KR20110093815A - Process and system for the addition of promoter metal in situ in a catalytic reforming unit - Google Patents

Abstract

One exemplary embodiment may be a method of promoting in-situ addition of a promoter metal to one or more catalyst particles in a catalytic naphtha reforming unit. The process includes introducing a compound comprising a promoter metal into a catalytic naphtha reforming unit, and carrying an effective amount of a promoter metal from the compound comprising a promoter metal under conditions to effect such addition and improve conversion of the hydrocarbon feed. It may include the step of adding to.

Description

PROCESS AND SYSTEM FOR THE ADDITION OF PROMOTER METAL IN SITU IN A CATALYTIC REFORMING UNIT}

The field of the invention generally relates to a process for the conversion of hydrocarbons in a catalytic reforming unit.

Many hydrocarbon conversion processes can be used to modify the structure or properties of hydrocarbon streams. In general, these processes areomerized from straight-chain paraffinic or olefinic hydrocarbons to higher branched-chain hydrocarbons, dehydrogenation for the production of olefins or aromatic compounds, hydrocyclization for the production of aromatics and automotive fuels, Alkylation, transalkylation and the like for the production of commodity chemicals and automotive fuels.

Typically, this process uses a catalyst to promote the hydrocarbon conversion reaction. As the catalyst is deactivated, it is generally desirable to regenerate it and / or add a new catalyst to improve yield and profitability.

Various catalysts and processes have been developed for converting hydrocarbons. Often, this process requires periodic regeneration to recover contact activity and / or selectivity lost due to deactivation. Stationary bed reforming units generally perform closure of the production unit to regenerate the catalyst, while for mobile phase or circulating reforming units it is possible to regenerate the catalyst without closing the unit. After all, catalysts can be replaced for a variety of reasons, one of which is that new and more profitable catalysts are available. The new catalyst may provide advantages such as increased activity, improved selectivity, reduced deactivation and / or extended catalyst life. It is known in the art that various promoters can be included in standard catalytic naphtha modified catalysts containing platinum to improve catalyst performance. Prior to loading the catalyst into a commercial reforming unit, these promoters are incorporated into the catalyst in the catalyst preparation. In general, one of the disadvantages of replacing an existing catalyst with a new catalyst is the cost of replacing a large volume of catalyst, especially if the existing catalyst is not at the end of its useful life. It may be desirable to provide a process that enables in-situ changes of catalysts by adding one or more promoter components to existing catalysts in commercial units to improve performance to save catalyst reload costs and minimize the amount of downtime. .

Summary of the Invention

One exemplary embodiment may be a method of in-situ addition of a promoter metal catalyst component in a catalytic naphtha reforming unit. The method may include introducing a compound comprising a promoter metal catalyst component into the catalytic reforming process under conditions to effect deposition of the promoter metal on the catalyst particles and to improve conversion of the hydrocarbon feed. The selectivity of the catalyst particles may be improved, the activity of the catalyst particles may be improved, the deactivation of the catalyst particles may be reduced, the unwanted coking behavior of the catalyst particles may be reduced, or Can be any combination.

Another exemplary embodiment may be a method of adding an promoter metal, such as indium, to one or more catalyst particles in a reduction zone or reaction zone of a reforming unit. It is common to add promoter metals, such as indium, to large amounts of catalyst particles such as those present in commercial catalytic naphtha reforming units, but for the sake of simplicity and simplicity of understanding and without narrowing the scope of the invention, the catalyst particles It will be described herein on the basis of.

A further exemplary embodiment may be a system for in situ addition of a promoter metal to catalyst particles in a reforming unit comprising a first zone having a reducing atmosphere and a second zone having an oxidizing atmosphere. The system can include a reforming unit that includes one or more compounds that include promoter metals added to one or more catalyst particles. The reforming unit may be operated under conditions that promote the addition of an effective amount of promoter metal to one or more catalyst particles to increase the effectiveness of the catalyst particles to catalyze the reforming reaction. Thus, the methods and systems disclosed herein can provide several advantages. In general, compounds comprising promoter metals include effective amounts of promoter metals such as Group IIIA (IUPAC 13) metals such as indium; Group IVA (IUPOAC 14) metals such as tin, germanium; Rare earth metals such as cerium, lanthanum, europium; And other metals such as phosphorus, nickel, iron, tungsten, molybdenum, titanium, zinc or cadmium can be added to the catalyst particles. That is, the compound containing the promoter metal may react to add the promoter metal to the catalyst particles. Such additions produce large quantities of significantly desired product (selectivity), increase conversion (activity), and / or reduce unwanted deactivation properties of catalyst particles that originally contained or did not have an insufficient amount of promoter metal. To improve performance. Such addition may increase the level of promoter metal in the catalyst particles to provide additional performance benefits. In one embodiment, a compound comprising a promoter metal can be introduced into a fixed bed continuous regeneration naphtha reforming process unit in an oxychlroination zone or other regeneration zone. In another embodiment, when the catalyst is regenerated, the compound comprising the promoter metal is introduced into the regeneration gas of the fixed bed naphtha reforming unit during the oxychlorination step or other regeneration step.

Justice

The term "zone" as used herein may refer to an area that includes one or more equipment items and / or one or more subzones. Equipment items may include one or more reactor or reactor vessels, heaters, separators, hoppers, drums, exchangers, pipes, valves, pumps, compressors, blowers, and controllers. In addition, equipment items such as reactors or vessels may be included in one or more zones or subzones.

As used herein, the term "stream" refers to a variety of hydrocarbon molecules such as straight, branched or cyclic alkanes, alkenes, alkadienes and alkynes, and optionally other materials such as gases such as hydrogen, or impurities such as heavy metals, And a stream comprising sulfur and nitrogen compounds. The stream may also include aromatic and nonaromatic hydrocarbons. In addition, the hydrocarbon molecule may be abbreviated as C1, C2, C3 ... Cn, where "n" represents the number of carbon atoms in the hydrocarbon molecule.

As used herein, the term "metal" generally means an element that forms a cation when the compound thereof is in solution.

As used herein, the term “contact effective amount” generally means an amount on the catalyst support to catalyze the reaction of one or more compounds in a hydrocarbon stream. Typically, the catalytically effective amount is at least 0.005%, preferably at least 0.05% and optimally at least 0.10% by weight of the catalyst.

As used herein, the term “promoting effective amount” generally means an amount on the catalyst support to increase the contacting performance, such as in the conversion of a hydrocarbon stream to facilitate the reaction of one or more compounds in the stream. Typically, the promoting effective amount is at least 0.005%, preferably at least 0.05% and optimally at least 0.10% by weight of the catalyst.

As used herein, the term “effective amount” includes an amount capable of improving contact performance and / or promoting the reaction of one or more compounds of a hydrocarbon.

As used herein, the term “condition” generally refers to process conditions such as temperature, reaction time, pressure and space velocity, and may include an atmosphere including an oxidizing agent or a reducing agent.

As used herein, the term “oxidation” generally refers to an environment that promotes the reaction of a substance with an oxidant such as oxygen.

As used herein, the term "reduction" generally refers to an environment in which a substance facilitates obtaining electrons with a reducing agent such as hydrogen.

As used herein, the term "support" generally refers to a porosity that can optionally be combined with a binder prior to the addition of one or more additional contact active ingredients, such as precious metals, or prior to subsequent support such as oxychlorination or reduction. Means a carrier material.

As used herein, the term "halogen component" generally means halide ions or any molecule containing a halide. Halogen may include chlorine, fluorine, bromine or iodine. By way of example, the halogen component may include halogens, hydrogen halides, halogenated hydrocarbons, and compounds comprising halogens and metals. Typically, the halogen component is included in the particles and / or catalyst.

As used herein, the term "halogen containing compound" generally refers to any molecule comprising a halide. Halogen may include chlorine, fluorine, bromine or iodine. Typically, the halogen containing compound may be part of a gas stream and may include compounds such as chlorine, hydrogen chloride or perchloroethylene and provide a halogen component to the catalyst.

As used herein, the term "particle" generally means a catalyst particle containing an accelerator metal. The term “catalyst” may refer to a catalyst that is active or less active or even inert while treating and converting the feed through, for example, deposition of coke.

As used herein, the term "compound comprising promoter metal" generally refers to a molecule or species containing at least one promoter metal.

1 is a schematic of an exemplary contact naphtha reforming or reforming unit.

details

In-situ addition of an effective amount of promoter metal can occur in units having a fixed or mobile phase. Preferably, the unit comprises a mobile phase for continuous catalytic regeneration. In general, at least one compound comprising an accelerator metal is provided on an existing catalyst of at least one catalyst particle in a commercial reforming unit. Typically, the existing catalyst is a commercially prepared catalyst charged in a reactor vessel and is ready to facilitate the conversion of the naphtha feed or is already present in the feed conversion process. Existing catalysts may also be present in the regeneration process, which is periodically necessary to restore the catalytic activity as described below. By adding a compound comprising a promoter metal, the performance (ie activity, selectivity and / or deactivation properties) of the catalyst particles that do not originally contain metal or may contain less than a predetermined amount may be improved. Such addition may also increase the level of metal promoter of the catalyst particles, providing further performance benefits.

Referring to FIG. 1, an exemplary contact naphtha reforming unit 100 may include a first zone 200 comprising a reducing atmosphere and a second zone 300, which may be a regeneration zone, comprising an oxidizing atmosphere. . Lifts 120 and 124 may generally transport catalyst particles between zones 200 and 300 in the form of tablets, spheres and / or extrudate. Several access points 390 are also shown, which are discussed below. Such unit 100 can provide continuous catalyst regeneration, and exemplary units are described, for example, in US 5,958,216; US 6,034,018; And US 2006/0013763 A1. Unit 100 may have portions operated at the same or different pressures, which may be above atmospheric pressure. In one exemplary embodiment, system 110 for in situ addition of promoter metal is associated with unit 100 and is discussed further below.

Typically, after the hydrocarbon feed 205 and the hydrogen containing stream 210 are combined in the stream 220 and heated, the first zone 200 may comprise a reduction zone 240 and a reaction zone 280. ) Can be accommodated. In general, the operating temperature in the first zone 200 is 100 to 600 ° C, preferably 350 to 600 ° C, optimally 500 to 600 ° C. The pressure can range from 100 to 1700 kPa absolute pressure. The first zone 200 combines the combined hydrocarbon and hydrogen stream 200 with one or more particles or catalysts, as further described below, and halogen components, such as compounds containing fluorides or chlorides, preferably chlorides. It may include. Typically, the concentration of hydrogen in 210 is at least 15 mol%, preferably at least 50 mol%. Generally, hydrocarbon feed 205 for catalytic reforming is a petroleum fraction known as naphtha with an initial boiling point of 82 ° C. and a final boiling point of 204 ° C. The catalytic reforming process is particularly applicable to the treatment of process naphtha consisting of direct current naphtha feeds as well as relatively large concentrations of naphthenes and paraffin hydrocarbons.

Generally, regenerated catalyst (described in more detail below) enters the reduction zone 240 of the first zone 200 from the lift 120. Reduction zone 240 may include one or more subzones and / or reduction vessels, and typically includes a reducing gas, such as hydrogen, for reducing one or more metal components present in the regenerated catalyst. Reducing gas may be provided via line 250. Typically, the concentration of hydrogen in the gas is at least 15 mol%, preferably at least 50 mol%, optimally at least 75 mol%, with the remainder optionally C1 to C6 hydrocarbons. In some preferred embodiments, the concentration of hydrogen in the gas is 60 to 99.9 mol%. The temperature may be 120 to 570 ° C., preferably 200 to 550 ° C. at 450-1500 Pa absolute pressure. The molar ratio of halide: H ₂ O, preferably Cl ⁻ : H ₂ O, is 0.2: 1 to 0.6: 1.

Thereafter, the regenerated catalyst may pass through reaction zone 280. Combined hydrogen and hydrocarbon feed stream 220 may be introduced to zone 280. Reaction zone 280 may include one or more bottom zones and / or reaction vessels with heaters between reactors or bottom zones for carrying out the reforming reaction. Modifications include dehydrogenation of cyclohexane and dehydroisomerization of alkylcyclopentane to obtain aromatics, dehydrogenation of paraffins to obtain olefins, dehydrocyclization of paraffins and olefins to obtain aromatics, isomerization of n-paraffins, cyclohexane It can be defined as the total effect produced by isomerization of alkylcycloparaffins, isomerization of substituted aromatics, hydrocracking of paraffins and dealkylation of aromatics. Preferably, reaction zone 280 includes a mobile catalyst, which may be countercurrent, cocurrent, countercurrent, or a combination thereof, and the catalyst phase may be any suitable shape such as rectangular, cyclic, or spherical. The reaction zone 280 may be at a temperature of 450 to 550 ° C., an absolute pressure of 270 to 1500 kPa, a hydrogen to hydrocarbon ratio of 1 to 5, and a liquid hourly space velocity of 0.5 to 4 hr ⁻¹ . Can be. In some preferred embodiments, the concentration of hydrogen in the gas can be 55 to 65 mol%. After the reforming reaction, the hydrocarbon stream can be sent for further processing and the catalyst can be passed to lift 124 for regeneration.

Spent catalyst may exit the lift 124 and go to the regeneration zone 300. Typically, catalyst particulates may be separated and removed before going to regeneration zone 300. Generally, the temperature is 40 to 600 ° C. and the pressure is 100 to 520 Pa absolute pressure. Most of the regeneration zones 300 may operate at 350-700 ° C. Regeneration zone 300 may include an inlet gas stream comprising a halogen containing compound in one or more subzones.

The regeneration zone 300 may include an oxidation zone 320, a redispersion zone 340, a drying zone 360 and a cooling zone 360. Note that the term “zone” may refer to a zone that includes one or more equipment items and / or one or more subzones. The equipment item may include one or more vessels, heaters, separators, hoppers, drums, exchangers, pipes, pumps, compressors, blowers, valves and controllers. In addition, the item of equipment may further comprise one or more zones or subzones. In addition, in the fixed bed mode, the regeneration zone may include at least a coke burning step, a proof burn step and an oxychlorination step. In the mobile phase embodiment of FIG. 1, the oxidation zone 320 may comprise an oxidizing atmosphere of 0.5 to 1.5 volume percent oxygen. In some cases, the atmosphere may comprise more than 1.5 volume percent oxygen. Typically, spent catalyst is contacted with an oxidizing atmosphere to remove accumulated coke on the catalyst surface. In addition, chlorides on the catalyst can also be stripped. Within zone 320, the coke is oxidized at a gas temperature of generally 450-600 ° C. The pressure may be above atmospheric pressure. The catalyst may be preheated before exiting the oxidation zone via the hot outlet gas from the oxidation zone.

After exiting the oxidation zone 320, catalyst particles may be passed through the redispersion zone 340. In redispersion zone 340, a gas is provided that includes a halogen containing compound, such as a chloride compound, for redispersing the catalytic metal. In general, the redispersible gas also contains chlorine or other chloro species that can be converted to chlorine. Typically, chlorine or chloro species are introduced into the stream of small amounts of carrier gas which are added to the redispersion gas. In general, the redispersion is carried out at a gas temperature of 425 to 600 ° C, preferably 510 to 540 ° C. Typically, a concentration of 0.01 to 0.2 mol% chlorine in the gas in the presence of oxygen is used to promote redispersion. Halide: H ₂ O, preferably Cl ^-: H ₂ O molar ratio of 0.07: 1 to 16: 1, preferably 0.07: 1 to 3.2: 1.

The catalyst particles may pass through redispersion zone 340 and then through drying zone 360. Usually, the catalyst particles are dried with air heated to 600 ° C or lower, preferably 538 ° C or lower. The catalyst particles are then passed through the cooling zone 380 at a temperature of 40 to 260 ° C. before passing the catalyst particles through various other subzones and then through a lock hopper to the lift 124 to repeat in a continuous manner. You can.

Referring to FIG. 1, the catalyst and combined hydrogen and hydrocarbon feed stream 220 may be passed through a first zone 200 and the catalyst may be regenerated in a second zone 300. One exemplary application is to introduce a compound comprising a promoter metal into the catalytic reforming process, for example to add the promoter metal to the catalyst particles in situ. A compound comprising a promoter metal can be added anywhere in the unit 100, but preferably it is added to a first zone 200 comprising a reducing atmosphere or a second zone 300 comprising an oxidizing atmosphere. Compounds comprising an accelerator metal may also be added to both zone 200 and zone 300 simultaneously. In addition, several different compounds, each comprising the same or different promoter metal, may be added in multiple combinations to zone 200 and zone 300 at multiple locations.

When a compound comprising a promoter metal is added to the first zone 200, the compound comprising a promoter metal is preferably added to the naphtha feed stream 205 and / or the hydrogen containing gas stream 210 and / or the combined hydrogen. / Naphtha feed stream 220 and / or reduction zone 240 and / or reaction zone 280 are added via one or more access points 390. Alternatively, compounds comprising an accelerator metal may be added to the regeneration zone 300, preferably the oxidation zone 320 and / or the redispersion zone 340 and / or the drying zone 360 and / or the cooling zone 380. Can be added through one or more access points 390. In one embodiment, a solution of HCl, water and indium chloride may be provided to facilitate the addition of indium to zone 300. In addition, a compound comprising an accelerator metal may be added to the lifts 120 and / or 124 at the access point 390.

The system 110 disclosed herein can provide one or more catalyst particles in the reforming unit 100. The one or more catalyst particles may be one or more catalyst particles circulating through the unit 100 as described above. Each catalyst particle may comprise a support and one or more additional components that may be incorporated into the support during or after formation of the support. In general, the support may be formed or extruded by an oil drop method, but other methods may be used. The support may comprise a porous carrier material such as a refractory inorganic oxide or molecular sieve and a binder in a weight ratio of 1:99 to 99: 1, preferably 10:90 to 90:10. Carrier material

(1) refractory inorganic oxides such as alumina, magnesia, titania, zirconia, chromia, zinc oxide, thoria, boria, silica-alumina, silica-magnesia, chromia-alumina, alumina-boria Or silica-zirconia;

(2) ceramic, porcelain or bauxite;

(3) Silica or silica gel, silicon carbide, clay, or synthetic or naturally occurring silicates that may or may not be acid treated, such as attapulgus clay, diatomaceous earth, clay, kaolin Or porous kieselguhr;

(4) crystalline zeolite aluminosilicates, such as X-zeolites, Y-zeolites, mordenites, β-zeolites, Ω, in the hydrogen form or in the non-acidic form with one or more alkali metals most preferably occupying cation exchangeable sites Zeolite or L-zeolite;

(5) non-zeolitic molecular sieves, such as aluminophosphate or silico-alumino-phosphate; or

(6) Combinations of one or more materials from one or more of these groups.

In one preferred embodiment, the porous carrier is alumina, such as gamma alumina.

The binder may comprise alumina, magnesia, zirconia, chromia, titania, boria, toria, phosphate, zinc oxide, silica or mixtures thereof.

The catalyst particles may contain one or more other components which are added during formation of the support and / or incorporated thereafter. These components may be one or more metals or nonmetals, including (1) group VIII (IUPAC 8, 9 and 10) elements, (2) group IIIA (IUAC 13) elements, (3) group IVA (IUPAC 14) elements, and ( 4) may comprise a halogen component.

Preferably, the group VIII element is platinum and the catalyst particles contain a catalytically effective amount of platinum. Typically, the catalyst contains 0.01 to 2% by weight of a Group VIII element, preferably platinum, based on the weight of the catalyst. The metal component can be incorporated into the support in any suitable manner, such as co-precipitation, ion exchange or impregnation. Preferred methods for preparing the catalyst may involve impregnating the porous carrier material with a soluble, degradable Group VIII compound. By way of example, the platinum metal can be added in admixture with an aqueous solution of chloroplatinic acid, chloroiridium acid or chloropalladic acid. Other water soluble compounds or complexes of Group VIII metals may be used in the impregnation solution, which includes platinum nitrate, platinum sulfite, ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, platinum tetrachloride hydrate, platinum dichlorocarbonyl dichloride, dinitrodiamino Platinum, sodium tetranitroplatinic acid (II), palladium chloride, palladium nitrate, palladium sulfate, diamine palladium hydroxide (II), tetraamine palladium chloride (II), hexaamine rhodium chloride, rhodium carbonyl chloride, rhodium trichloride hydrate, rhodium nitrate Sodium hexachlororodate (III), hexanitrolodate (III) sodium, iridium tribromide, iridium dichloride, iridium tetrachloride, sodium hexanitroiridium acid, or sodium chloroiridium or chloroiridium, or Potassium rhodium oxalate. The use of these compounds may also provide at least some of the halogen components, in particular by adding an acid such as hydrogen chloride. In addition, consolidation may occur after firing of the support.

Similarly, the catalyst particles may contain Group IIIA metals incorporated into the support in any suitable manner, such as co-precipitation, ion exchange or impregnation. Preferred methods for preparing the catalyst may involve impregnation of the porous carrier material with a soluble, degradable Group IIIA compound. As an example, an indium metal may be added by impregnating an aqueous solution of indium chloride (InCl ₃ ) or indium nitrate (In (NO ₃ ) ₃ ) and hydrochloric acid. The use of these compounds may provide at least some of the halogen components. Other solution modifiers that can be used include nitric acid and ammonia hydroxide.

Typically, the catalyst particles contain from 0 to 1% by weight of Group IIIA elements, preferably indium, based on the weight of the catalyst. Indium may be present as a metal on the catalyst or as one or more compounds, including but not limited to indium oxide, platinum, tin and indium, or indium chloride.

The catalyst particles may contain other promoters from Group IVA and / or other elements. Preferred Group IVA elements are tin, germanium or lead, more preferably tin. Another promoter that may optionally include is rhenium; Rare earth metals such as cerium, lanthanum and / or europium; sign; nickel; iron; tungsten; molybdenum; titanium; zinc; Or cadmium. In addition, the catalyst may contain a combination of these elements. In general, the catalyst may contain from 0.01 to 5% by weight, based on the weight of the catalyst. Optionally, the catalyst may also contain 0.01 to 5% by weight of one or more Group IA and Group IIA metals (alkali and alkaline earth metals) based on the weight of the catalyst.

In the production of catalyst particles, an accelerator, such as a Group IVA metal, is used to achieve homogeneous dispersion, such as co-precipitation with a porous carrier material, ion exchange with the carrier material, or impregnation of the carrier material at any stage of preparation. It may be incorporated into the catalyst in a suitable manner. One method of incorporating a Group IVA metal into a catalyst composite involves impregnating and dispersing the metal throughout the porous carrier material using the soluble, degradable compounds of the Group IVA metal. The Group IVA metal component can be combined before, simultaneously with or after the addition of the other component to the carrier material. Accordingly, the carrier material may be selected from the group consisting of stannous bromide, stannous chloride, stannous chloride, or stannous chloride pentahydrate; Or germanium oxide, germanium tetraethoxide or germanium tetrachloride; Or by mixing with an aqueous solution of a soluble compound such as lead nitrate, lead acetate or lead chlorate or an appropriate metal salt, a Group IVA metal component can be added to the carrier material. The use of metal chloride compounds may also provide at least some of the halogen components. In one preferred embodiment, one or more organometallic compounds, such as trimethyltin chloride and / or dimethyltin dichloride, are incorporated into the catalyst during peptization of the inorganic oxide binder, preferably during peptising of alumina to hydrogen chloride or nitric acid.

The catalyst particles may also contain a halogen component, which may be fluorine, chlorine, bromine, iodine, asstatin or combinations thereof. Preferably, the halogen component is chlorine. The catalyst particles may contain typically 0.1 to 10% by weight, preferably 0.5 to 2.0% by weight, optimally 0.7 to 1.3% by weight of halogen components, preferably chlorine, based on the weight of the catalyst. The halogen component can be added with at least one metal and / or at least one promoter. In addition, the halogen component can be adjusted using a halogen-containing compound such as chlorine or hydrogen chloride at a temperature of 370 to 600 ° C. in an air or oxygen atmosphere. Water may be present during the contacting step to aid in the adjustment.

For catalyst particles, the components may be impregnated together, such as co-impregnation, or separately impregnated with one or more of any firing steps therebetween. Catalyst particles or catalysts can be prepared according to methods known to those skilled in the art as disclosed in US 2006/0102520 A1 and / or US 5,883,032. The support may be formed of a sphere or extrudates, optionally containing one or more components.

The amount of material containing catalyst particles can be measured by methods known to those skilled in the art. As an example, the UPI method 274-94 may be used for platinum and other Group VIII metals, the UPI method 303-87 may be used for tin and other Group IVA metals, and the UPI method 873-86 may be used for precious metals and variants. And indium in the catalyst, in particular by inductively coupled plasma atomic emission spectroscopy. Halogen components, in particular chlorides, can be measured by UPI method 979-02 by x-ray fluorescence or by UPI method 291-02 by potentiometer titration.

Some classes of suitable compounds containing promoter metals are those that are dissolved in the hydrocarbon naphtha feed. Compounds of this type include carbon-metal bonds, including but not limited to organometallic compounds, namely tetrabutyltin, tetrabutylgermanium, tetraethyllead, tetraethylgermanium, tetraethyltin, triphenylindium and tetrapropylgermanium It may be composed of a compound. Another class of suitable compounds containing promoter metals are those that can be prepared from water or solutions with water and acids. Compounds may include halides, nitrates, acetates, tartrates, citrates, carbonates, rhenates, tungstates and molybdates. Preferred compounds are halides, more preferably chlorides including but not limited to indium chloride, tin chloride, germanium chloride, cerium chloride, lanthanum chloride, lead chloride and europium chloride. Chloride compounds are particularly advantageous because they may also add the chloride component of the catalyst and may not introduce potential unwanted impurities. Other class of compounds may also be used, including promoter metals.

Generally, from a compound comprising an accelerator metal, a catalytically effective amount is added to the catalyst particles. Typically, at least 0.005% by weight, preferably at least 0.05% by weight, optimally at least 0.1% by weight, based on the weight of the catalyst particles, of Group IIIA elements, Group IVA elements, rare earth metal elements or other elements such as phosphorus, nickel, Iron, tungsten, molybdenum, titanium, zinc or cadmium are added to the catalyst particles.

In general, for the addition of a compound comprising a promoter metal, a solution of the compound is prepared, added to a holding tank, and then typically pumped to zone 200 and zone 300 at addition point 390. The pipe or line may be heated to assist in the transport of the compound to the zones 200 and 300. Optionally, an inert carrier gas, such as nitrogen, may be added to the line to assist in the transport of the compound to the zones 200 and 300. The content of the solution depends on the class of compound used. For a class of compounds that dissolve in water and / or inorganic acids such as water and HCl, solutions are prepared with compounds, acids and water containing promoter metals. For inorganic metal compounds containing promoter metals, other organic compounds having from 6 to 12 carbon atoms which may include a small portion of naphtha feed or such as benzene, toluene, n-hexane, n-heptane, methylcyclohexane and mixtures thereof As a solvent, a solution of an organometallic compound can be prepared. Preferred locations of addition of the organometallic compound are streams 205, 210, 220 and zone 280. In general, for all compounds added to zones 200 and 300, the compounds decompose and / or react while vaporizing under reforming conditions, adsorbing to the catalyst, and / or leaving accelerator metal deposited on the catalyst. something to do.

The following examples are intended to further illustrate the invention. This embodiment and proof of the invention are not intended to limit the claims of the invention to the specific details of the examples.

Example

200 kW of fresh commercial continuous regeneration catalyst comprising Pt, Sn and Cl on gamma alumina was charged to a four-phase quartz reactor containing 50 kW of each catalyst. Phases were numbered in sequential order with phase 5 nearest the top of the reactor and phase 2 nearest the bottom of the reactor. The phases were separated by quartz wool. In Phase 1 at the bottom of the reactor, 200 μs of a phase of gamma alumina support was charged. The initial indium level of the catalyst and the support was 0% by weight. The spacer was positioned above on the top.

Regeneration procedure was performed in the reactor. The steps of the regeneration procedure include (1) Cl ₂ and HCl, as described below, during the heating period of air ramping from room temperature to 510 ° C. at 1.4 ° C./min, and (2) the oxychlorination step for 8 hours at 510 ° C. Introduction of the containing solution, (3) cooling period for the total air to reach 93 ° C, (4) reheating / ramping period using 15 mol% hydrogen stream ramping from 93 ° C to 566 ° C at 1.5 ° C / min, (5) 15 The final cooling period to 93 ° C. in mol% hydrogen was included.

2.67 g of InCl ₃ , 15.35 g of HCl solution (36.5 wt.% HCl) and 87.16 g of water were mixed to prepare a 100 kPa solution of HCl, InCl ₃ and water. The solution was flowed through the pump into the reactor. A total of 48.65 cc of solution was injected continuously over 8 hours during the oxychlorination step. Inside the reactor, the solution fell into the spacer above phase 5. The solution was vaporized and flushed out with the catalyst by the air stream entering through the second reactor inlet line.

At the completion of the regeneration process, each catalyst phase was lowered while keeping each phase separate and analyzed by inductively coupled plasma atomic emission spectroscopy using the UOP method 873-86. Phase 5 contained 0.502 wt% indium, Phase 4 contained 0.011 wt% indium, Phase 3 contained 0.008 wt% indium, Phase 2 contained less than 0.001 wt% indium, and 1 contained less than 0.001% by weight of indium. A significant amount of indium was added to phase 5, the upper catalyst phase, and smaller amounts were added to phases 3 and 4. This experiment demonstrated that compounds containing indium can be introduced into the regeneration system while continuously adding indium to the finished catalyst in the system. In mobile phase applications, the catalyst particles in the phase physically closest to the introduction site of the indium periodic addition of the compound containing indium may contain a large amount of indium additive, but the particles may migrate through the regeneration system and indium may be periodically added. As such, indium may be added over the inventory of the catalyst over time.

Claims (10)

At least one promoter metal in the contact naphtha reforming unit, comprising introducing a compound comprising the promoter metal to the contact naphtha reforming unit under conditions effective to add the promoter metal to the catalyst particles, the temperature comprising less than 600 ° C. A method of in situ addition to catalyst particles, wherein the promoter metal is effective to increase the selectivity or activity of the catalyst particles for naphtha modification or to reduce the deactivation of the catalyst particles. The process of claim 1 wherein the contact naphtha reforming unit is a mobile phase continuous regeneration unit and introduces a compound comprising an accelerator metal into a zone operated at a temperature of 40 to 600 ° C. and an absolute pressure of 100 to 520 kPa, the zone being a mobile phase. The addition method selected from the group consisting of an oxidation zone, a redispersion zone, a drying zone, a cooling zone or a combination thereof of the continuous regeneration unit. The method of claim 1, wherein the contact naphtha reforming unit is a fixed bed unit, and when the catalyst is regenerated, a compound comprising an accelerator metal is subjected to a coke burning step, a proof burn step, an oxychlorination step or a combination thereof. The addition method of introducing into the regeneration gas during the step selected from the group consisting of. The process of claim 1 wherein the compound comprising the promoter metal is introduced into a naphtha feed stream entering the catalytic naphtha reforming unit or as a co-feed with halogen containing compound and water. The method of claim 1 wherein the promoter metal is selected from the group consisting of Group IIIA (IUPAC 13) elements, Group IVA (IUPAC 14) elements, and rare earth elements. The method of claim 1 wherein the compound comprising the promoter metal is present in solution. The method of claim 1, wherein the promoter metal comprises indium and prior to in-situ adding the one or more promoter metals to the catalyst particles, the catalyst particles comprise up to 1.0 weight percent of indium based on the weight of the catalyst particles. . The reforming unit of claim 1 wherein the reforming unit is
Reduction zone;
Reaction zone; And
Regeneration zone including oxidation zone, redispersion zone, drying zone and cooling zone
Including;
And adding the compound comprising the promoter metal to at least one of a reduction zone, a reaction zone, and a regeneration zone. The compound of claim 8, wherein the compound comprising the promoter metal is introduced into a reduction zone or reaction zone and the addition of the promoter metal to the catalyst particles occurs in a reducing atmosphere comprising hydrogen, or
The compound comprising the promoter metal is introduced into the regeneration zone and the addition of the promoter metal to the catalyst particles occurs in an oxidizing atmosphere comprising oxygen. A system for in situ addition of a promoter metal in a reforming unit comprising a first zone comprising a reducing atmosphere and a second zone comprising an oxidizing atmosphere, the system comprising at least one compound comprising a promoter metal added to at least one catalyst particle. And a reforming unit, wherein the system operates under conditions that promote adding an effective amount of promoter metal to the one or more catalyst particles to increase the selectivity or activity of the catalyst particles or reduce the deactivation of the catalyst particles.

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