor surface. Yay from this the compound could be introduced as a vapor that decomposed and reacted with the hot walls of the tube or reactor in a reducing medium. LS Ye Bla states that reforming reactor systems prone to carbonization, aerating and coking can be remedied by applying a biodegradable tin-containing coating to those areas most susceptible to carbonization.This technique works particularly well in a controlled furnace Such control is not always present If “hot spots” appear in the reactor system vs.s, especially in the furnace tubes where the organometallic compound may decompose

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and forms a precipitate. 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 includes pre-heating of the entire reactor system, where Aa is heated from inlet to accelerator, preferably from 87 °C to 7 °C, preferably more than 176 °C, with a hot stream of hydrogen gas, and after preheating, a cooler gas stream is introduced at a temperature ranging from from 4107m to 77m preferably from 1001m to a TY and best of all at about 784m; This stream contains an organometallic compound in vapor form in the preheated reactor system. This gas mixture can be introduced at the onset of stream 0 and can provide a "ware wave" of decay through the complete reactor system. And this process works; mainly; ON Hot hydrogen gas produces a uniformly heated surface that decomposes the cooler MOG as it travels as a wave through the reactor system. The colder organo-metallic tin compound decomposes on the hot surface and covers it, and the metallic organo tin vapor continues to move 5 . in wave form to treat the hot surfaces in the heart of the process from the reactor system. Therefore, the entire reactor system may have a uniform coating of the Lorgano-metallic tin compound and it may be desirable to perform several cycles of hot and cold temperatures to ensure that the entire reactor system is coated with the organometallic tin compound. a In the reforming reactor system of the present invention the naphtha is refined into aromatic compounds. and feeding naphtha Gall, which is a light hydrocarbon, preferably with a boiling point within the range from about 17 C to 777 C; it is more preferable from about a TA to a 19/7, and the naphtha feed contains alpha hydrocarbons or paraffinic and transformation of aliphatic compounds Lida coda at least ve; to aromatic compounds in the cleavage reaction zone.

The low Ya of the invention, it is better that the feed contain sulfur and in the sulfur system 00 preferably more than at least sulfur ppb of sulfur at least 001 than if necessary a sulfur absorption unit can be used sulfur Parts per billion sulfur sulfur To remove slight excesses of sulfur sulfur The preferred refinement process conditions include a temperature between the mother and 815 C. pressure between zero and 00; Atmospheric pressure of 5 00 Y, preferably more than 684 m hydrogen is sufficient, and 1560 atmospheric pressure is enough; And a hydrogen recycling rate of 16, preferably between to a hydrocarbon in hydrogen to produce a percentage of the gram molecular weight of hydrogen, a speed of 01 and 1,9, and more preferably between Yoo and 0,1 Feeding to the trimming reaction zone between 0 and 0.1 space fluid per hour for the hydrocarbon feed stream above the trimming catalyst is between 0 05 0 and preferably between 0 and to achieve the appropriate trimming temperatures; It is often necessary to heat the tubes of the M7117 furnace to high temperatures; These temperatures often range from and most of the time from 487 °C to 49 °C. a 7/17 °C; Usually from £08 0 to GAY to It was found, as mentioned above, that the problems of carbonization, coal build-up and metal fragmentation in vo systems and these low fan are associated with high local process temperatures sulfur sulfur The problems are particularly severe Especially in the system furnace tubes where particularly high temperatures prevail. In traditional refining techniques where high levels of sulfur are usually present. Tal «ed; The temperature of the surface of the furnace tube reaches 174 C, which is considered excessive, coal accumulation, or metal fragmentation. An SU, however, did not notice any effect of the low Ye. The carbonation, coal accumulation, and sulfur fragmentation of the excessive metal were detected in the molybdenum and chromium-molybdenum sulfur systems containing chromium steel and the rapid increase in the types of steels. The degrees of stainless steel and types of stainless steel ao 01 increase the temperature to a temperature of 807 °C.

Tv. Accordingly, the other distinctive aspects of the invention are the low temperatures of the metallic surfaces inside the furnace tubes, transmission lines, and/or reactors of the tempering system below the previously mentioned levels. for example; Temperatures can be monitored using thermocouples. Thermocouples can be attached to Aa surfaces distributed at several locations in the reactor system. in the outer tubes of the furnace; Preferably at the hottest point of the furnace (usually near the outlet of the furnace) 5 In case of necessity, adjustments can be made in the operation of the process to maintain temperatures at the desired levels. There are other techniques to reduce undesirable high temperatures at the system surfaces, for example; Heat transfer zones by means of resistance tubes (and usually more expensive) can be used in the last stage where temperatures are usually higher. Between reactors in the Tas hot hydrogen system additionally hydrogen can be added for refinement. A large incentive charge can also be used. The stimulus can be identified more regularly. In this case; It is best achieved using a layer-moving process where the catalyst is drawn from the last layer and regenerated and charged to the first layer. The carbonization and metal fragmentation can be reduced in the reduced reactor system of the present invention with the use of new sulfur-refining equipment constructs and other process conditions. for example; The reactor system can be built with tubes and/or staged heaters. Also, heating devices or tubes that are subjected to temperature conditions can be made from reforming reactor systems; Any materials du SU severe in the reactor system are more resistant materials such as those described above. And it is possible to continue making heating devices or pipes that are not made of traditional materials. generally more expensive than conventional materials) while a reactor system that is sufficiently resistant to carburizing and metallising can still be provided under low tempering conditions. In addition, this should facilitate the retrofitting of existing sulfur sulfur reforming reactor systems to make them resistant to carbonization and metallisation under Yo sulfur operating conditions.

It is phased. It is JB). The reactor system can also be operated using two thermal zones, at which the temperature in one of them is the highest, and the temperature in the other is at its lowest value. This method is based on the phenomenon of fragmentation of a metal that has a temperature High and low °C, where the fragmentation of the metal decreases to its lowest value at a temperature more than the upper and at low temperatures, meaning that the temperature at which 0 temperatures are less than the low is carried out, or close to it, refinement operations occur; At a temperature lower than that at which the fragmentation of the metal begins, which causes a problem. When operating parts of the reactor system in different regions, the temperature must be reduced vs metal by an amount equivalent to what it would be if the reactor system was at a temperature Heat stimulates the dissociation of the metal. Other benefits of such a system include improved heat transfer efficiencies; And the ability. On reducing the size of the equipment due to operating parts of the system at higher temperatures, as operating parts of the reactor system at levels lower or higher than that (dl) that help metal fragmentation occur only reduces the thermal range in which fragmentation occurs ve without completely eliminating it. This is unavoidable due to the temperature fluctuation that occurs from day to day during the operation of the reforming reactor system. In particular, the fluctuation that occurs during system start-up and shutdown, as well as the temperature fluctuation during circulating and during heating of the process fluids in the reactor system. Minimum hydrogen with the use of highly heated raw materials (such as hydrogen) through the walls of the furnace. hydrocarbons Possible limitation of the need to heat the hydrocarbons Tube diameters Ge Upright trimming Jolie Another process design method includes providing a system wider and/or have greater tube velocities to minimize exposure of the heating surfaces in the 'hydrocarbons' vo reactor system

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As previously mentioned, catalytic refinement is well known in the oil industry and involves processing naphtha gall 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 into aromatic compounds by dehydrogenation 1 and the conversion of JS cyclopentanes into aromatic compounds by conformation and dehydrogenation Converting non-cyclic hydrocarbons into aromatic cyclic compounds by removing hydrogen from them. A number of other reactions also occur, including dealkylation of alkylbenzenes, formation of paraffins, and hydrocracking reactions that produce light gaseous hydrocarbons such as methane 0, ethane, propane, and butane. butane Hydrocracking reactions should be reduced to a minimum during refinement because they reduce results whose boiling points are close to that of gasoline and also reduce hydrogen and so on; Refarming in this statement refers to the processing of a hydrocarbon feed by using one or more Jeli with transpiration of aromatic compounds to provide a product rich in aromatic compounds (i.e. the proportion of aromatic compounds in it is higher than that of aromatic compounds in the feed). While The present invention is primarily directed towards catalytic reforming and will generally be useful in the production of aromatic hydrocarbons from various hydrocarbon feedstocks under low sulfur reforming conditions. Other feedstocks similarly to ve provide a product rich in aromatic compounds.Thus, while the conversion of naphtha compounds is an embodiment of Saba, the present invention can be useful for the conversion to various feedstocks such as paraffin hydrocarbons and olefin hydrocarbons hydrocarbons, acetylene hydrocarbons, cyclic paraffin hydrocarbons, and cyclic olefin hydrocarbons

cyclic olefin hydrocarbons and mixtures thereof, specifically saturated hydrocarbons. Examples of paraffin hydrocarbons are those that contain from 1 to 0 carbon atoms, Jie carbon p-hexane and methylpentane (lu). The obedience is p-heptane n- heptane 0, methylhexane, dimethylpentane and p-octane n-heptane Examples of acetylene hydrocarbons are those with from + to 01 Carbon atoms, such as hexyne, heptyne, and octane, etc. Examples of cyclic paraffin hydrocarbons are those that contain from 1 to 10 carbon atoms, such as Jie methyl cyclic paraffin cyclopentane, cyclohexane ye, and methyl cyclohexane, Sy methylcyclohexane, methyl cyclohexane. dimethylclohexane, and one of the typical aromas for olefin hydrocarbons is paraffin hydrocarbons, those in which from “to 10” carbon atoms, Jia carbon, is methylpentene cyclo pe Sa methylcyclopentene cyclohexene and methyleyclohexene and dimethylcyclohexene .dimethylcyclohexene and the present invention will be Take to reformation under low sulfur conditions by using different types of catalysts for reformation. These catalysts include the unlimited eighth group metals carried on heat-resistant inorganic oxides such as platinum on alumina, platinum, tin 2057 on alumina, platinum and rhenium, PURe on alumina, and the unlimited eight group metals contain zeolite. zeolite as platinum ¥- or platinum, tin, PURe, platinum and rhenium PURe on Je zeolite zeolite type (L) and zeolite Anah »2 type (ZSM-5) and silicate silicalite and beta, and the unlimited group VIII minerals contain zeolites of the type Lzeolites (L), alternating alkaline and alkaline earth. It includes a better embodiment of the invention using a large-pore zeolitic catalyst | 0 includes an alkali or alkaline earth metal charged with one or more protective metals

Group VIII metals. It is best to use a catalyst in refining a feed of -naphtha and the term "large-pore zeolite" generally refers to a zeolite having an effective diameter of + plus to 10 angstrom. The crystalline zeolites ° crystalline zeolites with a wide diameter are preferred and useful in the present invention on type L zeolite (L), zeolite (X) zeolite, zeolite (Y) zeolite, and faujasite, and these zeolites have pore sizes Apparently, it ranges from 7 to 9 angstroms, and the best of all is zeolite type (1).The composition of zeolite type (L) can be expressed as molecular weight ratios of 0 grams between the following oxides: My, 0 : AL,05(5.2-6.9) SiO, : Y H,0 (0.9-1.3) In the above formula (JM) stands for cation and « stands for the valence of 5M 7 and it can be any value from zero to Approximately 49. The x-rays of (L) zeolite are deflected and the property and method of preparation are mentioned in detail in US Patent No. 77117845, the statement of which is incorporated into this specification for reference.The actual formula may vary without changing the crystal structure. Dad The gram-molecular ratio of silicon to 1 for aluminum may vary from 001 to Ye (Say) Write the chemical formula for zeolite 7 Tous (Y) zeolite about it as gram-molecular ratios between Oxides in the form: xSi0;: YH,0 - : rumate NagO (0.7-1.1) and in the above formula # is a value greater than ? and reaches up to about .1 and the value of BY reaches about 4. And for zeolites (Y) zeolite is a deflected X-ray sample of the characteristic powder that can be used with the above formula for identification.(Y) zeolite is more fully described in US Patent No. 7070017 the content of which is incorporated into this statement as vo reference.

vo is a crystalline zeolite molecular sieve that can be represented (X) zeolite and zeolite z by the formula: (0.7-1.1) 11/00 : Ro: Ml (2.0-3.0) SiO, : Y 0

M valence of an especially alkali metal or alkali earth metal and OB and in the above formula 34 stands for zeolite and “7” may have a value of about / depending on the identity of 14 and the degree of hydration of the zeolite - its properties and method Ad ath X-ray model of crystalline zeolite. The zeolite is more fully prepared in US Patent No. 7,887,744, the content of which is incorporated into this statement for reference. It is preferable to have an alkali metal or an alkaline earth metal in the wide-pore zeolite or barium strontium, and it could be the earthy metal Alkali barium large-pore zeolite Ve The alkaline earth metal can be combined into barium preferably calcium or strontium over barium by composition, impregnation or ion exchange. Barium zeolite is preferred, as the zeolite is somewhat less acidic. Acidic catalyst Other alkaline earth metals produce an acidic catalyst, and strong acidity is not desirable in the catalyst because it stimulates fracturing, producing less options. By using barium, a part of the metal can be exchanged. Alkali with barium AT and in the Vo embodiment with zeolite This includes contact with the zeolites known ion exchange techniques for zeolites *387. In this embodiment the ion is a solution containing an excess of barium diions from better AYO zeolite weight; From 750.1 to cbarium the barium .zeolite used in the invention should compose large-pore zeolites and charge Ye ruthenium zeolites catalysts. And ruthium nickel with one or more of the metals of the eighth group, such as nickel, platinum metals, platinum, iridium, paladium, palladium, rhodium, and rhodium, and these are platinum options, especially platinum iridium. The eighth preferred group is Iridium and that it is more stable under hydrogen is greater with regard to the formation of dehydrogenated cyclic compounds than the metals of the hydrogen group. The reaction conditions for the formation of dehydrogenated cyclic compounds ve

The other eighth. If used, the preferred percentage of platinum weight in the catalyst is between Jog 708.1. Group VIII metals are incorporated into large-pore zeolites by compounding, impregnation, or ion exchange in an aqueous solution of a suitable salt. And if (Bo) wants to combine two metals from the eighth group in the zeolite, the process can be carried out simultaneously or sequentially. To make the present invention more clear, the following examples show certain distinctive features of the invention. It should be realized that this invention is not limited to Al A picture of the pictures of the specific details mentioned thereof. 01 Example (1) Substitution tests were carried out on the effect of sulfur and water by carbonization in the reforming reactors. External used as a reactor to study the carbonization of 1 47 series stainless steel wires and their transformation into brittle wires.Three wires of 1 faa stainless steel wire of 1,075 inch diameter each were inserted into the tube While a part of the tube with a length of ½ inch was kept at an equal temperature along its length equal to 1977 m by means of a furnace The system pressure was kept at VE standard atmospheric pressure Jad hexane in the reactor at a rate of Yo microliters/min or what This equates to 0.0mL/hour at a hydrogen flow rate of ov of about 5*cm/?min (pe) being 0860:1070 hydrogen to hydrocarbons (0:* Jad hydrocarbons). The amount of methane in the resulting flow was measured to determine the presence of exothermic methane reactions. A successful experiment was conducted using basically pure hexane containing less than 57 parts per million sulfur and it was found that the tube was mid with carbon after vo only three hours. Not only did this stop the hydrogen and hexane feed flow, but vv actually ruptured the pipe and caused swelling in the reactor. The percentage of methane was close to carbon, because the increase in carbon reached 7850 before clogging. 0 in the resulting flow is about methane. Parts V01 Another experiment was carried out using almost the same conditions except that an hour was added before it was stopped to check the wires. Did not notice 50 The experiment continued for one million sulfur sulfur during the experiment. And it remained stable at about 717. by weight due to methane. No increase in methane 0, and no sulfur carbonation was observed by thermal cracking. There were no blockages arising from the accumulation of sulfur in steel wires, sulfur ppm sulfur 1. A similar experiment was conducted with only one furnace, which is addition (i.e. ten times less than the previous experiment), and this experiment showed a slight formation of michen Small amount of steel watch. Examination of EA steel wires or clogging after methane 0 carbon revealed bands of surface carbon A, however, no carbon was found ppm water (at a ratio of 70.1) 0001 Another experiment was conducted except that It took Lsulfur as methanol 0608001. No hexane was added to the hexane, an hour was added, and no blockage occurred in the reactor. Where it was discovered when the tube cleaved that the experiment 17 was not carbon, except that the accumulation of carbon, about 7200 of the tube, was filled with dangerous carbon ae, as happened in the successful experiment. (Y) Example: The tests were carried out. To select materials suitable for use in low mild steel sulfur reforming reactor systems; That is, materials that may show better resistance to carbonization than mild steel, low sulfur. °C with the thermocouple positioned on the alumina in. Afo outer surface of the tube in the hot zone. The furnace tube had an inner diameter equivalent to carrying out several experiments at a used temperature equivalent to 7149 C, using a thermocouple suspended in the hot region (about 7 inch cm) of the tube. The thermocouple vs

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Internal temperatures range from 0 ° C to 10 ° C with less stability than the external thermocouple. It contains carbon steel (mild steel). Stainless steel 0 Y, Yo with chromium and chromium for an hour. Under sulfur-refining conditions the samples of various materials were placed in an open boat inside the hot zone of the furnace tube.It was 0.77 inch and held well Y/Y cm. The boats were 7.94 cm long and one inch wide. Within the heated zone of ¾ cm 7 of the tube. Each boat is connected to a glass rod for positioning and lifting. An internal thermocouple is not used when boats are placed inside a silica .0 tube. For a few minutes then nitrogen occurs Before the preliminary operation, the tube was washed with nitrogen hydrogen in propane, bubbles of commercially packaged carbonated gas consisting of a 1 liter propane mixture at a capacity of toluene inside a flask filled with propane at a rate of 79 propane in the mixture feed invader. Toluene 71 room temperature was maintained to withdraw about ve cm / min and at a pressure equivalent to atmospheric pressure within Yo to YO on gaseous flows from

Ved the device. The temperature of the samples was raised to temperatures suitable for operation at a rate of degrees per minute. After exposing the materials to the carbonated gas for the desired period at the desired temperature, the device is switched off with an air stream that is directed at the outer surface of the tube. When the device is cold vo and the boat is raised for inspection, nitrogen sufficiently, the hydrocarbon gas is displaced with nitrogen and analysis. After each pre-treatment, such as cleaning or roasting, the samples are weighed. The weight of most is mg. Typically, each of the experiments was conducted with three to five Yoo samples. The samples were less than vo

in the same boat. A sample of TY series stainless steel was placed in each of the experiments as an internal standard sample. After the completion of each of the experiments, the condition of the boat and each of the materials was carefully observed. Also photographing the boat. Each of the materials is then weighed to determine the changes with 0 preserving any 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 analysis to determine the responses of coal accumulation, metal fragmentation and carbonization for each of the materials. It is essential that the residence time of the carbonation gas used in these tests be significantly higher than that of a typical commercial process. Thus, it is believed that the experimental conditions were more severe than the experimental conditions in the commercial operations. Some materials that fail (in terms of durability) these tests can be relied upon for commercial production. Nevertheless, the test provides a reliable indication of the relative resistances of gall to coal build-up, carbonization, and fragmentation.

The results are shown in the table below: For the percentage of overweight homeostasis | Dinitate for alkyls ss as a result of the accumulation of carbon AA 1 chromium 0016: FAA eevee eo Cr pos Hy +C3Hg 780 + C;Hg 75 * (by weight) 0 Of course, the above results are qualitative and depend on the shape of the surface. That is, the microscopic surface roughness of the metals. The percentage indicates the increase in weight due to the accumulation of carbon on the self-catalytic surface.

(£Example (¥) The same techniques as previously used were used to ferment a wide variety of J gallons at a temperature of 2149°C for VT h. The results are shown in the table below. Each group represents a side-by-side Dos comparison in a single boat under Matching conditions ° Table (1) carbon accumulation ee ed Nive ese edema Lh sees rn

Ns mew] Le ewes 8 nickle 4

Ni we eat a l pee) d e

Rossi H (Suwon) ‎Ley | a Tin can Zero No Nitin Carbon (c steel 0) 719 11 + Hy +C;Hg 7 81 (by weight) (Y) Roasted in air for Two hours at a temperature of 1000 °C to produce a thin layer of oxide.Example (4) Additional materials were tested using the techniques described in Example (7) again (unless otherwise indicated).Stainless steel samples were placed 445 series and stainless steel YEY series in the de boat and I tested Ll in the carburizing apparatus at a temperature of #97 C over two weeks.A thin layer of charcoal formed on the surface of the stainless steel series £67, as no other change was observed.On the cial side, large amounts of coal were deposited on the surface of the VEY series stainless steel, and a hole 100 cm deep formed from which coal and metal fragmentation emerged. Carbon steel was electroplated with tin, silver, copper, and chromium. The thickness of the coating on the samples was equivalent to 60 cm. And after 17 hours of carbonization tests at a temperature of a TES No vo coal formed on the tin and chromium coated grids and coal did form on the silver and copper coated grids but in places where the paint had peeled off. The carbon steel grids, on which no coating was applied, and which were subjected to the test conditions at the same time with the coated grids, showed severe carbonization and metallurgy. I tested samples of 704 series stainless steel mesh and plated each vy. Sample with either tin or chromium and I tested these samples with the Yad ty 00 AY series £ 67 in a carbonization test at a temperature of sinless steel to rust the samples for a period of © weeks. At the end of each week, the samples were cooled to room temperature for observation and documentation using imaging. Then it is heated to 049°C. The grid was painted

Lad Charcoal Free chromium Charcoal Free Lad chrome tin tin The charcoal has accumulated chromium except for some local areas where the chrome plating is peeling off. 447 stainless steel chain uniformly layered on the stainless steel piece (7975 nickel) one of which is 0001 06006! Two samples of Inconel steel were tested. The coal accumulated 17 m for VES at the temperature of the uncoated tin and the other tinned and crumbled, but not to the level of the uncoated sample. The following experiments were carried out to study the reaction of low methane formation. sulfur during the formation and burning of coal balls during refinement under sulfur conditions. methane as an additive to reduce methane formation tin. In addition to the low tin test, deposits of sulfur coal were found. Molten sulfur-refining reactor systems during molten iron. It is believed that the fron iron contains iron particles 1 in the forging at temperatures between 87 °C and 149 °C due to the extreme exothermic reactions that occur during the forging. It is believed that the only way to generate these temperatures is through extreme exothermic. The high temperatures are surprising as methane, especially since the refinement is endothermic in nature and actually tends to cool the reactor system. methane catalyst that stimulates the formation of methane fron within the sites of iron fragmentation residues hydrogen coke and hydrogen in methane to study the formation of methane steel wool in this experiment used steel wool 178 diameter stainless steel experimental station tiny. The stainless steel tube casing was placed in an oven at steel wool (grams of steel wool +, VE in) with Y,Y0 cm Yo tt over iron 1:00 and hydrogen was analyzed And hydrogen, hexane, has a temperature of 278 C. Hexane passed the outstream steel wool treatment in terms of feed ingredients and results. The steel wool was treated and then hexane was introduced an hour before the introduction of hexane 71 hydrogen for a pre-incubation into hydrogen at a rate of about hydrogen in the reactor at a rate of 75 μL/min with hydrogen hexane per minute. Y/auYe - 0 was low as it continued to increase with the continuation of methane. At the beginning, methane was formed in ctetrabutyl tin cm from tetrabutyltin 01 of the experiment. In the end, it reached 4,5 7. Then, it was injected into about methane. The formation of iron methane decreased in the purified feed stream before it reached the iron for a period of ? 71 hours later. Continue at level 1. The experimental data are summarized in the following table. 0 Table Time in hours methane ethane propane hexane

Hexane Propane Ethane CH,4 tetrabutyl tin Tin Jf sn A fourth was added

$0 From the results above, it can be seen that adding tin to steel wool stops the acceleration of methane formation and reduces methane formation to acceptable levels in the product. Example (1)

° Additional tests were carried out using steel wool coated with Buse tetrabutyl tin, specifically; As in example (5); Three injections were injected, each consisting of 0.1 cm tetrabutyl tin dissolved in ? “ons hexane in a stainless steel tube with a diameter of 178 cm (0 X,Y inch) containing 1g56 steel wool. The solution was loaded over the steel wool in

: m EAY at hydrogen temperature 0 hydrogen current

Then Lud old hydrocarbon ja da de 275 m_ flow rate

For hydrocarbons, Yo equals µl/min, and for hydrogen, the flow rate is about Yo cm'/min. Then the gas was analyzed for the presence of methane, and it remained below the level of 721 for YE hours. After YE hours no presence could be detected

1 hydrogen or feed at the outlet of the tube. The internal pressure rose to 70.4 atmospheres. when slitting the reactor tube; It was found that the coal had completely blocked the pipe.

Thus, it can be seen that organo-tin compounds can prevent carbonization of steel wool 5681 under tempering conditions. Example (7)

vo Another experiment was conducted such as the successful experiment in example (1) to investigate the effect of carbonization conditions on DU stainless steel 52101655 tin-coated by steaming in a gold-coated reactor tube, the only difference from the experiment Most successful is the use of a higher hydrogen flow rate of 100 ml per minute.

The experiment continued for A hours without obstruction or excess methane and when the tube was incised and examined; No dad or carbon streaks were observed and only one black carbon band appeared on the wire. It is believed that this defect is due to the method of coating. This experiment shows that tin can protect stainless steel ° from carbonization in a similar way to carbonization. Unlike sulfur, it is not necessary to inject it continuously into the feed. Whereas, sulfur should be continuously injected into the feed to maintain partial pressure of hydrogen sulfide in the system at a level sufficient to maintain surface sulfur on the steel. Any removal of sulfur from the feedstock will lead to the start of carbonization after stripping. Sulfur from the reactor system. This sale 01 occurs within 10 hours after the sulfur p0100?. While the invention is described in terms of preferred applications it should be recognized that obvious changes and modifications can be made for those skilled in the art. For example, parts of steel in the reactor system can be coated with niobium, zirconium, silica, ceramic, tungsten, or chromium, although these are Cll 1 .Tas may be too difficult to implement, use, or too expensive to implement. Alternatively, the use of heat exchangers can be reduced to heat the hydrocarbons to the reaction temperature. Or it is possible to reduce the exposure of heating surfaces to hydrocarbons by using tubes with wider diameters or by using higher tube velocities. Principally there are changes and modifications that may be made to the preferred embodiments above so as to be apparent to those of you © - skilled in the art - which may be deemed to fall within the scope of the invention as defined in the following claims.

Claims (1)

tv security elements And dl for hydrocarbons catalytic reforming a method for catalytic reforming 1-1 using a zeolite catalyst 1 containing platinum paraffinic hydrocarbons Y including: aromatics for the production of aromatic compounds platinum L-zeolite catalyst 7 preparing a feed stream containing A low paraffinic hydrocarbon (i) by conducting a low sulfur paraffinic hydrocarbon-containing feed process 8 in the sulfur content stream processing 1 to less than about paraffin containing stream Contains paraffin for stability to achieve parts per billion (pbb) stability level 0 A acceptable for the activity added zeolite-1 catalyst and level 1 ¢ platinum L-zeolite catalyst Vo on Commercial range Representing you Resisting reforming reactor system Refining Jeli Supply system (i) 1 The mentioned system includes cimproved carburization resistance Improved carbonization VY furnace tubes At least one with tube assembly for furnace VY furnace To touch the aforementioned low-fat hydrocarbon feed stream 0 and heat the said feed stream to degrees Tow sulfur hydrocarbon feed 1 and a group of reactors catalytic reforming temperatures 1 in contact with the feed stream walls have walls reforming reactors reforming the heated VY low sulfur hydrocarbon feed a low sulfur hydrocarbon feed where at least one of the mentioned reactors 4 contains a reforming catalyst of the type zeolite-1 containing platinum Ye mentioned and for some At least of the platinum L-zeolite reforming catalyst 71 tubes exceeding that of the carburization resistance steel mentioned in the furnace, the resistance of YY 0:71 with a ratio of Mo and Cr and exceeding that of the wrought mild steel ‎ YY EA Cr 1 Mo steel Y¢ 2% f (i) Yo Passing the aforementioned low sulfur hydrocarbon containing feed 75 through the aforementioned reaction system in contact with paraffinic hydrocarbons with a refinement catalyst of YA type zeolite-[1] containing platinum platinum L-zeolite reforming catalyst 19 mentioned for the production of aromatic compounds .aromatics 1 "- catalytic reforming method for paraffinic hydrocarbons Y using a zeolite-1 catalyst containing platinum L-zeolite catalyst 1 to produce aromatic compounds including: (i) Preparing a sulfur paraffinic hydrocarbon-containing feed #10 by performing a process 1 treatment that includes reducing the sulfur content in a paraffin containing stream to Less than about 50 ppb A to achieve an acceptable stability and efficiency level for the platinum-1 ¢platinum L-zeolite catalyst (ii) 1 supplying a commercially scale reforming reactor system having improved carburization resistance and the refining system comprising at least one VY furnace equipped with furnace tubing to contact the VY feed stream The mentioned low sulfur hydrocarbon feed, heating the mentioned feed stream to catalytic reforming temperatures, Vo, and a group of reforming reactors with walls in contact with the Ahn 1 low sulfur hydrocarbon stream heated feed VY where at least one of the aforementioned reactors A contains a platinum-containing zeolite-1 reforming catalyst £9 aforementioned platinum L-zeolite reforming catalyst 3; At least some of said 0 furnace tubes and said walls have a carburization resistance YY greater than that of 0110 malleable steel and greater than that of YY consisting of Cr and Mo by > 7 Cr1Mosteel 14 2; and (i) YY passing said low sulfur hydrocarbon containing feed Y¢ through said reaction system Yo to contact the paraffinic hydrocarbons with the platinum-containing 4-zeolite-1 reforming catalyst The aforementioned platinum L-zeolite reforming catalyst TV to produce aromatic compounds. \*- A method for the catalytic reforming of paraffinic hydrocarbons Y in accordance with claim 7; Where at least some of said furnace tubes and said walls have a carburization resistance ¢ greater than that of 300 + series steel Yo. 1 4- A method in accordance with Article 1 of protection, in which at least some of the said furnace tubes Y have a tin-containing coating; interactive; decomposable, reactive, tin-containing paint 7 placed on their surfaces in contact with the low sulfur hydrocarbon feed 8 the paint reduces when heated in a reducing environment reactive tin 1 Where a metallic stannide forms with the pipes, it does not provide the aforementioned carburization resistance. 1#- method a of the claimant; Wherein said coating comprises (i) a decomposable tin compound 0:080:rt” and (ii) a solvent system (iv) and ¢finely divided tin metal (iii) “solvent system ¥ tin oxide 1¢ = method according to claim © where hydrogen decomposable tin Compound Y in question is DNA octanoate. -1/1 method under claim 0 wherein said finely divided tin metal Y has a particle size of about 1 to microns = A 1 . Method of claim 5 where said one-member solvent system contains the least hexane cisopropyl alcohol chosen from isopropyl alcohol Y and pentane .1 +- Method of claim © where the system contains The said solvent is alcohol .isopropyl alcohol .sprayable for spraying SUE method of claim © where said coating is 0 -1 1 -11 1 faa method, claim 3 wherein said coating comprises hydrogen decomposable tin Y tin compound and tin oxide .tin oxide and =-\Y \ method according to the claim; The said paint contains a non-reactive material Y that prevents the reactive tin from reacting with the part of the oy of the etching reaction system on which the paint is applied. Method according to claim 2 where said paint is sprayable -\Y \ protection ¢ where said paint includes tin metal ain] Method according to —-\¢ \ finely divided tin metal 43 alll (38. Y ) Wherein the finely divided tin metal VE has a method according to claim Yo 1 to © 1 micron. A particle size of about finely divided tin metal ¥ of claim wherein said coating additionally includes a Gig compound METHOD 11-1 One or more. Iron compound by weight. ve 7 The aforementioned iron compound where the iron compound VT method according to the claim VA 1 -Fe,03 is Y