SA98180865B1 - Refining process with catalyst pre-treatment - Google Patents

Abstract

Abstract: This invention relates to a catalytic reforming process using a zeolite catalyst. A platinum-containing halide in a metal-coated reactor system where the halide acid is removed from the catalyst prior to loading the catalyst and refining. The process ignites the supply of a metal-coated reforming reactor system and a supply of a platinum-containing zeolite halide catalyst prepared in such a way as to include removal of volatile halide acid, loading of the said catalyst into the said reactor system, and catalytically reforming the hydrocarbons to aromatic compounds where the metal does not chelate from the catalytically active metal-coated reactor system. The coating metal preferably contains tin and the zeolite catalyst is preferably a platinum catalyst carried on L-zeolite. The invention further relates a method for minimizing contamination of the catalyst with a metal used to coat a reactor system. The method includes a halide catalyst pretreatment with hydrogen to remove volatile halide acid. The resulting catalyst is then carried to a metal reactor system and the hydrocarbons are converted, in two forms

Description

i | Refining process with catalyst pretreatment Full description BACKGROUND: This invention relates to a method for reforming hydrocarbons in which the catalyst is pre-treated to avoid inactivation of the catalyst during reforming in plated reactor systems. The invention is particularly applicable to catalytic reforming processes in the presence of low percentage sulfur in systems© of tin reactors using halide catalysts and in particular platinum carried on L halide zeolites. This invention also relates to a method for reducing catalyst contaminants from a metal used to coat a reactor system. I discovered platinum catalysts carried on IL zeolites for low sulfur refinement in the early 1980s. After about 10 years of relentless pursuit and 0 continual research, the low sulfur refinement process was implemented on a commercial scale in the early 1990's. Progress in applying the process on a commercial scale required several discoveries. The two main discoveries are the importance of the ultra-low sulfur levels and the effect of these levels on the reactor metals; That is, the discovery of the need to prevent coking, carbonization and metallic dusting. A preferred method uses a metallic protective layer, particularly a tin-containing layer, to prevent coking, carbonization, and metal dusting. While the reformation process continued to be applied on a commercial scale in the presence of an extremely low sulfur content, a second class of 1.1 zeolite catalysts was discovered that is highly susceptible to sulfur. These new halide catalysts, for example, were treated with freon or ammonium halide salts. These catalysts allow operations in severe Ale conditions, tolerate a wide range of xo hydrocarbon feed streams, have high efficiency and a long service life. Recent attempts to use this second class of catalysts in the ultra-low sulfur reforming process have unexpectedly and undesirably reduced the catalyst's effectiveness. After conducting many researches and experiments, it was discovered that these halide catalysts were partially poisoned by the protective layer metal dy lil, especially tin; used to prevent carbonation Try

. And metallic dust on the surfaces of the reactor system. Somehow some of this tin gets transferred and deposited on the catalyst. In contrast, when conventional zeolite-based platinum 1 catalysts are used for annealing in the presence of very low sulfur content in a tin-coated reactor system, neither tin transfer nor catalytic immobilization due to tin transfer is observed. The cause of these problems is now attributed to the low levels of volatile hydrogen halides that are released from the catalysts themselves under certain conditions. These hydrogen halides react markedly with tin surfaces and may immobilize the catalyst. Hence the present invention aims to reduce the inactivation of the catalyst with metals produced by a system: a metal coated reactor. Another objective of the invention is to reduce catalyst contamination from a freshly coated reactor system that might somehow inactivate the catalyst. This new process also improves the re-capability of catalytic processes; Especially the refinement processes using platinum-based zeolite op because catalyst efficacy and lifetime can be better predicted. It defines the use of metallic coatings and metallic protective coatings; in particular tin protective films; in hydrocarbon conversions. These layers ensure improved resistance to coking, carbonization and metallurgical dusting, particularly in the presence of a very low percentage of sulfur. For example, Hayes et al. describe in International Patent Application No. 1889/97 the coating of steel reactor systems for use in a platinum-based zeolite-1 reforming process with metallic tin-containing coatings. See also US Patents 0Y0 £40.0 and 0.497.706 on behalf of Hayes et al. Metallized reactor systems are also known to prevent carbonation©, coking and metal dusting in low sulfur dehydrogenation and hydrogenated alkyl radical dehydrogenation; See what was reported by Hayes and those with him in US patent 64, international patent application A E/VOART, and US patent © VE £4. Example (7) shows the reaction of a tin bar with hydrocarbons, methyl chloride, and hydrogen at a temperature of 0001 d. F (degrees Fahrenheit) and 18101 d. ob and the rod did not dissolve at a chloride concentration of 0001 Audie ve gfa m (ppm) and at 0001 d. This indicates that the tin coating layer does not dissolve in the presence of halogens at the tempering process temperatures. Also known is the use of catalysts treated with halogen-containing compounds in a catalytic reforming process. See, for example, US Patent No. 5,051,751 in Murakawa's name

And who is with him. Murakawa prepared a platinum catalyst carried on 1 zeolite, then dalle with a halogen-containing compound. The resulting catalyst had a significantly long useful life and was useful for the preparation of aromatic hydrocarbons such as benzene, toluene, and xylenes from aliphatic hydrocarbons containing > to A carbon atoms with a high (zl) rate. Other patents describing oo zeolite LL platinum catalysts include US Patents TAY ATO £ and YTV ONY £5,177,107 in the name of Katsuno et al. and US Patents 8,195,771 and 0,760,778 On behalf of Murakawa and who

With him and the European patent 498.187 a. None of these patents or patent applications described any problems related to metal plated reactor systems. It did not concern itself with the problems associated with halide catalysts, especially platinum-refining catalysts

0 carried on zeolite 1 reacts with metallic coatings such as tin coatings.

It does not describe the desirability or need for a catalyst pre-treatment step to remove volatile halide acid(s) particularly after catalyst loading or prior to hydrocarbon treatment. In fact, the technique mentions the advantages of incorporating one of the favorite metals in paint, tin. With a refining catalyst and in particular with a platinum catalyst mounted on pL zeolite and US Patent 779,994 cited.© Bassem

vo Molasky et al. show that improvements in efficiency and fouling rate are associated with treatment of the outer surface of the 1,1-zeolite platinum catalyst with metallic tin particles with an average size of 1 to ¾ micron (tin dust). For example, Table (1) in Molasky's patent shows an improved performance of the catalyst when metallic tin dust is combined with a fluoride-treated platinum catalyst carried on a zeolite according to US Patent Process 4,181,856.

le Y. Light of the Teachings ASL surprisingly found that the catalyst activity decreases during the reforming process in a freshly tin-plated reactor system using a platinum catalyst carried on an L-halide zeolite (see example (0) below).

He has recently discovered problems associated with the use of metal-coated reactor systems, particularly as-coated systems, in the presence of halide catalysts, and discovered the cause of these problems.

vo and solve it. Hence the objectives of the present invention are to reduce catalyst contamination from a freshly plated reactor system. Another objective of the invention is to ensure that Se catalyst contamination is avoided when a halide catalyst is used instead of a conventional catalyst. General description of the invention:

In an embodiment the invention relates to a catalytic reforming process using a platinum halide catalyst mounted on a zeolite1, in which volatile halide acids are removed from the catalyst prior to catalyst loading and accelerating. The process includes a) supplying a reforming reactor system containing a metallic coating; and b) provide a zeolite-mounted platinum halide catalyst, 1 prepared by a method including removal of volatile m-halide acid; and c) loading said catalyst into said reactor system; and d) catalytically reforming hydrocarbons into aromatic compounds. preferably most of the volatile halide acid removed; so that the metal does not strip off the reactor system coated with catalyst metal during refinement. In a preferred embodiment the volatile halide acids are removed by catalyst contact with a reducing gas at 0°C. It is preferable that this gas contain hydrogen, and it is better that it contains a mixture of hydrogen in nitrogen, and it is preferable that the volatile halide acids be removed through a reduction step after preparing the catalyst. It is preferable that the reduction be carried out under conditions where the volatile halide acids are stable; Sia by alkaline leaching or by contact with solid adsorption materials that are discarded after use or recycled. The reduction step should be carried out under conditions such that the diffusion of the catalytic metal ve is not substantially reduced. Preferred metallic coatings include those made from compositions containing tin, germanium, antimony, and aluminium. It is preferable that the reacting metal include a tin-containing composition that includes elemental tin, tin compounds, or tin alloys. In a preferred embodiment the process according to the invention includes removal of a volatile halide acid including © 1101 (and may be HF) from a platinum halide catalyst carried on a zeolite 1. by contacting the catalyst with a hydrogen-containing gas and loading the treated halide catalyst into a metal coated reactor system and reforming the hydrocarbons to aromatic compounds.In another embodiment the invention relates to a method for reducing catalyst contamination with a metal used to coat a reactor system.The method involves contacting a halide catalyst with a hydrogen-containing gas at a temperature ve above about 7000 dF for a period of time sufficient to remove the halide acid It is preferable that at least part of the volatile halide acid is stabilized by contact with a washing solution or by adsorption on a solid.Then the catalyst is carried to the metal coated reactor system and the hydrocarbons are converted and the metal of the metal coated reactor system does not paralyze the catalyst activity significantly.It is preferable that this method be applied to YY reactor system

Newly annealed, preferably a tin-surfaced system. The newly plated reactor system is a system that has not been used to treat hydrocarbons since it was coated or coated and treated. Normally the conditions of the hydrogen contact step are chosen to avoid or minimize agglomeration and sintering of the catalytic metal (eg platinum).

Among other factors; This invention is based on the observation that platinum halide catalysts carried on 1, zeolite Als are partially deactivated during operation of a catalytic reforming process, particularly when the operation is performed in a freshly tinned reactor. This contrasts with what was observed when using conventional (non-halide) cule-mounted platinum catalysts” where in this case the inactivation of the catalyst due to the tin coating was not observed.

Ve It has been found that tinned reactor systems, especially those containing newly prepared tin interlayers, may lose tin from the tinned surfaces during the operation of a reforming process using a platinum halide catalyst carried on zeolite LL and these catalysts will release; if not pre-treated; halide acids including HCL and the reaction of tin with volatile halide acids will slightly reduce the activity of the catalyst. Thus it is observed that the reactor system

ve newly plated with tin, upon contact with halide acids (such as 1101 and/or HF) unexpectedly produces mobile tin that reacts with the active platinum catalyst Jal. Based on these discoveries, simple and inexpensive methods have been developed to remove volatile halide acids. When the treated catalyst is loaded into a metal-coated reactor system and hydrocarbon treatment begins, the catalyst is inactivated to a small extent or not at all due to the tin coating.

Brief illustration of graphs: Figure pe [1] HOI emission (right) from a halide reforming catalyst as a function of temperature

(left). Hydrogen was added at 9000 d. Q and at a time = 4 hours.

AF) two experimental forms of screening tests described in the example (pay [VY] Js

: detailed description vo

The present invention relates in its wide scope to a process for reforming hydrocarbons in a metal coated reactor system. The process includes: a) supplying a reforming reactor system containing a metallic coating; and b) providing a platinum halide catalyst mounted on a 1, zeolite prepared by a method including removal

a volatile halideic acid; and c) loading said catalyst into said reactor system; and d) catalytically reforming hydrocarbons into aromatic compounds. Most of the volatile halide acid is preferably removed; and the best of all intrinsically; So that the metal from the metal-coated reactor system does not paralyze the catalytic activity. The volatile halide acid removal conditions should be chosen to minimize degradation of the catalyst metal; For example reduce platinum spread. In another embodiment the invention relates to a method for minimizing contamination of the catalyst with a metal used to coat a reactor system. In a particularly preferred embodiment, the invention relates to a method for reducing contamination of a platinum-refining catalyst carried on a tin-zeolite 1 of a freshly tin-plated Jolie system on whose surfaces which will be in contact with the hydrocarbons there are tin interlayers. The method includes a halide catalyst pre-treatment with hydrogen to remove volatile halide acid. The resulting catalyst is then carried into a tin plated reactor system and the hydrocarbons are converted. The term “include” and its conjugation are used throughout this description to accommodate the terms “essentially consist of” and “consist of” in several preferred aspects and embodiments of the present invention. vo As used in this statement, the term "reactor system" includes the hot parts of chemical conversion units, in particular Shay hydrocarbon conversion. These units typically include one or more shunt reactors and one or more furnaces comprising several furnace tubes for heating the feed stream. The term "reactor system" also includes units that include furnace tube reactors where the transformation takes place in the furnace tubes (ie inside the furnace). The “hot parts” of these units are those parts where the feed stream temperature is equal to or higher than the reaction or process temperature and/or at which hydrocarbon transformation reactions occur. The term “metal-coated reactor system” when used in this statement includes reactor systems (see above) that have a metal-containing lamination, coating, paint, or other coating applied to at least part of the surfaces that will come into contact with VO hydrocarbons at process temperature or higher temperature. preferably coating at least half of the surface area; preferably at least three quarters of the surface area; and the most desirable of all surface area; which therefore contains a metallic layer which will come into contact with the hydrocarbons at the process temperature or higher. The term includes "metallic reactor system" as well

A

Interlayers prepared from coating layers or Jie reactor systems that contain protective layers of lamination, paint or coating. Depending on the metal a reactor system with a coating layer applied to its surface may be heated preferably in reducing medium to produce interlayers. In this case, the metal plated reactor system preferably includes a base material (such as carbon steel, chrome steel, or stainless steel) that has one or more bonded metallic layers © attached to it. Examples of metallic layers include elemental chromium, aluminum surfaces, and iron interfacial compounds, for example, those dias systems, and Fesny- and tin-coated reactor systems - such as those systems that have not been used to process hydrocarbons since they are coated with tin-coated dias or Since it has been coated and cured. The term “metal-containing layer” or “coating layer” when used in this statement means a coating, lamination, paint or other coating layer containing elemental metals, metal oxides or organometallic compounds. Or metal alloys or mixtures of these compounds and the like. It is preferable that the metal (or metals) or metallic compounds be a constituent(s) of the paint layer. Or brushing them is a preferred type of Led). supply of tin interlayers or tin coatings; However, it is believed that the interlayers containing germanium, arsenic and antimony, in particular, are reactive and that the discoveries also apply to these newly prepared layers of TH as well as Jods metals. The tin coatings or interlayers are described herein only as a preferred embodiment and the present invention is not limited to the tin coatings or interlayers © tin. Removal of volatile halide acids

HCl The term "volatile halide acid" halide acids including Jody as well as mixtures containing these gases. It also includes HI, HBr, HF and gases released from a halide catalyst such as a platinum halide catalyst carried on zeolite 1, when heated in the presence of hydrogen and preferably also in the presence of platinum. A volatile halide acid may also contain volatile halide acids are those gaseous or removed from NH catalyst under process conditions; That is, when suitable conditions are used for the catalyst

The volatile halide acids are preferably removed by a process including reduction after catalyst preparation. Preferably, the reduction should be carried out under Cum conditions stabilizing volatile halide acids; For example, by washing with an alkaline substance or by picking up an adsorbent that is discarded after use. Removal of volatile halide acids prevents corrosion of the ay coating (by these acids) in the 0 metal plated hydrocarbon conversion reactor and thus prevents inactivation of the catalyst. The volatile halide acids can be removed from the halide catalyst by ailing methods, preferably after the catalyst drying and calcination stages during its preparation. During calcination (oxygen heat treatment) the platinum composite decomposes and the halide content is then catalytically reduced by reductive treatment. This reduction can be carried out at temperatures lower than the calcination temperature but preferably 0 is carried out at a temperature higher than about 900 d. F. Reduction can be carried out in different types of equipment such as vacuum equipment, conveyor belt heat treatments, controlled rotary skirts, fixed bed heat treatments and the like. During reduction care should be taken to ensure that the catalyst is not contaminated” eg with sulfur by-products or other corrosion products produced during the reaction of the acid halide gases with the catalyst or with the metals of the process equipment. In a preferred embodiment the volatile halide acids are removed by contact of the catalyst with a reducing gas at elevated temperatures. The preferred reducing gases include co and hydrogen, or mixtures of hydrogen with inert gases, or with “co.” It is preferable that the reducing gas be a mixture of hydrogen in nitrogen. The reducing gas may be used once or preferably recycled. x In this way, scrubbers, dryers and adsorbent systems that remove impurities and wash the gas before use or reuse reduce the cost of gas. When hydrogen is used, its concentration varies from dilute to pure hydrogen. The preferred concentration depends on the type of equipment used, the time required to remove the volatile halide acid, and All considerations. When a mixture of hydrogen and nitrogen is used, the ratio of xe hydrogen to nitrogen is not important. However, it is preferable that the ratio range from 10011 to 1: 1, and the best is from 1: 50 to 1: ; The most preferred is from 1:00 to 0:1. When using catalysts that are highly sensitive to sulfur, it is preferable that the reducing gas be sulfur-free, that is, it contains less than © gfb (ppb) of sulfur, and less is preferred.

From © JFP of Sulfur. In a preferred embodiment, sulfur-free nitrogen or sulfur-free hydrogen (eg a mixture of hydrogen in nitrogen at + (%)) is used to remove the volatile halideic acid. The water content of the reducing gas is preferably less than 0 g. Useful reduction conditions include 0 degrees Temperature higher than about Vor dF, preferably between 0860 and 17011 dF, and the best between about 9060 and 0001 dF, and gas flow rates between 001 and 10,000/hr, and the best between 9000 and 0080 2 / h. The pressure is not considered Loge, it may range from the vacuum pressure TO up psi, preferably between atmospheric pressure and Yoo psi. Generally, the pressure depends on the equipment used. Mid at Use 0. Separate pressurized vessel The process can be run at pressures between 0* and 151 psi, when using a conveyor belt processor it is preferable to run the process at atmospheric pressure and when using a vacuum vessel it is preferable to run at a pressure below atmospheric pressure. reduction conditions to avoid damage to the catalyst and in particular sintering and agglomeration of the metal (Pr) and platinum agglomeration leads to loss of catalyst efficiency and lifetime.therefore ve should choose the conditions to reduce the loss in platinum diffusion; For example, the gas flow rates should be high and the catalyst heating rates should be about 10 d. p/h or higher. The concentration of water in the treated gas should be less than about 961 by weight, preferably less than about 960.1 by weight, and the best is J of 01 gfm. The diffusivity of the platinum catalyst after halide acid removal should be the same or better than that of the platinum before halide acid removal. The diffusion of the metal can be monitored by the chemical adsorption of © of hydrogen or by the chemical adsorption of 0© or by other methods well known to those familiar with this technique. A preferred method for removing volatile halide acids is to use steps identical to those used during the catalyst run-up. Those familiar with this technique know the conditions of this type of operation well. For example, the process may involve drying the catalyst in a nitrogen atmosphere (eg by heating . from room temperature to 1 df £A Bad h) and then heating the catalyst in a hydrogen atmosphere (eg in a mixture of 9601 hydrogen in nitrogen From 00 dV to 7" dV at a rate of 10 dV/hour in a sea of about 500 hours and then maintaining the catalyst at about 97 dV for a period of YE hours). Gas flow rates are chosen in Time to ensure removal

Volatile halide acids, for example, can maintain the gas spatial velocity per hour at about del Fe during the drying and reduction period. Then the catalyst is cooled to room temperature. In a preferred embodiment, the catalyst is subsequently preserved in a nitrogen atmosphere, away from oxygen and water, until it is used. However, this is not important because the catalyst can be dried and reduced 01 during the Adee trimming operation and therefore oxidizes or absorbs water more or less. As those familiar with the technique will realize, the concentrations of +107 and HO during reduction should be below levels that would damage the halide catalyst carried on the zeolite 1 or reduce platinum diffusion. As mentioned above, limiting the reduction temperature, using high flow rates, and pre-drying the catalyst ensures that high diffusivity of the metal is maintained. 1 Since the reduction method can be carried out in various types of equipment such as vacuum equipment, conveyor belt heat treatments, rotary skirts under controlled conditions, fixed bed heat treatments and the like; There are various methods of adding reducing gas and heating the halide catalyst. For example, it is possible to use a flowing hot gaseous stream containing combustion gases or combustion gases indirectly. If equipment is available, it can be operated at | High Heat treatment can be carried out in effluent hydrogen in a separate reactor vessel; ba vo eg in a hydrotreatment reactor. The individual process details of the reduction step are not important as long as a reducing gas is used (preferably hydrogen-containing gas) and the acids are removed.

Aled) volatile halide. Key to this removal procedure are (a) removal of the volatile acid on the halide catalyst; and (b) maintaining the maximum diffusion of the catalyst metal; and (c) catalytic non-Cyl.; (d) treat the catalyst safely; For example, by avoiding possible explosions and combustion, and the like. Without being bound by a specific theory, it is believed that the halide acid released from the halide catalysts; Especially during normal catalyst operation; Attacks the protective coating of a metal coated reactor system. The volatile gop is released from the catalyst rapidly at the start of the trimming procedure. It was found that the ve impregnated chlorides in the 1,9660.7 wt platinum zeolite rectifying catalyst would rapidly release a volatile chloride acid during the rectification process. and after about 100 to Yoo hours; The rate of chloride loss is substantially reduced. After this initial period, about half of the chlorides remain

\Y on the catalyst. The loss of chlorides during this initial period may lead to the loss of a large metallic added Sal from the protective coating layer on the reactors and furnace tubes. From 965900 and when using catalysts prepared using ammonium salts, it was found that about 2 of the added fluoride were removed. readily by the methods described 9600 chloride added and approx above. Thus, this is a useful target for halide removal. In addition, nitrogen 0 may be released, especially when the remaining β catalyst is prepared in the form of ammonia during the halide acid removal step by impregnation using 1:11:01 and 111,7 as halide sources. volatile halides. These gases escaping using a solid or liquid HE and HCL stabilizer (Say Died) are considered toxic and dangerous. (Adsorbent or absorbent) captures these halide acids. Appropriate liquid adsorbents include 0 or Other basic solutions or solid adsorbents discard (NaOH) water and preferably alkaline washing solutions after use.The position of the adsorbent is not important although it is preferable to stabilize the volatile halide acids as quickly as possible so that they do not cause corrosion.The amount of a factor is not considered Stabilization is important although a sufficient amount is preferred to stabilize the released halide acids.Lamination, Coating, Paint and Other Coating Layers This invention is not applicable to all metal plated reactor systems. A metal with volatile halide acids will inactivate the catalyst under conversion process conditions.However, simple tests such as those described in the examples will readily identify the metals and coatings required in the catalyst pretreatment process according to the present invention. metal on reactor systems to improve process operability. These useful reactor systems according to this invention usually contain metallic protective layers designed to reduce coking, carbonization, and metallic dusting. The metal used in the coating layer depends on the requirements of the hydrocarbon conversion process, for example. Example temperatures of process and reactants; Etc. gl AY the subject of this vo It is especially preferred for metallic coating layers that melt at process conditions or low conditions and form interlayers with the base material. It can provide complete coverage of the primer faster. These metals include that group that consists of tin, antimony and germanium

Try

\Y arsenic, bismuth, aluminum, gallium, indium, copper and mixtures thereof, interlayers and alloys thereof. Preferred metal-containing coatings include metals chosen from the group consisting of tin, antimony, germanium, arsenic, bismuth, aluminum and mixtures thereof, interlayers and alloys thereof. Particularly preferred coatings include tin, antimony and germanium-containing coatings. These metals form continuous and fast adhesion 1 protective layers. Tin coatings are particularly preferred for their ease of application to steel, or preferably Spain, for their low cost and because they do not pose a risk to the environment. Most metals interact with the base material of the reactor system to produce a continuous or fast-adhesive metallic protective layer at the specified hydrocarbon conversion process temperature or at a lower temperature. It is preferable that the coating layers be of sufficient thickness to cover the base metal surface ve completely and that the resulting protective layer remains intact after removing the mobile metal so that it protects the steel for several years of operation. At the same time, the thin layers are chanted; Thin layers are easily produced and are less expensive than thick layers and are less likely to crack under thermal stress. Thus, it depends for the protective layer on the desired conditions of use and the special metallic paint layer. (Bal) thickness is up to 7 mm inch, preferably from about 1. For example, paint layers are applied with (wet) thicknesses ranging from vo ov to 1. 1 to; milliinch. In general, it is preferable that the thickness range after processing from about 1 mm inch, and the most preferable is about 01 to 1.0 mm inch, and the best is from about an interlayer produced initially at least hard with steel A Also, the adhesion of the paint layer is sought, or this can be achieved, for example, by curing at high temperatures.For example, ad df 01101, a layer of tin paint placed in a hydrogen atmosphere can be cured at © h. Ye Coatings containing metal can be applied by various methods well known in the technique. These methods include, but are not limited to, electroplating, chemical vapor deposition, and spray coating. Preferred methods for layering coatings include painting and lamination. Practically preferred The application of a coat of paint in a paint-like composition (hereinafter it shall be called a “coat vo paint”). Such a coat of paint may be applied by spraying, brushed, roller, etc.” onto the surfaces of the reactor systems.

€\ Tin is the preferred plating metal and has been mentioned in this statement as an example. The description of this statement about tin is usually applied to other metals such as germanium. Preferred paint layers include a metallic component chosen from the group consisting of a hydrolyzed metallic compound such as an organometallic compound, a micro-fractionated metal, a metal oxide, and preferably a metal oxide that can be reduced at 0 process temperatures or furnace tube temperatures. In a preferred embodiment a curing step is used to produce a protective interlayer bonded to the steel through a bonding intermediate such as a carbide-rich bonding layer. This is described in US Patent VE 0 £0 © on behalf of Hayes et al. which is fully cited herein for reference. Some of the preferred coatings and paint compositions are described in US Patent Serial No. 807.057 in the name of Hayes et al. corresponding to International Patent Application 157057/97 and which are mentioned in full herein for reference. At least one particularly preferred tin paint coat contains at least four components or functional LES: (1) a hydrolyzed tin compound; (7) a solvent system such as isopropanol; (5) (7) microfractionated tin metal; and (£) oxide Tin Examples of particularly useful hydrolysed tin compounds include organometallic compounds such as tin lactanoate or tin neodecanoate Compound (4), tin oxide, is a porous tin-containing compound that can adsorb to the organometallic tin complex and can Reduced to tin. It is preferable that the paint layers contain finely fragmented solids to reduce sedimentation to a minimum. Also, tin metal is added finely fragmented; the compound (?) coded to ensure that tin metal is available to interact with the surface © which should be covered at a low temperature It is preferable that the size of the tin particle be small; the die ranges from 1 to ¾ micron. When applying tin paint layers of suitable thickness, heating under reducing conditions will cause the tin to transfer to cover small areas not Jha (such as joints Welded).This will fully coat the base metal.Some coating compositions need heat treatment to produce continuous, fast-adhesive protective layers; The curing conditions depend on the particular metallic coating and hydrocarbon conversion process to which the invention is applied. For example, gas flow rates and contact times depend on the successive stages of the process, the metallic coating, the compositional components of the coating, and the curing temperature. Curing conditions are chosen to produce a continuous and uninterrupted protective film that adheres

on the steel base material. Processing conditions can be easily determined. For example, coated rods can be heated in the presence of hydrogen in a simple test apparatus and the formation of a bonded protective layer can be determined using petrographic analysis. As described above, contact of the metal-coated reactor system with the exfoliants is preferable after the curing step, particularly when interlayers form during the heat treatment. It is preferable to treat the tin paint layers at a temperature ranging from 1,000 d. P to 150860 d. It is preferable to carry out curing within hours and often with increasing temperatures with time when the paint layer contains reducible organic metal compounds containing oxides and/or oxygen. It is preferable to conduct reduction and treatment hail gas containing hydrogen and the best in the absence of 0 hydrocarbons. As an example of a paint coat curing system suitable for a tin paint coat, the system includes painted parts that can be compressed with flowing nitrogen and then by adding a stream containing hydrogen. The temperature inside the reactor can be raised to 8060 d. q at the rate of a Veo q/hr. Then the temperature can rise to 58-979 a q F Jara © Dr. p/h. This temperature vo is maintained for about EA hours. In a preferred embodiment the metal plated reactor system includes a dyn layer containing an interlayer. This layer (which covers the basic composition material such as the steel base material) contains two metals or “ST” and the metals are found in an equivalent ratio; Ie such interstitial compounds. Interfacial compounds are well defined in the technique and are more synthetic than molecular mixtures or alloys. Moreover, it has unique physical properties (Jie (color) and chemical properties) that are unique to the interlayer. For example, a stalin interface contains tin interlayer compounds that include tin and at least one other metal, and tin and the other metal (or other metals) should exist in compounds having a stoichiometric ratio of elements that change only within a limited range. Examples of these interfacial interfacial compounds include FerSn, FeSny, and NirSn¢ 9 NirSn©. Other examples include a metal-scrambled interfacial (Jie) (Fe, where Fe can be substituted for Ni or easily vice versa that they exist together in an even ratio with tin.Although he does not wish to be bound by any theory, he thinks it can go especially in a freshly plated reactor system which has interfacial layers; a small amount of the metal has not reacted with a substance

Basic composition. This unreacted coating metal is believed to be at least a partial cause of catalyst poisoning during exposure to volatile halide acids. Metal plated reactor systems are particularly useful in low sulfur processes because the coating provides improved resistance to coking, carbonization and metal dusting. Thus—in a particularly favored embodiment of this invention,” Adee performs the conversion of hydrocarbons in the presence of a reduced sulfur content. In these low sulfur content systems the feed stream should preferably contain less than 50 gfm of sulfur, preferably less than 10 gfm of sulfur and most preferably less than 10 gfm of sulfur. In another preferred embodiment the process of the invention is carried out in the presence of an extremely low percentage of sulfur. 0 Preferably in this embodiment, the sulfur percentage is less than 001 cfb, the best is less than 0 cfb, and the most preferable is less than Ye cfb of sulfur, but it is particularly preferred that the sulfur percentages of less than 01 JFB, especially those less than © JFB. Primer ASE A wide range of primer materials can be used in Adee ve patented this. In particular, a wide range of steel and alloy materials can be used in the reactor system. In general, steel materials are chosen to meet the minimum strength and flexibility requirements for the desired hydrocarbon transformation process. These requirements, in turn, depend on the process conditions Jie operating temperatures and pressures. In addition; Steel is chosen so that it is not exposed to expected corrosion risks. 0 Suitable steel materials include carbon steel and low alloy steel materials such as chromium steel 0.75, 7.70, 50 and ? with or without molybdenum and 9060 series stainless steel materials including Type 04, YAN and 7 stainless steel;?? and heat-resistant steels including 106-48 and 10-0 and Manuerite as well as processed steels such as aluminum or chrome steels. vo catalytic trimming process The present invention is particularly applicable to trimming and/or ring forming processes. catalytic dehydrogenation; Such operations are described in US Patent 0YY £6071 in the name of Boss et al. and International Application 47/1887 in the name of Hayes et al.

A preferred embodiment of the invention includes a catalytic reforming process using a halide zeolite catalyst having medium or large pore size comprising an alkali or alkaline earth metal and charged with a single metal or a particularly preferred embodiment is the use of a catalyst of this A more Of the group metals such as in the process of refining or dehydrogenation ring formation of a paraffin oil feed stream containing an iodox process ingot containing Jie to produce aromatic compounds Ad hydrocarbons as 6 and/or carbon atoms. The invention is particularly applicable to a refinement process in the presence of ultra-low AT sulfur using a zeolite catalyst having medium or large pore size containing additional halogens and in particular a non-acidic platinum halide catalyst carried on

Lads) and a zeolite by "medium pore size" means a zeolite that has an effective pore opening in the range of about 1. These zeolite catalysts allow Ho angstroms when the zeolite is in the form 10-0 for hydrocarbons to have some branching in the zeolite void space. And you can distinguish between regular alkanes and slightly branched alkanes compared to more branched alkanes that contain, for example; carbon atoms. Medium pore size zeolite catalysts include Lal VE and 317 AAT described in US Patents ZSM-0 Beneficial 1 described in US Pat. 7,768,914 and 2624-17 described in 2584-11 and 2.011.774 and 2824-71 described 8 US Patent 7.877.449 AS ya Preferred zeolite catalysts include .4.051.77 and silicate described in US Patent ; and 2824-11. A platinum catalyst carried on a preferred zeolite in ZSM-0 silicalite and is described by Dietz et al. £ VEY VIE US Patent © “large pore size zeolite” means a zeolite with an effective pore opening of about angstroms . Favorite and useful large pore size zeolite catalysts in this Yo-7 include Phogsite. vy and a type X zeolite of the invention describe a type 1 zeolite and a type zeolite » in US Patent 7.10.0507 and a description of the zeolite # in US Patent 7 The preferred zeolite catalysts in particular have effective pore openings ranging from CY AAY YEE vo to 4 angstroms. In a preferred embodiment, the invention uses a medium or large pore zeolite catalyst containing an alkali metal or an alkaline earth metal charged with one or more metals.

A group

The zeolite catalysts used in this invention are charged with one or more of the Jie A metals, nickel, ruthenium, rhodium, palladium, iridium and platinum. One of the preferred group A metals is iridium, especially platinum. If platinum is used, it is preferable that its weight ratio in the catalyst range from 960.1 to 965. Group +4 metals can be added to 0 zeolite catalysts by synthesis, impregnation, or exchange in a solution of (Sle) for a suitable salt. When it is desired to add two metals from Group + metals to the zeolite catalyst the addition can be done simultaneously or sequentially.Particularly preferred catalysts for use in the present invention include Asana A group metals on large pore size zeolites and Jie .1 zeolite catalysts containing platinum;0 preferably Platinum carried on zeolite 1. is non-acidic. Platinum halide catalysts carried on zeolite 1. are particularly preferred. The composition of zeolite of type 1 can be represented in terms of the molar ratios of the oxides in the following formula: 0T: 0N (°.Y-1.9) tiles : Mx,O (.9-1.+%) and in the above formula represents “MISE fn Jiags” cation, and y represents a value ranging from zero ve to about 4. Zeolite 1 has been described and its X-ray diffraction pattern Its properties and preparation methods are detailed, for example, in the US patent VOY YAS whose contents are mentioned in this statement for reference.The actual formula may change without changing the crystalline structure and includes platinum catalysts carried on zeolite | Also useful are those catalysts described in US Patent 174.0 as Boss and Hughes; and in US Patent 5,097,771 in the name of Murakawa and from .cana and in US Patent 099,197 .; Bassem Wortel; And in the American patent, EEA AT, in the name of Biobelmir and those with him, all of which are mentioned in this statement for reference. Preferably, the catalyst should not be substantially acidic. In a preferred embodiment; The invention relates to a catalytic reforming method using a platinum-containing halide zeolite catalyst. Prior to loading the catalyst into a metal coated reactor system, volatile halide acid (ve) was removed from the catalyst. The catalyst then carries and refines the hydrocarbons; The process includes: a) the provision of a metal-coated reforming reactor system; and b) provide a platinum-containing zeolite catalyst that has been pre-hydrogenated to remove volatile halide acids containing SHC and

ii) loading the treated halide zeolite catalyst into the reactor system; and d) reforming the hydrocarbons into aromatic compounds. It is preferable that the metal plated reforming reactor system contain tin surfaces and that the pretreatment process also preferably removes volatile HF. The HOI is preferably stabilized by contact with a 0 washing solution or by adsorption on a solid. In a particularly preferred embodiment, the catalytic reforming process uses a platinum catalyst carried on zeolite1, and includes: a) coating the reforming reactor system with a layer of tin-containing paint and contacting the coated reactor system with a hydrogen-containing gas at a temperature of 1900-8060°C . p ve for the production of tin ferric compounds; and b) supplying a platinum-based zeolite-based halide catalyst, 1 prepared by a process including impregnation of the catalyst with NH:Cl and 1111:7 and treating the halide catalyst with hydrogen to remove volatile halide acid; and c) loading the platinum-treated halide catalyst carried on .1 zeolite into the reactor system; and d) Refining of hydrocarbons to aromatic compounds in the presence of an extremely low sulfur content of less than 10 GFP. Preferably, substantially all the volatile halide acid is removed in step (b). A preferred embodiment according to this invention then uses catalysts treated with halogen-containing compounds herein referred to as halide catalysts. These special types of catalysts have been described recently. For example, US Patent 5,091,751 © - Murakawa et al. describes the preparation of a platinum catalyst carried on zeolite1 and then treated with a halogen-containing compound. Other patents describing zeolite halide catalysts mounted on zeolite L include European patent EAA VAY A describing co-impregnation with NH: Cl 101,8 and US patent 141.4856.; 5,771,217 and © CYT TOY in the name of Katsuno and co. and US Patents 8,197,771 and 0,760,778 for Murakawa and co. > Halide catalysts also include spent catalysts; In particular spent catalysts to which die halides have been regenerated by the addition of halogen-containing compounds (see, for example, Patent 5,770,774)” where the aad is first removed from the spent catalyst in a reducing or oxidizing atmosphere. Then halide is added to it by impregnation with an aqueous solution of ammonium chloride and fluoride, and then calcined. Try

All these patents have been mentioned in this statement for reference. The halide catalysts mentioned in these patents have been treated with halogen-containing compounds, usually with chlorine and/or fluorine-containing compounds. It is preferable that the catalysts be treated with compounds containing both chlorine and fluorine, or with one or more compounds. More contains both chlorine and fluorine. These halide catalysts have a long useful life and a promising efficiency. It is particularly suitable for the preparation of aromatic hydrocarbons (Jie benzene, toluene and xylene) from aliphatic hydrocarbons containing AT carbon atoms. ail It has been observed that these halide catalysts release small amounts of HCl and/or HF when ma (ma) these particular types of catalysts are at elevated temperatures (such as at process conditions) or when they come into contact with hydrogen at higher temperatures From about 500 DV to 0 500 DV the resulting acid halide reacts with a reactant metal present in Gli coated reactor systems and therefore the present invention is needed.It should be noted that the aforementioned treatment with halogen-containing compounds differs from that The treatment that is usually associated with platinum loading, for example by impregnation or ion exchange with compounds containing platinum and halogen. This treatment also differs from that associated with wash solutions used before, during or after impregnation or ion exchange with conventional catalysts where ALB amounts are added In some applications, for example in an ultra-low sulfur refinement process using non-acidic platinum catalysts mounted on LL zeolites, it is preferable that the feed stream to the catalyst be substantially sulfur free; Sulfur levels at less than 50 gfb and preferably less than 01 gfb and preferably dil of ov.#0 gfab. Preferred touch-up conditions include a temperature in the range of 700 to 60°C. q to 0 d. P and the best in the range of 8060 d. P to 0175 d. q and pressure in the range from zero to ¼ psi and best in the range 15 to 151 psi' and a proportion of recycled hydrogen sufficient to produce a molar ratio of hydrogen to hydrocarbon for the vo stream fed to the reduction reaction zone in The range is from 0.1 to Ye and the best in the range from 0.5 to the best in the range of 0.5 to 01 and the liquid spatial velocity per hour of the hydrocarbon feed stream over the catalyst for trimming in the range from 1.1 to 01 and the best in The range is 1.5 to ©

In order to obtain tempering temperatures AD it is often necessary to heat the furnace tubes to high temperatures. These temperatures often range from 8080 d. q to a 1 q and usually from 856 d. F to 1701 d. P and mostly from 900 d. P to 6 DF and to understand the invention more fully; The following examples illustrate some aspects of the invention. However, we should be aware that this invention is in no way limited to the particular details shown in the examples. 1 (1) Jud preparation of a platinum-on-zeolite halide catalyst (comparative example) A platinum-on-zeolite halide catalyst was prepared in a manner similar to the method of preparation described in example (8) of the European patent EAA YAY AY 71 added Part by weight of Bake a bond of silica to 100 parts by weight of zeolite type 1. With mixing, kneading and molding, then calcining the molded mixture obtained in this way in air at 00 d.m. (977 d.f) for a period of time. 2 hours vintage zeolite, 1 molded containing a binder of silica, and an impregnation liquid was prepared containing 1.6099 gm of ammonium fluoride and #la.; gm_ of ammonium chloride and 1.1971 gm of platinum tetraamine chloride and EA g of ion exchange water and then this liquid was slowly poured into 10 g of molded zeolite type 1. With stirring, the resulting zeolite was dried at room temperature overnight and then cured at 00 d C OY d. q) YBa hours in the air. The temperature and time of calcination should not be exceeded to determine the agglomeration of platinum. It was found that the calcined catalyst contains about 960.7 by weight fluorine and 960.7 by weight of chlorine. Similar catalysts were prepared at high halide ratios, Sli. This 1.1 zeolite-mounted platinum halide catalyst was carried to a freshly tin-plated experimental unit. This catalyst was then subjected to primary processing. This treatment includes drying the catalyst in nitrogen atmosphere from room temperature to 1,000 d. q for VA hours; Then the catalyst is heated in a mixture of Hy in Ny at a ratio of 9601 from 0000 to 977 d. F at a rate of 01 d. q/hour over a time period of approximately 7 vo; hour; Then maintain the catalyst at about 977 d. F for YE hours. The gas spatial velocity per hour at del Yee was maintained and the gas was passed in one pass through the drying and reduction periods. Then the total reactor was cooled to room temperature.

YY

When heated to HE and HCE, and during the course of this experiment, it was observed that the catalyst began to release, as a function of Hel, the amount released from [V] d. p or higher and hydrogen was added. Figure 0 shows the HCl gastic tubes used to measure the gE concentration over time. A decrease was also observed and the halide ratios were measured on the catalyst and it was found that elu VA hydrogen was added at a time equal to about 9650 of the originally added chloride (in the form of ammonium chloride) and about 0 of the originally added fluoride (in the form of ammonium fluoride) 9 (9) In addition, this catalyst was used in the catalytic reforming process (see example above). The inactivation of the catalyst compared to an ideal catalyst was observed in a non-tin coated reactor. AT is the cause of this paralysis in the spe, and the initial treatment has reacted with the released halide acids with the newly tin-coated surface, which produced mobile tin that paralyzed the catalyst activity. Primer (comparative example) A platinum catalyst mounted on zeolite 1, was prepared in two phases.It was believed that the pre calcination step before platinum loading would lead to the production of low levels of halide acid 1 zeolite catalytic base 1 of about 0.4 96 by weight. of volatile Bale.In a first step I drank fluoride and 960.05 by weight of chloride, both in the form of ammonium salts. Then the resulting halide base material was calcined in air at 9060 d. F for two hours. Then I drank the base material, d. This catalyst calcined with platinum as shown in the example was calcined for an hour OV and then calcined at (1). The final halide ratios were measured on the catalyst. It was found that no significant loss of chloride or fluoride occurred compared to a similar catalyst. Prepared without calcination prior to loading the platinum. Yo in a reactor made of stainless steel from (VAN-V EE) experimental The first experiment was conducted The gases are recycled and the released halide acids are drained. The aly was not coated with tin. YY type before layer Other catalysts of 1 prepared according to the example Glial cm of 11 and loaded ry 110: The catalyst acts as a source of [1-7] cm'. Use the arrangement shown in Figure 01 its size An initial treatment of the catalyst was carried out, this treatment includes drying the catalyst in an atmosphere of HE and VA 1 dF h for 000 dF at a temperature ranging from room temperature dF to 477 dF 9060 of 9001 with a concentration of Ny in Hy then heating the catalyst in a mixture of and then maintaining dele £7 d. q per hour over a time period of about 10 at a rate of 0 hours. The spatial velocity of the catalyst YE was kept at about 977 d. P for a period of time at 10'10/h during drying and reduction periods. Then the total reactor was cooled to room temperature. The top catalyst layer was removed under nitrogen atmosphere. Catalyst performance was tested at lbs/in and spatial velocity 100 using only the catalyst bottom layer. The reaction conditions were 0 hydrocarbon amounting to ? The desired production rate (Hy) and the ratio (del) of the liquid per hour for aromatic compounds is 9647.6 by weight. The feed stream was an iodox infusion from an aromatic compounds extraction unit (AT) and [Y-Y] was used according to the arrangement shown in the figure (187-1£2). The second experiment was carried out with VEY coated in This experiment had a freshly tinned reactor and vo stainless steel rods. The ratio of surface area of tinned to lead was freshly tinned. Because of an order of one times that ratio for equipment used on a commercial scale Yo the overall catalyst volume is about 1/2 larger than the prepared tin-coated rod (1) and loaded 860 cm" of the newly prepared catalyst according to the example. Another catalyst layer was loaded Its size is 80 cm after the tin-coated rods.Then, the operation step was carried out for the first experiment.After cooling, the upper catalyst layer and the rod were removed in an atmosphere of nitrogen.The performance of the catalyst was tested (as in the first experiment) using only the bottom catalyst layer After the performance test, the bottom catalyst layer was analyzed and it was found to contain 0001 gm of tin. By completing the resulting line for the required temperature by extrapolation to achieve the desired production rate ve of the aromatic compounds again to time zero. The operating temperatures of the two experiments show that the catalyst is believed to be (1) d.f reacted tin from the catalyst of the experiment 01. Experiment (7) is less effective by approx

Ye reacted with the released halides; Including (110; from the first catalyst layer, resulting in mobile tin. This mobile tin inactivated the catalyst activity in the second catalyst layer. (4) Example Zeolite 1. Suitable for use in this invention J sand Preparation Platinum catalyst The effect of removing volatile halide acid before loading the catalyst was estimated by a test in an experimental unit o where a catalyst was prepared according to the example method (1) and dried in an atmosphere of nitrogen gas flowing at a spatial speed equivalent to 1000 / hour. Then it was placed in an experimental unit devoid of tin ferrites and heated df at this flow rate hydrogen was added and reduced ©0800 from room temperature to the nitrogen flow rate keeping the total flow rate constant keep the flow rate of Jill of the total flow. The catalyst was activated by treating it with 96010 hydrogen at a rate of 0 dv/h of 10 hydrogen in nitrogen (ratio = 1/11, 3) while heated at a rate of 1 hour. The catalyst was maintained at 0 dV to 977 dV over a period of approximately 1 hour using HOT in the absence of feed current, and the release of YE was monitored at about 977 dV for a period of chloride added to the catalyst after This action. 969 0 JASTIC tubes. Then the catalyst was allowed to cool to room temperature in nitrogen atmosphere and carried to the vo system. Inactivation of the catalyst with tin. Badly A freshly tinned reactor. After running the catalyst, the efficiency of the catalyst was not nearly identical to that of a catalyst subjected to a refinement process in an experimental unit other than (°) Example: removal of volatile halide acid from a regenerated catalyst | Y. (1) Deactivated a spent catalyst originally prepared in a manner similar to that described in the example by using it for a long time in an ultra-low sulfur refinement process. The resulting catalyst lost most of the fluoride and chloride originally added. This catalyst was oxidized With a mixture of oxygen in nitrogen, its concentration is 967 at atmospheric pressure, and it was heated for one hour at each of the then cooled to room temperature. The percentage of pone was measured at temperatures 06, 50660, and ve halide. g of chloride solution 1.784 He renewed 7 g of this catalyst by impregnating it with a mixed solution of 1 g of solid ammonium fluoride 100948 aqueous ammonium (concentration 7.7 96 by weight) and

Yo at room temperature in pda) g of deionized water. The catalyst was dried for 1.6 hours each. This returns 1 d. uncle for a period of 50,660 d. m and 171 m at night, then calcified in the air at the catalyst with its original percentage of fluoride and chloride, which amounts to about 961 for both. Then, the example method (£) was carried out to release volatile halide acids. The catalyst treated for the catalytic reforming process was used in a tin-coated reforming reactor. It was not observed that the catalyst activity was inactivated by the tin produced from the © coating of the reactor. (1) Jad preparation Useful catalysts in the invention: 1 Step A catalyst was prepared by treating a halide catalyst of platinum mounted on zeolite 1. Pretreatment 1 with hydrogen to remove halide acids. (1) A dried and calcined catalyst was prepared in a manner similar to that of the example lL nitrogen at a gas spatial velocity per hour equal to 11011/h and a pressure equivalent to dV in a period of 1 hour, then it was fixed at one pound/inch. temperature to Ve, then the reactor was heated to 1: 9 dV for 0 hours, then a mixture of 18001 was added at a ratio of 101 vo h., then YE dV/h, then the temperature was fixed at 977 dV. p for 10 df at a rate of 7 The catalyst was cooled in a nitrogen atmosphere and stored The volatile halide acids adsorbed upon contact with a solid layer of the solid adsorbent This method allows the volatile halide acids to be removed from the catalyst before loading it into Tin plated reactor and before running the process. By removing the volatile halide acids, they do not react with the tin coating of the reactors and dependent hardware, thus reducing the contamination of the catalyst to a minimum. Hydrogen to remove halide acids. The pretreatment was carried out in a conditions-controlled mobile bed device. In the first region, a dried and calcined catalyst prepared in a manner similar to that of vo d. With passing nitrogen released in a different way, 9000 from room temperature to (1) example 000 directly through the catalyst layer. The residence time was approximately two hours. A second area was kept at 122117 df for one hour. approximately and then convert the gaseous medium into a preheated mixture of

' (Hydrogen percentage 967 by volume). In a third area, the catalyst was rapidly cooled to room temperature in a dry nitrogen atmosphere and emptied into nitrogen-lined barrels for storage. Example (V) Extensive Testing 0 This example describes a large-scale test and illustrates a preferred innovation of the invention. A small commercial catalytic reformer operated at ultra-low sulfur rectification conditions using a 1. zeolite-mounted platinum catalyst and a feed stream of K7-K8 iodex ingot. The sulfur content in the feed stream that touches the catalyst is less than GFP. The reactor system includes a sulfur conversion unit and a sulfur adsorption unit, followed by four reforming reactors and their associated furnaces and tube furnaces. The reactors shall be made of 1/7 chromium-molybdenum steel, and the furnace tubes shall be made of Yet Tams steel. Prior to catalyst loading, the reactors, furnace tubes, and tubes accompanying the reactor system shall be treated in a reducible tin paint layer. Several rods are also placed in the reactor system. The coating layer shall be applied to the rods and to all surfaces of the reactor system which shall be in contact with the hydrocarbon feed stream at or above tempering temperatures. The primer is made up of 1 part Tin Ten Cem 9671 (manufactured by _Money Chemical Inc.; DK City Ohio), 2 parts tin oxide powder and 2 parts tin metal powder. Finely ground (particle size ranges from 1-5 microns) and isopropyl alcohol (for flowability). Tintin-cm contains 96780 tin in the form of tin-lactonate in lactanoic acid. And after applying a wet coat of about 1 to 2 mm thick; The plated reactor system is heated in a flowing mixture of hydrogen and nitrogen (at a YE Bad ratio) 1/1 hour and then kept at about 100,000 °C. P for about 5/8 hour. Then it cools down to room temperature. This procedure ve tins the painted surfaces (with iron and nickel tin). The tin moves to cover small areas that have not been coated (such as soldered joints). The reactors and furnace tubes are inspected and any easily removed lumps of tin removed. When the rods are analyzed by petrographic microscopy, the presence of shiny, microscopic tin balls is evident. vy

And in separate experiments, halide-reduced catalysts were carried from platinum carried on zeolite 1. (from steps 11 and 7b) to tin-coated reactors and an ol ya plate) for the operation shown in example (1). The feed ingot was tempered to aromatic compounds at Temperature ranged from 806 to 0001 dF, and after 706 hours of operation, no catalyst showed a decrease in activity as measured by the operating temperature of the experiment compared to what is expected for a halide catalyst in a non-tin coated reactor system. Thus, the two steps were shown. A and 7b that the pretreatment processes are effective.The present invention has been described above in terms of preferred embodiments but those familiar with the technique are aware of several changes and modifications to this invention.In fact several changes and modifications to the embodiments described above will be readily apparent to those familiar with the technique that are within the scope This invention is as defined by the following claims.

Claims (1)

YA Protection Elements 1-1 A catalytic reforming process using a platinum halide catalyst carried on zeolite 1. In a metal-coated Y reactor system where volatile halide acid is removed from the catalyst before loading the catalyst and carrying out the Y reforming, the said process includes: ¢ A- supplying the reactor system metal-coated trim; and ° b- providing a platinum halide catalyst mounted on a zeolite,1 prepared by a method including removal of volatile halide acid1; and 7c- loading said catalyst into said reactor systems; and A, D- catalytically reforming hydrocarbons into aromatic compounds. 1 ?- A process according to Claim (V) where in step (b) a volatile halide acid is fixed. 1 *- Process according to protection claim Cus (1) In step (b) volatile halide acid Y is stabilized by contact with a washing solution or by adsorption on Ada 1 4- Process according to protection claim (1) (Where volatile halide acid is removed from a platinum-impregnated catalyst, Y, by reduction.) Process according to protection claim (1), where in step (b) volatile halide acid 7 is removed by contact of a halide catalyst with hydrogen gas at a temperature of about 3 6 dv to 0001 dv.-1-1 process according to claim (1) where said volatile halide acid contains HCL ¥ “- A process according to the protection claim (1) where the mentioned metallic coating layer contains a metal 1 selected from compositions containing tin, germanium, antimony and aluminum. Y ra A<A is a process according to the claim (1) where said metallic coating includes tin or 1 tin compounds or tin-metal alloys. 7 4- A process in accordance with the protection requirement (1) where the mentioned metallic coating layer, which is new, is applied to at least one part of the reactor system. Y 0- A catalytic reforming process using a halide zeolite catalyst in a metal-coated Jolie system and 1- Said process includes: l a- supplying a metal-coated reforming reactor system; and 1b-providing a halide zeolite catalyst that was pre-hydro-treated to remove 10g; and 3c- loading said catalyst into said reactor systems; and °d - catalytically reforming hydrocarbons into aromatic compounds. . 1- A catalytic reforming process according to protection claim (01) where the metal is tin. 1 -1" process according to Claim (01) where said HOE is established by contact with a washing solution or by adsorption on a solid. Adee-1?Y catalytic reforming using a platinum halide catalyst carried on zeolite 1. Process 1 includes: Y a) Coating the Reactor System with a tin-containing varnish and contacting the tin-containing reactor system 1 with hydrogen-containing gas at a temperature of 1-6 ¢ dF to produce tin compounds and ° b) supplying a zeolite-mounted platinum halide catalyst [prepared by a process including impregnation 1 of the catalyst with 101:01, NHF, and hydrogen treating the halide catalyst to remove volatile l-halide acid; and a c) loading the platinum-treated halide catalyst carried on .1 zeolite to system 9 reactor; and 0 d) refinement of hydrocarbons to aromatic compounds in the presence of very low r.11 sulfur less than 01 gfb.-14 process as required Protection (OF) where substantially all the volatile halide acid is removed. Y Yo 1 Process according to protection requirement (VY) where said volatile halide acid is stabilized by contact with a washing solution or by adsorption on a solid. X-11 process to reduce the contamination of the catalyst with a metal used to coat the celia system. The process includes the contact of a 'halide' catalyst with a gas containing hydrogen at a temperature higher than about ¢ d. F for a period of time sufficient to remove the volatile halide acid and load said catalyst ° into a metal coated reactor system and convert hydrocarbons where the metal from the metal coated reactor system does not lynch the catalyst activity. -17 1 Process according to claim (V1) where the metal includes tin. VAY is a process according to protection requirement (V1) where the process is applied to a metal coated reactor system. Y recently. -119 1 A process according to Claim (V1) in which said halide acid is stabilized by contact with a solution of Y wash or by adsorption on a solid.