LU86278A1 - PROCESS FOR STABILIZING SILICALITY-TYPE CATALYSTS - Google Patents

Abstract

1. Process for stabilizing the activity of crystalline silica polymorph of the silicalite type used as hydrocarbons conversion catalyst, characterized in that it consists of : a) halogenating said silicalite by contacting it with a gaseous stream comprising : (i) an halogenation agent selected from the group comprising the organic saturated aliphatic chlorinated compounds, the organic saturated aliphatic brominated compounds, the organic saturated aliphatic fluorinated compounds and mixtures thereof, having a vapor pressure of at least 13 kPa at a temperature of 200 to 230 degrees C and having an halogen/carbon atomic ratio equal to or higher than 1 ; and (ii) a non-reducing gaseous vehicle ; at a temperature comprised between 200 and 500 degrees C and during a period of time sufficient to fix from 0.1 to 5% by weight of halogen on the silicalite ; b) recovering or using the so-formed stabilized and halogenated silicalite.

Description

F-534

PROCESS FOR STABILIZING SILICALITY-TYPE CATALYSTS

The present invention relates to a process for stabilizing silicalite type catalysts.

More particularly, the present invention relates to a process for stabilizing polymorphic crystalline silica catalysts of the silicalite type, in particular for using them in catalytic processes under pressure.

The present invention also relates to the stabilized silicalite type catalysts obtained by the process of the invention, with a view to using them in the processes of catalytic treatment under pressure.

It is well known that silicalite type catalysts are relatively stable when used in catalytic treatment processes which take place at atmospheric pressure.

This is the reason why silicalite has already been used in processes such as the isomerization of hydrocarbons, the dimerization of olefins, the aromatization and the reforming of paraffinic charges and more generally the conversion of hydrocarbons, provided that the process is carried out at atmospheric pressure.

However, it is generally advantageous to carry out these processes at pressures higher than atmospheric pressure.

To be able to operate at higher pressures while retaining a certain stability and activity with the silicalite type catalyst, it has already been proposed in US Pat. No. 4,414,423 to incorporate a metal from Group IIB of the Periodic Table of 2

Elements, usually zinc or cadmium. The incorporation can be carried out by any known method, such as impregnation and other usual techniques. This type of catalyst has been used in a catalytic treatment process containing gaseous olefins. It should however be noted that despite the attempt to stabilize the silicalite, there is a significant decrease in yield after a relatively short operating time.

It would therefore be advantageous to be able to have a process for stabilizing the silicalite with a view to its use in processes for catalytic treatment at high pressure.

The present invention therefore relates to such a method for stabilizing the silicalite.

The present invention also relates to a process for stabilizing silicalite by halogenating it with a chlorinated derivative, a brominated derivative or even a fluorinated derivative.

The present invention also relates to the stabilized silicalites obtained by the process of the invention.

The process of the present invention for stabilizing polymorphic crystalline silica of the silicalite type is characterized in that it consists in: a) halogenating this silicalite by bringing it into contact with a gas stream comprising: {i) a chosen halogenating agent in the group comprising saturated chlorinated aliphatic organic compounds, saturated brominated aliphatic organic compounds, saturated fluorinated organic compounds and mixtures thereof, having a vapor pressure of at least 13 kPa at a temperature of 200 to 230 ° C and having a low hydrogen content; and (ii) a non-reducing gaseous carrier; at a temperature between 200 and 500 ° C and for a period of time sufficient to fix from 0.1 to 1% by weight 3 H 'halogen on the silicaiite, · b) recover or use the halogenated and stabilized silicaiite thus formed.

In the process of the invention, a silicaiite is used, that is to say a polymorphic crystalline silica which has no exchange capacity compared to zeolites. Aluminum can be present in these catalysts, but only in the form of impurities originating from the starting materials and in particular from the source of silica used. The methods for obtaining these materials are given in US Patent 4,061,724 to Grose and Flanigen.

Silicalites are microporous materials prepared hydrothermally using a reaction mixture comprising tetrapropylammonium cations, alkali metal cations, water and a source of reactive silica.

According to the process of the invention, the stabilization of the silicaiite is carried out by halogenating it at a temperature between approximately 200 ° C and approximately 500 ° C, and preferably between approximately 250 ° C and approximately 300 ° C when 'Chlorinated or brominated agents are used, and preferably between about 450 and about 500 ° C when using fluorinated agents.

The halogenation of the silica is carried out by contacting with a gas stream comprising the halogenating agent and a non-reducing gaseous carrier. It has been found that this treatment must be carried out under specific conditions so as to obtain stabilized and halogenated catalysts which are active for long periods of time when they are used in these processes under pressure.

One of the conditions lies in the choice of the halogenating agent. This agent is preferably a volatile chlorinated, brominated or fluorinated saturated aliphatic organic compound, having a vapor pressure of at least 13 kPa at a temperature of about 200 to 230 ° C. It is preferable to use a hologenic compound having a vapor pressure of about 40 to 53 kPa or even more in this temperature range.

As active halogenating agent, there may be mentioned volatile halogenated compounds having a halogen / carbon atomic ratio equal to or greater than 1, containing from 1 to 4 carbon atoms, and which may contain oxygen. As halogenating agents which are particularly suitable for producing the catalysts of the present invention, mention may be made of halogenated paraffins containing from 1 to 4 carbon atoms and halogenated ethers containing from 2 to 4 carbon atoms and which meet the conditions indicated above of volatility and number of halogen atoms. As typical examples of halogenated paraffins, mention may be made of tetrachloride, tetrabromide, or carbon tetrafluoride, chloroform, bromoform, fluoroform, hexachloroethane and pentachloroethane, as well as ^ 2 ^ 2 'As others halogenating agents, mention may also be made of di-trichloromethyl ether, di-pentachloroethyl ether "and their brominated counterparts.

Among the compounds mentioned above, carbon tetrachloride and di-trichloromethyl ether are particularly suitable as halogenating agents, while chlorine and molecular bromine as well as hydrogen chloride or hydrogen bromide are less effective.

The non-reducing gaseous carrier which can be used is generally nitrogen, carbon dioxide, oxygen or their mixtures.

The total amount of halogenating agent to be used as well as the contact time with the silicalite are also controlled so as to produce catalysts containing about 0.1 to about 5% by weight of chlorine and / or bromine and / or fluorine. The contact time required depends on many factors such as the number of halogen atoms in the halogenating agent and the concentration of halogenating agent * in the gas flow or the vapor pressure of this agent. In general, it is between & and 96 hours, more particularly between 1 and 12 hours. The preferred halogen content of the catalyst depends on many factors. For example, in the majority of cases, the activity of the catalyst is higher the higher the halogen content.

However, it has been found that in most cases it is more advantageous to have a halogen content of between 0.1 and 1% by weight.

If the catalyst is not produced in situ in the reactor intended for carrying out the process under pressure, the halogenated catalyst is then discharged from the halogenation reactor and is introduced into storage containers.

The catalysts prepared according to the process of the invention can be produced in any known form, such as for example in the form of granules, powder, beads or the like.

It has been found that the halogenated catalysts prepared according to the process of the invention are particularly suitable for use in hydrocarbon conversion processes, such as for example the isomerization or dimerization of olefins, the reforming or the aromatization of paraffinic charges, when these processes are carried out under high pressure, in particular between 2.10 ^ and 7.10 ^ Pa, and especially when steam is introduced at the same time as the charge, as described in another application for patent filed the same day in the name of the Applicant and entitled "Catalytic treatment process".

Indeed, there is an essential difference between zeolites and the halogenated catalyst prepared according to the process of the invention: zeolites generally do not support the presence of water (whether in the form of liquid or vapor), so that the catalysts of the invention resist them, or even exhibit increased stability.

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It was found that the activity of the stabilized and halogenated silicalites was maintained over a much longer period when the quantity of water vapor introduced was such that the water / charge molar ratio is between 0.5 and 1.5.

If, despite the stabilization provided by the process of the present invention, it is desired to regenerate a catalyst of the halogenated silicalite type as described above, it can be regenerated according to techniques well known to those skilled in the art, by burning the hydrocarbon products which have accumulated there, for example by calcining them at temperatures between 450 ° C and 550 ° C in the presence of nitrogen containing progressively increasing oxygen contents, until the content of Οθ £ in the effluent gas is less than 0.1% in urn volume.

The following examples are given to better illustrate the present invention, but without limiting its scope.

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Example 1

Silicalite was charged to a reactor which was heated at 500 ° C for 3 hours under a stream of nitrogen having a gas hourly space velocity (GHSV) of 500 (ml / ml). It was cooled to 280 ° C. while maintaining the nitrogen flow rate, then the nitrogen sent to the reactor was saturated for 4 hours with CCI,.

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On the chlorinated silicalite, containing 0.8% by weight of chlorine, was made posser, at a temperature of 340 ° C, under a pressure of 14.7.10 ^ Pa and with a liquid hourly space velocity (LHSV) of 30 , a charge of C C hydrocarbons having the following composition: 53.3% (by weight) of n-butenes 1,2 of isobutene 44.6 of butanes 0.9 of lighter hydrocarbons, as well as water vapor in a water / charge molar ratio of 1/1.

. The following values were obtained (expressed in% by weight) for the conversion of n-butenes and the selectivity for gasolines (hydrocarbons having a boiling temperature between 36 and 200 ° C); the yield of gasolines was calculated (= conversion x selectivity): after conversion selectivity yield 9 hours 94.6% 86.8% 82, 1% 29 "91.6% 87.6% 80.2% 53" 90, 0% 85.4% 76.9% 73 "89.5% 84.8% 75.9% 95 90.1% 81.9% 73.8% 143" 88.7% 78.1% 69.3 %

Comparative example n ° l

The same charge was passed as in Example 1, as well as steam in a molar ratio <water / charge 1/1, over untreated silicalite at a temperature of 325 ° C under a pressure of 14.8.10 Pa and with an LHSV of 41.2.

The following results were obtained (% by weight): conversion of selectivity into yield of n-butenes gasolines after 12 hours 91.6% 65.2% 59.7% 26 hours 87.3% 80.7% 70, 5% 52 hours 60.7% 80.4% 48.8% 75 hours 20.4% 88.6% 18.1%

Comparative example 2

The same charge was passed as in Example 1, as well as water vapor in a water / charge molar ratio of 0.51 / 1, over untreated silicalite at a temperature of 323 ° C under a pressure of 14.8.10 Pa and with an LHSV of 31.

After 7 hours, the conversion of n-butenes was 70.6% by weight and the selectivity to essences 87.8%. After 25 hours, the conversion of n-butenes was only 6.85%.

Example 2

The experiment described in Example 1 was repeated, except for the water / charge molar ratio which was 0.45 / 1.

The following results were obtained (% by weight): conversion of selectivity into yield of n-butenes gasolines after 10 hours 89.2% 80.3% 71.6% 24 hours 88.6% 84.1% 74, 5% 54 hours 82.0% 81.8% 67.1% 78 hours 79.1% 81.1% 64.2% 97 hours 76.2% 79.8% 60.8% 122 hours 66.5% 80.4% 53.5% 9

Example 3

Silicalite was charged to a reactor which was heated at 500 ° C for 3 hours under a nitrogen GHSV of 500. It was cooled to 284 ° C while maintaining the nitrogen flow, then saturated for 110 minutes the nitrogen sent to the reactor with CCI ..

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A silicalite thus chlorinated, containing 0.4% by weight of chlorine, was passed, at a temperature of 340 ° C, under a pressure of 14.9.10 ** Pa and with an LHSV of 30, a filler having the same composition as in Example 1 as well as water vapor in a water / charge molar ratio of 0.7 / 1.

The following results were obtained (% by weight): conversion of selectivity into yield of n-butenes gasolines after 8 hours 94.5% 84.3% 79.7% 24 hours 92.9% 85.3% 79, 2% 48 hours 91.5% 82.3% 75.3% - 75 hours 90.8% 83.9% 76.2% 96 hours 89.4% 84.7% 75.7% 126 hours 89.2 % 80.2% 71.5% 149 hours 88.2% 80.6% 71.1% 157 hours 87.4% 80.5% 70.4%

Claims (14)

1. Method for stabilizing polymorphic crystalline silica of the silicalite type, characterized in that it consists in: a) halogenating this silicalite by bringing it into contact with a gas stream comprising (i) a halogenating agent chosen from the group comprising saturated chlorinated aliphatic organic compounds, saturated brominated aliphatic organic compounds, saturated fluorinated organic compounds, and mixtures thereof, having a vapor pressure of at least 13 kPa at a temperature of 200 to 230 ° C and having a low content of hydrogen; and (ii) a non-reducing gaseous carrier, at a temperature between 200 and 500 ° C and for a period of time sufficient to fix from 0.1 to 5% by weight of halogen on the silicalite; b) recovering or using the halogenated and stabilized silicalite thus formed. 2. Method according to claim 1, characterized in that the halogenating agent is chosen from the group comprising saturated chlorinated aliphatic organic compounds, saturated brominated aliphatic organic compounds and their mixtures. 3. Method according to claim 2, characterized in that one carries out the ha 1ogenation at a temperature between 250 and 300 ° C. 4. Method according to claim 1, characterized in that the halogenating agent is chosen from saturated fluorinated aliphatic organic compounds and their mixtures. "1 1 5. Method according to claim 4, characterized in that the halogenation is carried out at a temperature between 450 and 500 ° C. i · 6. Method according to one of claims 1 to 5, characterized in that the halogenating agent has a vapor pressure greater than 40 kPa at a temperature of 200 to 230 ° C. 7. Method according to claim 6, characterized in that the halogenating agent has a vapor pressure between 40 and 53 kPa at a temperature of 200 to 230 ° C. 8. Method according to one of claims 1 to 7, characterized in that the halogenating agent is chosen from compounds having a halogen / carbon atomic ratio equal to or greater than 1, and their mixtures. 9. Method according to one of claims 1 to 8, characterized in that the halogenating agent is chosen from halogenated paraffins containing from 1 to 4 carbon atoms, and their mixtures. 10. Method according to one of claims 1 to 9, characterized in that the halogenating agent is chosen from the group comprising carbon tetrachloride, tetrabromide and tetrafluoride, chloroform, bromoform, fluoroform, 1 hexachloroethane, pentachloroethane and diuoroornethane. 1 Method according to one of claims 1 to 8, characterized in that the halogenating agent is chosen from halogenated ethers containing from 2 to 4 carbon atoms, and their mixtures. 12 12. Method according to claim 11, characterized in that the halogenating agent is chosen from di-pentachloroethyl ether, di-tri-chloromethyl ether, their brominated counterparts, and their mixtures. 13. Method according to any one of claims 1 to 12, characterized in that the non-reducing gaseous carrier is chosen from nitrogen, carbon dioxide, oxygen and their mixtures. 14. Method according to any one of claims 1 to 13, characterized in that the contacting takes place for a period of time sufficient to fix from 0.1 to 1% by weight of halogen on the silicalite. 15. Polymorphic crystalline silica of the silicalite type stabilized using the process according to any one of claims 1 to 14. Brussels, the Par Pon of the company called LABOFINA S.A.