JP3589669B2 - Paraffin raw material reforming method - Google Patents

Description

実施例２から明らかなように、触媒Ｂ〜Ｄの耐用期間は触媒Ａ（水素化用金属成分を含まない）よりかなり長い。また、触媒Ｂ〜Ｄの耐用期間は、縮合反応に水素を添加することによって延びる。C5＋の収率は、使用した水素化条件に起因するアルキレート収率の低下が検出されないことを示している。The present invention relates to a method for upgrading a paraffinic feedstock. More specifically, the present invention relates to a method for alkylating paraffinic feedstocks by condensation of paraffins with olefins.
The production of highly branched hydrocarbons such as trimethylpentane is important because they can be used as high octane gasoline blending components. Highly branched hydrocarbons have traditionally been produced by condensing isobutane with light olefins using large amounts of common liquid strong acid catalysts, such as hydrofluoric acid or sulfuric acid. The light olefin is usually butene, but sometimes a mixture of propene and butene, and optionally, pentene is also used. The catalyst and the reactants obtained by stirring the emulsion of the immiscible acid and the hydrocarbon are emulsified and refrigerated to suppress the highly exothermic reaction. Fine tuning of the complex correlations of process variables can maintain the production of high quality alkylates. The acid is recycled after use. What is desired is the use of less environmentally friendly methods with lower risk and toxicity.
Various methods have been proposed to solve the above problem by using a solid acid as a catalyst. However, paraffin-olefin condensation results in both desirable alkylates and undesirable oligomerization products. When the alkylation was catalyzed with a solid acid, it was found that the catalyst was progressively deactivated by the formation of hydrocarbon deposits. However, regeneration methods for removing hydrocarbon deposits from solid acids and restoring catalytic activity are known. This method typically consists in raising the catalyst temperature and oxidizing the deposit. Nevertheless, solid acid catalysts deactivate faster than liquid acid catalysts, which is a drawback.
There is a need for an environmentally acceptable alkylation process that selectively produces highly branched alkylates at an acceptable rate over a longer period of time during production.
Co-pending European Patent Application Nos. 92201015 and 92201016 provide feeds and olefins to a reactor containing a solid acid catalyst, preferably a zeolite β catalyst, at a specific paraffin to olefin ratio, followed by reforming. Discloses a method for reforming a paraffinic raw material, which comprises removing the produced product. The process is carried out at high olefin conversion in internal and external circulation reactors, respectively, where the fluctuations in the residence time distribution of the liquid reactor contents and the external circulation of the liquid reactor contents are large, respectively. Under these conditions, it has been found that the alkylated product can be obtained with a longer catalyst life than known solid acid catalyzed processes.
The present invention surprisingly provides a solid acid catalyzed alkylation process that produces product alkylates at an acceptable rate with a high degree of selectivity to reduce catalyst deactivation by hydrocarbon deposits. It has been found that the condensation of paraffins with olefins can be carried out using alkylation processes carried out under suitable conditions. It has also been found that the length of condensable time during production before the unreacted olefin in the reactor effluent leaks out is longer than with another solid acid. Alternatively, if the regenerative capacity is the same, use of the catalyst of the present invention may allow one to operate at a higher product alkylate production rate than using another solid acid. Surprisingly, it has been found that the conditions used do not, contrary to expectation, adversely affect the quality of the product alkylate.
Accordingly, the present invention comprises contacting a feedstock and an olefin with a solid acid catalyst at a paraffin to olefin ratio of greater than 5 v / v, carried out under hydrogenation conditions, wherein the hydrogenation conditions are for hydrogenation having a liquid form. Provided is a method for reforming a paraffin-based raw material, the method including addition of a fluid and addition of a hydrogenated functional body.
As used herein, a hydrocarbonaceous deposit refers to a compound or radical formed upon catalytic condensation of paraffin and an olefin. These compounds or radicals are considered to have a semi-permanent deactivating effect on the catalyst. These deposits are presumed to consist of oligomerization products and fragments thereof formed and retained in the pores of the zeolite. If the nature and sedimentation of the deposits are not known, systematically solve the problem of suppressing the formation or deactivation of these deposits or of removing them without interrupting the condensation reaction It is not possible.
Alkylate as used herein refers to the mixed condensation product of isoparaffins and olefins, and the term oligomerization product refers to the condensation product of a plurality of olefin molecules. Alkylates are characterized by having a higher motor octane number (MON) than the oligomerization product. Typically, alkylates containing highly branched paraffins having 5 to 12 carbon atoms have a MON of 86 or greater, e.g., in the range of 90 to 94, and the corresponding oligomerization products typically have a MON of It may consist of a mixture of less than 85, for example 80 to 82, paraffinic and olefinic hydrocarbons.
Hydrogenation conditions herein refer to a reaction to the catalytic environment such that a hydrocarbon effluent from the oligomerizable fragment that would otherwise combine to form a hydrocarbon deposit is obtained. Means the condition to achieve hydrogen transfer. Without wishing to be limited to a particular theory, it is believed that under conditions that do not effectively effect the transfer of hydrogen to the catalytic environment, substantially no effluent from the oligomerizable fragment will be obtained. Effective transfer also results in selective hydrogenation of the fragments at a faster rate than oligomerization, resulting in a significantly reduced rate of adsorption as hydrocarbon deposits on the catalyst and a reduced rate of catalyst deactivation. It seems to occur under such conditions. Thus, the hydrogenation rate is appropriately controlled by the type of hydrogenation conditions and the concentration of hydrogen that can participate in the hydrogenation, provided that the rate of formation of the oligomerizable fragments during the condensation reaction is the same. The efficiency of the hydrogenation can be determined from the composition of the effluent, preferably the effluent consists of low-saturated hydrocarbons derived from oligomerizable fragments.
Surprisingly, it has been found that under the above-mentioned hydrogenation conditions, substantially no reduction in the yield of alkylate occurs. It is believed that the process of the present invention is practiced by selective hydrogenation of materials other than the desired reactants.
Hydrogenation conditions include the addition of a hydrogenation fluid in liquid form and a combination of a hydrogenating function such as a hydrogenation metal component. The metal component for hydrogenation may be selected from the group VIII or group IB metal components, combinations thereof, and combinations of these metal components with other components, for example, group VIB metal components. You can choose. The hydrogenated functional body may be chemically bound to the solid acid catalyst, for example by ion exchange, mixed with the catalyst as separated particles on a suitable support, or physically bound to the catalyst throughout the condensation reaction. The hydrogenated functional body is in the form of metal, ion or alloy, a metal component selected from platinum, palladium, copper and nickel, a combination of these components, and another metal selected from tungsten and molybdenum. It preferably consists of a combination of components. The hydrogenated functional body is preferably contained in the catalyst. Suitably, the hydrogenated function is present in an amount of 0.005 to 10.0%, preferably 0.01 to 1.0%, more preferably 0.05 to 0.5% by weight of the solid acid present.
The added hydrogenation fluid should be in the same phase as the reactants. Suitable hydrogenation fluids may consist of a mixture of a source of hydrogen, such as hydrogen gas, with an inert fluid diluent. Suitably, the reactants and the hydrogenation fluid are in liquid form, the hydrogenation fluid comprising, for example, hydrogen dissolved in an inert liquid diluent. It is appropriate that the paraffinic reactant used in the condensation, for example, the liquid lower alkane contained in the paraffinic raw material is also dissolved together. The hydrogen source may be present in the diluent at a ratio of 99: 1 to 1:99 v / v. Suitable hydrogenation fluid sources that are readily available are refinery dry gases that typically contain hydrogen, methane, ethane and traces of ethene and propene but do not contain hydrogenation metal poisons such as hydrogen sulfide. obtain. It is particularly advantageous to use the sulfur-tolerant component alone or in combination with the hydrogenation function while using the refinery dry gas as the hydrogenation fluid.
The present invention, in another embodiment, relates to a cyclic process for catalytically reforming paraffinic feedstock and improving the activity of a deactivated catalyst. The process comprises the steps of: a) feeding a feedstock and an olefin to a reactor containing a solid acid catalyst at a paraffin to olefin ratio of greater than 5 v / v and removing an effluent containing the reformed product; Exposing the catalyst to a medium for improving the activity of the catalyst by removal of hydrocarbonaceous effluent, wherein step a) is performed under hydrogenation conditions, wherein the hydrogenation conditions comprise hydrogen having a liquid form. And the addition of a hydrogenating functional body.
The medium for improving the activity of the catalyst is preferably any known medium for regenerating a solid acid catalyst. The medium is more preferably a medium for hydrogenation as described in co-pending EP-A-93202515.8. The contents of this prior patent application published specification are incorporated herein by reference.
The process of the present invention may be performed in any suitable reactor or reactor configuration. The process may be carried out continuously with regeneration of the catalyst by known methods for regenerating the solid acid conversion catalyst, or when olefin reactants in the reactor effluent leak or accumulate in the reactor And may be performed batchwise or continuously. Preferably, it is operated in a fixed bed or slurry phase reactor, optionally using an external or internal circulation of the liquid reactor contents in step a). Multiple reactors may be operated in series with the feed and effluent lines to increase processing efficiency. The process of the present invention is preferably performed continuously in view of the advantage that alkylate can be produced continuously. Suitably, multiple reactors or reactor beds may be operated, with feed and effluent lines in parallel, with steps a) and b) being performed in anti-phase on at least two beds. For example, multiple fixed or slurry phase reactors may be operated with feed and effluent lines in parallel, as in a wobble bed system, so that the alkylate is continuously produced from any one catalyst bed and the catalyst Can be properly regenerated on at least one parallel bed.
Alternatively, the slurry phase reactor is continuously operated in a condensation reaction, for example using a continuous regeneration system, and a portion of the catalyst is continuously or periodically removed from the slurry reactor into a separate vessel and a suitable regeneration step is performed. It may be treated in (step b), returned to the slurry reactor, and used in the condensation reaction (step a).
The effluent containing the hydrogenated oligomerizable fragments may be retained in the system and recycled with the effluent containing unreacted feedstock and alkylate resulting from the condensation reaction. Preferably, the combined effluent may be distilled prior to recirculation to adjust the alkylate concentration in the recycle stream. Alternatively, a portion of the effluent is separated by non-selective means and recycled. The effluent containing the hydrogenated oligomerizable fragments can be used in chemical applications, in which case it is preferred to selectively separate it from the main effluent.
The addition of the hydrogenation fluid may be performed continuously or batchwise while the effluent is continuously or batchwise removed. The frequency of the batch introduction, or the continuous flow rate, is selected to maintain the available hydrogen that can be contacted with the catalyst within the range required for the selective hydrogenation of the oligomerizable fragment. Advantageously, a sample of the effluent, removed continuously or batchwise, or a sample of the reactor vessel contents, is observed to determine the selectivity of the hydrogenation. For example, the alkylate content of the hydrocarbon effluent component can be measured to determine the olefin condensation level, or the hydrogenated oligomerizable fragment content can be measured to confirm the effectiveness of the hydrogenation conditions. Suitable methods for observing distillate components are known to those skilled in the art and, for example, gas chromatography separation can be used in combination with flame ionization detection.
The appropriate flow rate or residence time of the hydrogenation fluid is determined by the concentration or partial pressure of hydrogen that can be used in the hydrogenation fluid, the type of hydrogenation function and the concentration relative to the weight% of (zeolite) crystals in the catalyst, and Alternatively, taking into account the choice of continuous operation, the degree of aging of the catalyst, the type of catalyst composition, and the conversion conditions, such as olefin space velocity, the extent of paraffin circulation, if any, and the ratio of paraffin to olefin, the present invention Can be determined to provide the hydrogenation selectivity.
Using the process of the present invention, operations can be performed with acceptable selectivity, ie, with acceptable alkylate yields throughout the production period. It is believed that the alkylation activity of the catalyst is maintained throughout the partial deactivation and until complete deactivation of all sites occurs, ie, when olefin leakage is observed. Thus, during the production period, hydrocarbon deposits will likely continue to bind to the acid sites of the catalyst and will not be detected in the product. In order to maintain higher production rates, it may be advantageous to operate at a predetermined production rate corresponding to a combination of partial deactivation of the catalyst and frequent sediment removal by regeneration.
The process of the present invention produces a highly branched paraffin of 5 to 12 carbon atoms, preferably 5, 6, 7, 8, 9 or 12 carbon atoms, most preferably trimethyl-butane, -pentane or -hexane. It is preferred to carry out. The process is preferably carried out from a paraffinic raw material consisting of iso-paraffins having 4 to 8 carbon atoms, suitably from isobutane, 2-methylbutane, 2,3-dimethylbutane, 3-methylhexane or 2,4-dimethylhexane. , Most preferably a paraffinic feedstock consisting of C4 or C5 iso-paraffins. Suitable feedstocks for the process of the present invention include petroleum conversion product iso-paraffin containing fractions such as naphtha fraction, and purified iso-paraffinic feedstocks such as purified iso-butane.
Suitably, the olefin-containing stream comprises a lower olefin-containing hydrocarbon, which may also optionally include non-olefinic hydrocarbons. The olefin-containing stream suitably comprises ethene, propene, iso- or 1- or 2- (cis or trans) butene or pentene, optionally diluted, for example, with propane, iso-butane, n-butane or pentane. . The process of the present invention may suitably be performed downstream of a fluid catalytic cracker, MTBE etherification unit or olefin isomerization unit.
The process of the present invention is preferably performed to control the initial contact of the catalyst with the olefin feed. Suitably, the reactor is first charged with a paraffinic feed. The internal or external circulation is advantageously continuously and quantitatively charged to the reactor at an acceptable olefin space velocity with a paraffin to olefin ratio of greater than 5 v / v while simultaneously supplying the desired hydrogenation fluid. Highly diluted paraffins can be performed as described in co-pending European Patent Application Publication Nos. 92201015 and 92201016. A suitable olefin space velocity is such that a conversion of greater than 90% is maintained. The raw material mixture can advantageously be filled via a plurality of inlets in a known manner to obtain a better dispersion.
When going from step a) to step b) in a reactor or bed operating in batch mode, the feed of olefins is stopped or switched to a feed line operating in parallel, so that the phase Supply to the floor operated by The residual alkylate in the reactor or the bed may be, for example, by stopping the supply of the paraffinic raw material, drying the reactor or the bed at high temperature and / or reduced pressure, or purging the hydrocarbon raw material with the residual alkylate in the reactor. And then the hydrocarbon feed is also removed by stopping the feed. The catalyst may then be fed continuously, for example, with optional recycle of the hydrogenation fluid, or as described above over a period of time until the desired partial pressure is obtained in the reactor. Contact with the application medium.
In the case of a transition from step a) to step b) of a process carried out with a slurry reactor and continuous catalyst regeneration, the catalyst is removed periodically or continuously from the reaction vessel and step b) is carried out. And the hydrogenation fluid is introduced periodically or continuously and the effluent is removed accordingly. Removal of the entrained effluent from step a) may be accomplished by drying at elevated temperature and / or reduced pressure in the hydrogenation vessel, or subjecting the catalyst to a non-olefinic hydrocarbon purge prior to hydrogenation to remove the entrained alkylated effluent. It is implemented by doing. In a continuous removal process, a purge may be performed in a separate vessel before transferring the catalyst to the hydrogenation vessel.
When the batch-type circulation process is repeated, the supply of the paraffinic raw material is restarted over a period until the catalyst is saturated, and then the supply of the mixed paraffin raw material and the olefin is restarted as described above, and the hydrogenation conditions are restarted. If the catalyst removed from the slurry reactor for the operation of step b) is reused in step a), saturation with the paraffinic feed may be carried out in a separate vessel before returning the catalyst to the reactor. .
If it is desired to operate using an internal or external circulation, as described, for example, in co-pending application Ser. Nos. 92201015 and 92201016, the extent of the circulation is determined by the desired frequency of removal of hydrocarbon deposits and It can be selected according to the degree.
It may be desirable to convert the alkylate to a further product. Thus, the process of the present invention can be performed using a feed line to introduce the alkylate into another processing step.
The process of the present invention may advantageously be carried out at a temperature below 150 ° C, for example at 60 to 100 ° C, preferably at 70 to 80 ° C, for example at 75 ° C. The pressure in the reactor may be between 1 and 40 bar, preferably between 10 and 30 bar. A suitable reactor pressure is a pressure slightly greater than the vapor pressure of the paraffins contained in the feed at the reactor temperature, so that the reaction is maintained in the liquid phase.
Suitably the ratio of paraffins to olefins is greater than 5 v / v, preferably in the range 10-50 v / v, more preferably in the range 12-30 v / v, most preferably in the range 15-30 v / v. . A paraffin to olefin ratio suitably in the low range of 5 to 10 v / v promotes the formation of higher alkylates, for example isoparaffins having 12 carbon atoms. Operating at higher paraffin to olefin ratios promotes lower alkylate formation, but can increase the cost of effluent distillation and external circulation.
Preferred olefin conversions are 95% or higher, more preferably 98% or higher, more preferably 99% or higher, for example 99.5%, 99.8% or 99.9%. Substantially complete olefin conversion, ie, 100% conversion, is most preferred.
A preferred operating range for the olefin space velocity is 0.05 to 10.0 kg / kg.h, preferably 0.1 to 5.0 kg / kg.h, most preferably 0.2 to 1.0 kg / kg.h.
Suitable hydrogenation conditions are such as to generate usable hydrogen dissolved in the reaction phase. In a suitable manner, a hydrogenating fluid is added during the condensation reaction to make available hydrogen 0.01 to 1.0 mol / mol, preferably 0.03 to 0.1 mol / mol, more preferably It is fed in an amount equal to 0.04 to 0.06 mol / mol, for example 0.05 mol / mol. The supply of hydrogen that can be used depends on the type of hydrogenation conditions that are in effect, for example, the type of hydrogenation function bound to the catalyst. In any case, the feed rate of the hydrogenation fluid is such that the oligomerizable fragments formed in the reaction mixture can be converted at a rate higher than the oligomerization rate, except that a secondary phase consisting mainly of hydrogen is introduced into the reaction vessel. It must be sufficient to hydrogenate so that it is not formed. Preferably, the hydrogenation fluid is co-fed as a solution with the isobutene feed to the reactor.
The process of the present invention advantageously monitors the effluent using, for example, known methods as described above, thereby adjusting the feed rate and feed line in response to multivariable constant control of selected operating parameters. It can be performed while performing. In the preferred operation of the process of the present invention, the effluent is monitored during operation and composition readings are provided to an improved process controller operating with the process model to achieve optimal treatment efficiency.
The process of the present invention can be performed using any solid acid catalyst. Particularly suitable catalysts include strongly acidic large pore molecular sieves, such as zeolites with pore diameters greater than 0.70 nm, sulfate supported metal oxides, amorphous silica alumina, metal halides on alumina, macroreticular acid cation exchange. Resins such as acidified perfluorinated polymers, heteropoly acids and activated clay minerals.
Specific examples of zeolite catalysts include zeolite β, zeolite ω, mordenite and faujasite, especially zeolites X and Y. The most preferred of these is zeolite β. The zeolite may be ion exchanged with, for example, an ammonium source and optionally calcined to increase the acidity. Specific examples of the sulfate-supporting metal oxide include zirconium oxide, titanium oxide, and iron oxide supporting a sulfate. Preferred is sulfated zirconium oxide. Specific examples of amorphous silica alumina include acidified, for example, fluorinated, amorphous silica alumina. Specific examples of the metal halide on alumina include hydrochloric acid-treated aluminum chloride and aluminum chloride on alumina. Specific examples of cation exchange resins include Nafion ™, an acidified perfluorinated polymer of sulfonic acid. Specific examples of the heteropolyacid include H_ThreePW₁₂O₄₀, H_FourSiMo₁₂O₄₀And H_FourSiW₁₂O₄₀Is mentioned. Specific examples of the clay mineral include smectite and montmorillonite.
Catalysts are described, for example, in the first reported synthesis, Newman, Treacy et al., Proc.R.Soc.London Ser.A.420, 375 or zeolite β crystals which conform to the structural classification of zeolite β as described in US Pat. No. 3,308,069. Zeolite β can be prepared by the method described in Zeolites 8 (1988) 46-53, using tetramethylammonium hydroxide as a template. Suitably, the zeolite is calcined before use, for example at 550 ° C. for 2 hours. The desired silicon to aluminum ratio of the calcined material can be selected appropriately. Zeolites can be ion exchanged with, for example, ammonium nitrate and calcined to a hydrogen form to increase acidity.
In a preferred embodiment of the present invention, the zeolite is further combined with a hydrogenation metal component as described above, preferably platinum, palladium, copper and nickel, combinations thereof, and another metal component selected from tungsten and molybdenum. Is ion-exchanged with a component selected from the combinations described above, and then calcined. The amount of said components is 0.005 to 10% by weight of the zeolite, preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight. The zeolite is preferably subjected to reducing conditions before it is used to convert the metal component for hydrogenation into metal form. It has been found that the use of ion exchange with the metal components as described above, during the condensation reaction, in proper combination with the hydrogenation fluids as described above, results in catalysts that provide useful selective hydrogenation. .
The zeolites can be used directly or additionally in combination with a support. For example, the zeolite can be present in combination with a refractory oxide that functions as a binder, such as silica, alumina, silica-alumina, magnesia, titania, zirconia, and mixtures thereof. Particularly preferred is alumina. The weight ratio between the refractory oxide and the zeolite is suitably from 10:90 to 90:10, preferably from 50:50 to 15:85. The binder is suitably combined with the zeolite before the final calcination of the zeolite, and the combination is optionally extruded and finally calcined before use.
The process of the present invention will now be described by way of non-limiting examples.
Example 1
Catalyst A consisting of zeolite β was converted to Zeolites using tetramethylammonium hydroxide.8(1988) 46-53. After synthesis, the solid was separated from the liquid, washed with deionized water, dried and calcined at 550 ° C. for 2 hours. The calcined material had a silicon to aluminum ratio of 14.7. The zeolite was acidified by ion exchange with ammonium nitrate and calcination at 450 ° C. for 2 hours.
A sample of catalyst A was filled with 0.1% by weight of palladium, copper and nickel by ion exchange with aqueous solutions of palladium tetraamine, copper nitrate and nickel nitrate, respectively, and finally calcined at 450 ° C. for 2 hours to form catalyst B, C and D were produced.
Example 2
Catalyst B with a mesh size of 60-140 was dried in air at 200 ° C. for 2 hours and then charged into a fixed bed recycle reactor. The reactor was pressure tested with hydrogen at room temperature and the temperature was raised to 250 ° C in a stream of hydrogen and maintained at 250 ° C for 16 hours. The reactor was brought to and maintained at a temperature for the alkylation reaction of about 90 ° C. The reactor was charged with isobutane until saturation. The effluent stream is withdrawn while continuously supplying isobutane, and the reactor effluent is recycled at a recycle ratio of about 250 at an olefin space velocity of 0.2 kg / kg. A mixture with an olefin ratio of 30 v / v) was co-fed with the hydrogen into the reactor at a hydrogen to olefin ratio of about 0.05 mol / mol. The effluent discharged from the reactor was analyzed online by GLC and separated into an atmospheric liquid and a vapor product. The reaction was continued until a butene leak was observed in the effluent.
The reaction was repeated substantially as described above, using catalysts C and D instead of catalyst B.
Olefin conversion was greater than 99.0 mol%. That is, the conversion was substantially complete. The results are shown in Table 1 below. The yield of C5 + product, essentially paraffinic, was 200% by weight of the olefin.
Comparative example
For comparison, substantially the same as above, but differs from the present invention in that firstly catalyst A is used in place of catalyst B and secondly catalyst B is used without the simultaneous supply of hydrogen. The reaction was repeated in the procedure. The results are shown in Table 1 below.

As is evident from Example 2, the lifetime of catalysts B to D is considerably longer than that of catalyst A (containing no metal component for hydrogenation). The service life of the catalysts B to D is extended by adding hydrogen to the condensation reaction. The C5 + yield indicates that no decrease in alkylate yield due to the hydrogenation conditions used is detected.

Claims (16)

A method for reforming a paraffinic raw material, comprising contacting the raw material and an olefin with a solid acid catalyst at a paraffin to olefin ratio of greater than 5 v / v, wherein the method is carried out under hydrogenation conditions. The above-mentioned method, wherein the hydrogenation conditions include addition of a hydrogenation fluid having a liquid form and addition of a hydrogenation functional body. The method of claim 1 in which the hydrogenation fluid consists of hydrogen source dissolved in a fluid inert diluent. Inert fluid diluent is reactive paraffin The method of claim 2. The method according to any one of claims 1 to 3, wherein the hydrogenation fluid comprises hydrogen gas. Hydrogenating functional element, a Group IB or a V III-group metal component, combinations thereof, and the selected hydrogenating metal from a combination of these and other components selected from the VI B group metal component The method according to any one of claims 1 to 4 , comprising a component. A metal, ionic or alloy form selected from the group consisting of platinum, palladium, copper and nickel, combinations thereof, and combinations thereof with another metal component selected from tungsten and molybdenum; 6. The method of claim 5 , comprising more than one type of metal component. The method according to any one of claims 1 to 6 , wherein the hydrogenated functional body is chemically or physically combined with or mixed with the catalyst. The hydrogenating function body, The method according to any one of claims 1 to 7 is present in an amount of 0.005 to 10.0% by weight of the solids present acid. The catalyst was selected from zeolites with pore diameters greater than 0.70 nm, sulfate-supported metal oxides, amorphous silica alumina, metal halides on alumina, macroreticular acid cation exchange resins, heteropoly acids and activated clay minerals the method according to any one of claims 1 consisting of components 8. The method according to any one of claims 1 catalyst comprises zeolite β component 8. Optionally using external or internal circulation of liquid reactor contents A method according to any one of claims 1 to 10 carried out in a fixed bed or slurry phase reactor. Included in a cycling process for catalytically reforming paraffinic feedstocks and improving the activity of deactivated catalysts is the process comprising: a) feeding a feedstock and olefins to a reactor containing a solid acid catalyst in paraffins greater than 5 v / v. Removing an effluent comprising a reformed product supplied at a ratio to olefins; and b) exposing the catalyst to a medium for improving the activity of the catalyst by removing the hydrocarbon effluent; step a) is carried out under hydrogenation conditions, the hydrogenation conditions include the addition of additives and hydrogenated for function of hydrogenating fluid having a liquid form, according to any one of claims 1 to 11 the method of. 13. The method according to claim 12 , wherein the medium for improving the activity of the catalyst is a hydrogenation medium. 14. The process according to claim 12 or 13 , wherein the reactor optionally comprises a fixed bed or slurry phase reactor using external or internal circulation of the liquid reactor contents in step a). 15. A process according to any of claims 12 to 14 , wherein the steps a) and b) are carried out in a plurality of reactors or reactor beds operating in parallel with the feed and effluent lines, with the steps a) and b) being carried out in antiphase on at least two beds. A method according to claim 1. Catalyzes the step b) of the separate container from the reactor for operation continuously or periodically removed and returned to the reactor for operation of step a), from claim 12 carried out in a slurry reactor The method according to any one of claims 15 to 15 .