MXPA01002100A

MXPA01002100A - A composition for use in converting hydrocarbons, its preparation and use

Info

Publication number: MXPA01002100A
Application number: MXPA/A/2001/002100A
Authority: MX
Inventors: Charles A Drake; Anhsiang Wu; Jianhua Yao; Scott D Love
Original assignee: Phillips Petroleum Company
Priority date: 1998-09-01
Filing date: 2001-02-27
Publication date: 2002-03-05

Abstract

A novel zeolite catalyst composition comprising a mixture of a zeolite, a binder, and a zinc borate compound wherein such mixture is calcined or treated with steam. Preferably, the zeolite has not been treated with an acid. Also provided is a process of making such composition, a product by such process, and the use thereof in the conversion of a hydrocarbon-containing fluid such as a gasoline-boiling range fluid or coker naphtha. Use of such zeolite in the conversion of a hydrocarbon-containing fluid also includes pre-treating such hydrocarbon-containing fluid with a nitrogen removal medium such as ion-exchange resin.

Description

A COMPOSITION FOR USE IN THE CONVERSION OF HYDROCARBONS, ITS PREPARATION AND USE BACKGROUND OF THE INVENTION The invention relates to a composition useful for the conversion of hydrocarbons and particularly to a zeolite catalyst composition and an improved method for the preparation of the zeolite catalyst composition, which has improved properties when compared to certain zeolite catalysts. The improved method is especially important because it provides a zeolite catalyst composition with reduced coke-forming properties and, in particular, simplifies the preparation of certain zeolite catalysts caused by metals. The invention also relates to a process for the conversion of hydrocarbons to a product that includes aromatics using the zeolite catalyst composition.

It is known to catalytically fractionate hydrocarbons from the boiling range of gasoline (in particular, hydrocarbons in the boiling range of non-aromatic gasoline, more in particular REF 127500, paraffins and olefins) to light olefins, also referred to as olefins. lower (such as ethylene and propylene), and aromatic hydrocarbons (such as BTX, ie, benzene toluene and xylene and also ethylbenzene), in the presence of zeolite-containing catalysts (such as ZSM-5), as described in the article by NY Chen et al. in Industrial & Engineering Chemistry Process Design and Development, volume 25, 1986, pages 151-155. The reaction product of this catalytic thermoforming process contains a multitude of hydrocarbons, such as non-converted C5 + alkanes, lower alkanes (methane, ethane, propane), lower alkenes (ethylene and propylene), C6-C8 aromatic hydrocarbons (benzene, toluene, xylene and ethylbenzene) and C9 + aromatic hydrocarbons. Depending on the relative prices in the market for individual reaction products, it may be desirable to increase the yield of certain of the most valuable products relative to others.

With regard to the use of zeolite catalysts in the conversion of hydrocarbons to aromatic hydrocarbons and light olefins, it is the excessive production of coke during the conversion reaction. The term "coke" refers to a semi-pure carbon, generally deposited on the surface of a metal wall or a catalyst. The coke formed during the aromatization of hydrocarbons catalyzed by zeolite tends to cause deactivation of the catalyst. It is desirable to improve the processes for the aromatization of hydrocarbons, and the formation of light olefins of the hydrocarbons, minimizing the amount of coke formed during such processes. It is also desirable to have a zeolite catalyst that is useful in the production of significant amounts of the aromatic products and olefin conversion.

Certain known methods for preparing the zeolite catalysts often require the modification of a zeolite or zeolite material with an acid to remove the components that hinder the reaction and / or promote the formation of coke. The removal of the step from the acid treatment or acid leaching process, the zeolite may be desirable with the proviso that it does not negatively impact the catalytic development of the modified zeolite. The removal of the acid treatment step may be particularly desirable if it results in an improved catalyst. There are also economic and safety benefits from the elimination of a process step that involves the use of a strong acid.

It is also known that a fluid containing thermally fractionated hydrocarbons in the boiling range of gasoline, especially coker naphtha, could be produced by a coking process, such as delayed coking, fluid coking or contact coking, all these processes being they know in the oil refining industry. Because the coking processes are well known to those skilled in the art, the description of such coking processes is omitted here.

The coker naphtha, which is produced by a coking process, has a low octane number, typically no greater than about 70, and is a volatile material that is highly olefinic and diolefinic. The coker naphtha also tends to form gums by the polymerization of diolefins and other unsaturated species that are present in coker naphtha. Although the content of unsaturated species is high, with bromine numbers (ASTM D1159) typically in the range of 50 to 80, there is no positive contribution to the octane rating of unsaturated species such as the low octane components. Because coker naphtha can be used anywhere in a refinery, the coker's naphtha must be hydrotreated severely to remove olefinic and diolefinic materials. Such treatment results in a still lower octane number. In this way, the coker naphtha must be further processed (eg, by reformation) before it can be used as a fraction in the boiling range of high octane gasoline, ie, before it can be used as a motor fuel.

Therefore, it is desirable to improve processes for raising the degree of a catalytically fractionated or thermally fractionated hydrocarbon-containing fluid in the boiling range of gasoline, such as catalytically fractionated gasoline or coker naphtha, to reduce gasoline levels. , or preferably remove, low olefinic and diolefinic materials (such as C5 + olefins and diolefins) of such hydrocarbon containing fluids, to produce a product containing high value petrochemicals, such as aromatics (such as BTX, ie, benzene, toluene and xylene) and light olefins (such as ethylene) , propylene and butylene). It is also desirable to have a zeolite catalyst composition that is useful in the improvement of such hydrocarbon containing fluids, such as catalytically fractionated gasoline or coker naphtha, in a simple step process.

It is also known that these fluids containing hydrocarbons are frequently contaminated with large amounts of nitrogen compounds. The presence of these nitrogen compounds can cause a loss of the activity and stability of the zeolite catalyst. Therefore, it is desirable to have a process that does not significantly decrease the activity and stability of a zeolite catalyst, when such a catalyst is used in the conversion of hydrocarbons, preferably during the improvement of hydrocarbon-containing fluids, such as naphtha. coqui zador.

BRIEF DESCRIPTION OF THE INVENTION The present invention involves at least partially converting hydrocarbons to aromatics (such as BTX, ie, benzene, toluene, xylene and also ethylbenzene) and light olefins (such as ethylene and propylene) using an improved zeolite catalyst composition, which has been prepared by various methods including treatment with or without acid, and in addition, such a zeolite includes a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound, more preferably, zinc hexaborate, Zn2B6011).

The invention provides a process for the preparation of an improved zeolite composition having such desirable properties, providing the production of lower coke and an improved yield of aromatics (such as BTX) and light olefins (such as ethylene and propylene), particularly with an improved ratio of olefins to aromatics in the product, when used in the conversion of hydrocarbons.

The invention also provides an improved zeolite material which, when used in the conversion of hydrocarbons, results in less coke formation than alternative zeolite materials.

The present invention further provides a method for making an improved zeolite material having such desirable properties by providing improved concentrations of benzene in the BTX fraction of a reaction product produced when such an improved zeolite material is used in the conversion of hydrocarbons., providing the aromatic yield increase with only a slight decrease in the yield of light olefins using the improved zeolite material in the conversion of hydrocarbons, or providing the increase in the yield of light defines with only a slight decrease in the yield of aromatics using the improved zeolite material in the conversion of hydrocarbons.

The invention further provides a method for making an improved zeolite material having such desirable properties, providing for the improvement of a thermally fractionated hydrocarbon containing fluid in the boiling range of gasoline, such as coker naphtha, in a process of a single stage, to reduce the levels of, or preferably remove, low olefinic and diolefinic materials (such as olefins and C5 + diolefins) and other low-value hydrocarbons from such fluids containing thermally fractionated hydrocarbons, to produce a product of high value containing a high concentration of aromatics (such as BTX), light olefins of high value (such as ethylene, propylene and butylene) and paraffins (such as methane, ethane and propane).

The present invention also relates to an improved process for the conversion of hydrocarbons, wherein the rate of coke formation during such hydrocarbon conversion is minimized.

The invention also provides hydrocarbon conversion processes having an acceptably low coke production rate and / or producing a conversion product containing appropriate quantities of aromatics (such as BTX) and light olefins (such as ethylene and propylene).

The invention also provides hydrocarbon conversion processes that produce a conversion product containing appropriate quantities of aromatics (such as BTX).

The invention also provides hydrocarbon conversion processes for the improvement of a thermally fractionated hydrocarbon containing fluid in the boiling range of gasoline, such as coker naphtha, in a process that does not significantly decrease the activity and stability of a catalyst. zeolite which results in an aromatic yield (such as BTX) that does not decrease rapidly over time during the improvement of such thermally fractionated hydrocarbon containing fluid.

One of the inventive methods provides for the conversion of hydrocarbons, preferably non-aromatic hydrocarbons, to aromatic hydrocarbons (such as BTX) and light olefins (such as ethylene and propylene), by contacting, under reaction conditions (ie, conversion conditions ), a fluid containing hydrocarbons with an improved zeolite catalyst composition prepared by a method that includes using a zeolite. The zeolite is combined, or incorporated, with a binder, a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound, and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, Zn2B6011), to form a mixture. The mixture is then calcined or treated with steam (depending on the desired reaction products), to form the improved zeolite catalyst composition. In this manner, one embodiment of the invention is a novel composition comprising a mixture that has been calcined, wherein the mixture comprises a zeolite (which has not been treated with an acid), a binder, a boron component and a component zinc (preferably the boron component and the zinc component are in the form of a zinc borate compound and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, ZnjBgOn).

Another embodiment of the invention is a novel composition, comprising a mixture that has been treated with steam, instead of calcination, wherein the mixture comprises a zeolite (which has not been treated with an acid), a binder, a component of boron and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound and, more preferably, the boron component and the zinc component are in the hexaborate form of zinc, Zn2B6011). The zeolite catalyst composition prepared by the new inventive method can be used to convert hydrocarbons, preferably non-aromatic hydrocarbons, to aromatics and light olefins, by contacting the catalyst under reaction conditions with a hydrocarbon-containing fluid.

The zeolite catalyst composition prepared by the inventive method can also be used for the improvement of fluids containing thermally fractionated hydrocarbons in the boiling range of gasoline, such as coker naphtha, in a single step process, to reduce the levels of, or preferably remove, the olefinic and diolefinic materials (such as C5 + olefins and diolefins) and other low value hydrocarbons of such fluids containing thermally fractionated hydrocarbons, to produce a product containing a high concentration of aromatics (such as BTX), light olefins of high value (such as ethylene, propylene and butylene) and paraffins (such as methane, ethane and propane).

The zeolite catalyst composition prepared by the inventive method can also be used in a process that does not significantly decrease the activity and stability of such a zeolite catalyst composition, when such a zeolite catalyst is used in the conversion of hydrocarbons, preferably during the improvement of a thermally fractionated hydrocarbon containing fluid, such as coker naphtha.

BRIEF DESCRIPTION OF THE DRAWING FIGURE 1 illustrates that activity (in terms of BTX production) and stability (in terms of BTX production over time) of a new zeolite catalyst composition, prepared by a new inventive method, can be improved when such The catalyst is used in the conversion of hydrocarbons, such as during the improvement of a thermally fractionated hydrocarbon-containing fluid, such as coker naphtha, by pretreating such hydrocarbon containing fluid with a nitrogen removal medium, such as ion exchange resin.

DETAILED DESCRIPTION OF THE INVENTION The inventive composition ines using a zeolite or zeolite material that has not been treated with an acid (i.e., an acid treatment stage or acid leaching stage is omitted). The zeolite is combined, or incorporated, with a binder, a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound and, more preferably, the boron component and zinc component are in the form of zinc hexaborate, Zn2B6011), to form a mixture, or combination, wherein such a mixture is calcined, to form a calcined or steam-treated mixture to form a vaporized mixture. The resulting calcined mixture can be used to provide an improved benzene concentration in the BTX fraction of the reaction product produced when such a calcined mixture is used in the conversion of hydrocarbons, preferably non-aromatic hydrocarbons.

The resulting calcined mixture or the resulting vaporized mixture can be used to provide an improved yield of light olefins and a higher ratio of olefins to aromatics, when used in the conversion of hydrocarbons, preferably non-aromatic hydrocarbons, than a catalyst that is made by certain methods other than the inventive method described here.

The resulting vaporized mixture can also be used to provide an improved product containing a high concentration of aromatics (such as BTX), high value olefins (such as ethylene, propylene and butylene) and paraffins (such as methane, ethane and propane) when it is used in the conversion of a thermally fractionated hydrocarbon containing fluid, such as coker naphtha. The term "fluid" is used herein to denote gas, liquid, vapor or combinations thereof.

An important feature of this invention is that the zeolite component of the composition is not treated, or leached, with an acid before mixing it with the binder, the boron component and the zinc component (preferably the boron component and a zinc component are in the form of a zinc borate compound and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, Zn2B601 :?).

The zeolite starter material used in the composition of the invention can be any zeolite or zeolite material that is effective in the conversion of hydrocarbons to aromatic hydrocarbons and light olefin hydrocarbons, when contacted under the appropriate reaction conditions. Examples of suitable zeolites include, but are not limited to, those described in Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 15, pages 638-639 (John Wiley &Sons, New York, 1981). Preferably, the zeolite has a coercion index (as defined in US Patent 4,097,367, which is incorporated herein by reference) in the range of about 0.4 to about 12, preferably in the range of about 2 to about 9. In general, the molar ratio of Si02 to Al203 in the crystalline structure of the zeolite is at least about 5: 1 and may be in the range to infinity. Preferably, the molar ratio of SiO2 to A1203 in the structure of the zeolite is in the range of about 8: 1 to about 200: 1, more preferably in the range of about 12: 1 to about 100: 1. Preferred zeolites include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and combinations thereof. Some of these zeolites are also known as "MFI" or "Pantasil" zeolites. The currently most preferred zeolite is ZSM-5.

An important aspect of this invention is the incorporation of a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, Zn2B6O?:?) in, on or with the zeolite or the zeolite material to produce a zeolite catalyst composition without the need to treat or leach the zeolite with a acid.

It has been discovered that there are certain benefits for the preparation of a zeolite catalyst having incorporated therein, on it or with it a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a zinc borate compound and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, Zn2B6011), without treating or leaching the zeolite with an acid prior to such incorporation. Depending on the use of the zeolite catalyst, such benefits include: lower coke production, an improved (ie, higher) olefin to BTX ratio in the reaction product, increased concentrations of benzene in the BTX fraction of the reaction product, and improvement of a fluid containing thermally fractionated hydrocarbons to a product with a high concentration of aromatics. These benefits result from the use of the improved zeolite catalyst composition (i.e., inventive).

To prepare the inventive zeolite catalyst composition, a zeolite initiator material is mixed or blended with a binder, a boron component and a zinc component (preferably the boron component and the zinc component are in the form of a compound of zinc borate and, more preferably, the boron component and the zinc component are in the form of zinc hexaborate, Zn2B6011), to form a mixture or combination, which has not been treated with an acid. The mixture is then calcined or treated under the appropriate steam treatment conditions, to form the inventive zeolite catalyst composition.

The zinc borate compound used in the preparation of the mixture to be calcined, or treated with steam, can be any borate compound which, when incorporated in, on or with the initiator zeolite material according to the methods and under the conditions described herein, provides a zeolite composition containing a zinc borate compound having the desired properties, such as good catalytic activity and resistance to coke formation. The zinc borate compound used in this invention could be any anhydrous zinc borate having a general formula xZnO • and B203 or any hydrated zinc borate having a general formula xZnO • yB203 • nH20, wherein x = 1 to 6 y = 1 to 5 n = an integer in the range of 0 to 14 Non-limiting examples of possible zinc borate compounds include zinc borate, zinc hexaborate, zinc diborate dihydrate, monohydrated zinc triborate, zinc tetrahydrate pentahydrate, dizinc heptahydrate hexaborate, zinc decaborate (dodecaborate) tetrazinc heptahydrate) and the like and combinations thereof. The zinc borate compound is preferably zinc hexaborate. Among the zinc hexaborate compounds, the most preferred is dizinc hexaborate heptahydrate (Zn2B6011 • 7H20).

The composition of the improved zeolite catalyst (ie, inventive) described herein, may also contain an inorganic binder (also called matrix material), preferably selected from the group consisting of alumina, silica, alumina-silica, aluminum phosphate, clays (such as bentonite), aluminate calcium, kaolin, colloidal silica, sodium silicate, titania, and the like and combinations thereof. The most preferred binders are bentonite and colloidal silica.

The relative amounts of a zeolite material, a binder and a zinc borate compound in the mixture or combination, which is to be calcined or treated with steam, should be such as to provide the inventive zeolite composition having the desired properties, such as good catalytic activity and resistance to coke formation.

In general, the mixture of a zeolite, a binder and a zinc borate compound that is to be calcined or treated with steam has a concentration of zeolite in the range of about 40 weight percent of the mixture (based on weight of the total mixture) to about 99.5 weight percent, preferably, in the range of about 50 weight percent of the mixture to about 90 weight percent of the mixture and, more preferably, in the range of 60 weight weight percent of the mixture to 80 weight percent of the mixture.

In general, the mixture of a zeolite, a binder and a zinc borate compound has a binder concentration in the range of about 5 weight percent of the mixture (on a weight basis of the total mixture) to about 40 weight percent. percent by weight of the mixture, preferably, in the range of about 10 weight percent of the mixture to about 35 weight percent of the mixture and, more preferably, in the range of 15 weight percent of the mixture to 30 weight percent of the mixture. In general, the mixture of a zeolite, a binder and a zinc borate compound has a concentration of the zinc borate compound in the range above about 30 weight percent of the mixture (on a weight basis of the mixture total), preferably in the range of about 0.5 weight percent of the mixture to about 30 weight percent of the mixture, more preferably, in the range of about 1 weight percent of the mixture to about 25 weight percent. weight of the mixture, and more preferably in the range of 2 weight percent of the mixture to 15 weight percent of the mixture.

Any suitable means for mixing a zeolite, a binder and a zinc borate compound can be used to achieve the desired dispersion of the materials in the resulting mixture. Many of the possible mixing means suitable for use in the preparation of the mixture of a zeolite, a binder and a zinc borate compound of the inventive method, for making the composition of the inventive catalyst, are described in detail in Perry's Chemi ca l Engin eers Handbook Six th Edi ti on, published by McGraw-Hill, Inc., copyright 1984, on pages 21-3 to 21-10. In this manner, appropriate mixing means may include, but are not limited to, such devices as drums, stationary sheets or hoppers, Muller mixers, which are of the intermittent or continuous type, impact mixers and the like. It is preferred to use a Muller mixer in the mixing of zeolite, a binder and a zinc borate compound.

The mixture of a zeolite, a binder and a zinc borate compound can then be formed or molded, preferably extruded or granulated. Any suitable means, known to those skilled in the art, for forming, preferably extrusion or granulation, the mixture of a zeolite, a binder and a zinc borate compound, can be used to achieve the desired formed mixture, preferably extruded mixture ( ie, extruded) or granulated mixture (ie, granulate) of a zeolite, a binder and a zinc borate compound. A liquid, such as but not limited to, water, could be used in the formation, preferably by extrusion or granulation, of the mixture of a zeolite, a binder and a zinc borate compound.

Suitable extrusion means may include, but are not limited to, devices such as screw extruders (also known as auger extruders or auger-type extruders) and the like. It is preferred to use a screw extruder in the extrusion of the mixture of a zeolite, a binder and a zinc borate compound.

Suitable granulation media may include, but are not limited to, wet granulation and dry granulation. Wet granulation consists of mixing the dry ingredients with a liquid, such as, but not limited to, water. The resulting wet paste is then dried, crushed heavily and screened to the desired size using the appropriate screen size. The dry granulation consists of densifying the dry ingredients in a reinforced tablet forming press to produce the granulates that are subsequently crushed to the desired size. It is preferred to use the wet granulation in the granulation of the mixture of a zeolite, a binder and a zinc borate compound.

It may be desirable that the mixture formed be an agglomerate of the mixture of a zeolite, a binder and a zinc borate compound. Any suitable means or method known to those skilled in the art can be used for the formation of such agglomerate. Such methods include, for example, molding, pressing, pe e ting, polishing and densification. Further discussion of such methods, including extrusion media and granulation media, is provided in a section entitled "Size Enlargement" in Perry's Ch em i ca l In gi n eers Ha n dbo ok Six th Edi ti on, published by McGraw-Hill, Inc., copyright 1984, pages 8-60 to 8-72. " In general, the zeolite, the binder and the zinc borate compounds are subsequently compounded and formed (such as stripping, extrusion or granulation) into a composite composition. In general, the surface area of the composite composition is in the range of about 50 m2 / g to about 700 m2 / g. In general, the particle size of the composite composition is in the range of about 1 mm to about 10 mm.

The mixture, preferably the mixture formed, more preferably the extruded mixture or the granulated mixture, of a zeolite, a binder and a zinc borate compound, can be subjected to the drying conditions in an atmosphere of air or inert gas (such as , but is not limited to, N2, H3, argon and the like and combinations thereof), by any of the methods known to those skilled in the art. The drying of the mixture, in general, is carried out at a temperature in the range of about 20 ° C to about 200 ° C, preferably at a temperature in the range of about 50 ° C to about 175 ° C, and more preferably at a temperature in the range of 100 ° C to 150 ° C. In general, the drying of the mixture is carried out at ambient pressure (ie, approximately 14.7 pounds per square inch absolute) or it can be carried out under The drying pressure is preferably in the range of about above ambient pressure to about 25 pounds per square inch absolute.The drying rate is controlled to avoid water vapor currents and distortions. in the range of approximately 0.5 hours to approximately 50 hours, preferably the drying time may be in the range of about 1 hour to about 30 hours, and, more preferably, the drying time may be in the range of 1.5 hours to 20 hours. The currently preferred drying is in a convection oven, under any pressure, at a temperature in the range of about 110 ° C to about 180 ° C, for a period of time from about 2 hours to about 16 hours.

The dried mixture, preferably the dry, formed mixture, more preferably the extruded, dried or dried granulated mixture of a zeolite, a binder and a borate compound, can then be calcined, by any method known to one skilled in the art. , to give a calcined zeolite catalyst composition having desirable properties, such as good catalytic activity and resistance to coke formation.

The dried mixture, preferably the dry, formed mixture, more preferably the extruded, dried or dried granulated mixture of a zeolite, a binder and a borate compound, can also be treated by exposing the mixture to a predominantly gaseous atmosphere, preferably a a completely gaseous atmosphere, comprising steam to give a final vaporized zeolite catalyst composition having the desirable properties, such as good catalytic activity and resistance to coke formation.

Calcination of the dried mixture, preferably the dry, formed mixture, more preferably the extruded, dried or dry granulated mixture of a zeolite, a binder and a zinc borate compound, could be carried out at any pressure condition and at any temperature condition that appropriately provide a final calcined zeolite catalyst composition. Preferably, the dried mixture of a zeolite, a binder and a zinc borate compound is calcined in air.

In general, the calcination could be carried out at a pressure in the range of about 7 pounds per square inch absolute (psia) to about 750 psia, preferably in the range of about atmospheric pressure (ie, about 14.7 psia) to about 450 psia, and more preferably in the range of approximately atmospheric pressure to 150 psia. The calcination temperature, in general, is in the range of about 100'C to about 1500 * C. Preferably, the calcination temperature is in the range of about 200"C to about 800 * C and, more preferably, the calcination temperature is in the range of 250" C to 700'C.

The period of time to carry out the calcination, in general, is in the range of about 1 hour to about 30 hours. Preferably, the calcination is carried out for a period of time in the range of about 2 hours to about 20 hours and, more preferably, the calcination is carried out for a period of time in the range of 3 hours to 15 hours.

The dried mixture, preferably the dry, formed mixture, more preferably the dry, extruded mixture or the dried, granulated mixture of a zeolite, a binder and a zinc borate compound, could also be subjected to vaporization conditions by exposing such a mixture to a predominantly gaseous atmosphere, preferably a completely gaseous atmosphere, comprising steam and, optionally, an inert carrier, such as nitrogen or helium to give a final vaporized zeolite catalyst composition. The vapor atmosphere, excluding the inert carrier, preferably has a vapor concentration exceeding about 90 mole percent and, more preferably, the concentration of the vapor atmosphere exceeds about 95 mole percent.

Treatment of the dried mixture of a zeolite, a binder and a zinc borate compound with steam, could be carried out at any pressure condition and any temperature condition that appropriately provide a final vaporized zeolite catalyst composition.

In general, the steam treatment could be carried out at a pressure in the range of below atmospheric pressure to about 3000 pounds per square inch absolute (psia). The most typical pressures, however, are in the range of approximately atmospheric to approximately 2500 psia. The steam treatment temperature, in general, is in the range of about 100'C to about 1500'C. Preferably, the steam treatment temperature is in the range of about 120 ° C to about 1300 ° C and, more preferably, the steam treatment temperature is in the range of 150 ° C to 800 ° C. It is preferred that the steam be overheated and not saturated.

In general, the period of time to expose the mixture of a zeolite, a binder and a zinc borate compound to a vapor atmosphere at the appropriate temperature conditions and the appropriate pressure conditions, may be in the range of about 0.1. hours at approximately 30 hours. Preferably, the steam treatment step is carried out for a period of time in the range of about 0.25 hours to about 25 hours and, more preferably, the steam treatment step is carried out for a period of time in the range from 0.5 hours to 20 hours In general, the final calcined zeolite catalyst composition or the final vaporized zeolite catalyst composition has a zeolite concentration in the range of about 40 weight percent of the composition (on a weight basis of the total composition) to about 95 weight percent of the composition, preferably, in the range of about 50 weight percent of the composition to about 90 weight percent of the composition and, more preferably, in the range of 60 weight percent of the composition. the composition at 85 weight percent of the composition.

In general, the final calcined zeolite catalyst composition or the final vaporized zeolite catalyst composition has a binder concentration in the range of about 5 weight percent of the composition (on a weight basis of the total composition) at about 50 weight percent of the composition, preferably, in the range of about 8 weight percent of the composition to about 40 weight percent of the composition and, more preferably, in the range of 10 weight percent of the composition to 30 weight percent of the composition.

In general, the composition of the final calcined zeolite catalyst or the final vaporized zeolite catalyst composition has a concentration of the zinc borate compound in the above range of about 30 weight percent of the composition (on a weight basis of the total composition), preferably, in the range of about 0.5 weight percent of the composition to about 30 weight percent of the composition, more preferably, in the range of about 1 weight percent of the composition to about 25 weight percent. one hundred weight of the composition and, more preferably, in the range of 2 weight percent of the composition to 20 weight percent of the composition.

In general, the concentration of zinc in the zinc borate compound in the final calcined zeolite catalyst composition or the final vaporized zeolite catalyst composition is in the above range of about 40 weight percent of the composition ( a weight basis of the total composition), preferably, in the range of about 0.3 weight percent of the composition to about 40 weight percent of the composition, more preferably, in the range of about 0.5 weight percent of the composition to about 30 weight percent of the composition and, more preferably, in the range of 0.7 weight percent of the composition to 20 weight percent of the composition.

In general, the concentration of boron in the zinc borate compound in the final calcined zeolite catalyst composition or the final vaporized zeolite catalyst composition is in the above range of about 20 weight percent of the composition ( a weight basis of the total composition), preferably, in the range of about 0.1 weight percent of the composition to about 20 weight percent of the composition, more preferably, in the range of about 0.3 weight percent of the composition to about 15 weight percent of the composition and, more preferably, in the range of 0.4 weight percent of the composition to 10 weight percent of the composition Any fluid containing suitable hydrocarbons comprising paraffins (alkanes) and / or olefins (alkenes) and / or naphthenes (cycloalkanes), wherein each of these hydrocarbons contains in the range of about 5 carbon atoms per molecule to about 16 atoms carbon per molecule, can be used as the fluid to be contacted with the zeolite catalyst compositions described herein under the appropriate process conditions, to obtain a reaction product, ie, conversion product, comprising light olefins (Alkenes, such as ethylene and propylene) containing in the range of about 2 carbon atoms per molecule to about 5 carbon atoms per molecule and aromatic hydrocarbons (such as BTX, ie, benzene, toluene and xylene). Frequently, the fluid containing appropriate hydrocarbons also contains aromatic hydrocarbons. The term "fluid" is used herein to denote gas, liquid, vapor or combinations thereof.

Non-limiting examples of the fluid containing suitable hydrocarbons available include gasolines from petroleum catalytic thermocracking processes (eg, FCC and hydrotherm fractionation), gasoline pyrolysis from thermo-fractionation processes of thermal hydrocarbons (eg, ethane, propane and naphtha), naphthas, gas oils, reformers, direct distillation gasoline and the like and combinations thereof. The preferred hydrocarbon-containing fluid is a fluid containing hydrocarbons in the boiling range of gasoline suitable for use as at least one gasoline mixture tank, which generally has a boiling range of about 30'C to about 210. 'C.

Another fluid containing appropriate hydrocarbons, could also comprise a fluid containing thermally fractionated hydrocarbons, which boils in the boiling range of gasoline. The preferred hydrocarbon-containing fluid of this type is coker naphtha, although other thermally produced fluids, such as gasoline pyrolysis, could also be used. Coke naphthas are unsaturated fractions that contain significant amounts of diolefins as a result of thermal fractionation. Coke naphtha is obtained by coking processes, i.e., thermal fractionation of a residual fluid, such as a residual petrol residual fluid, in a coker. As mentioned above, the coking processes are well established in the oil refining industry and are used to convert the waste fluid into liquid products of superior value. Because the coking processes are known to those skilled in the art, the description of such coking processes is omitted here.

Depending on the mode of operation of the coker and the refinery requirements, the coker naphthas could include: light naphthas (which typically have a boiling range of about 50"C to about 165 * C), full-range naphthas (which typically have a boiling range of about 25'C to about 215'C), fractions of heavy naphthas (which typically have a boiling range of about 125'C to about 210"C), or heavy gasoline fractions (which typically have a boiling range from approximately 165 * C to approximately 260'C). In addition, the present process could be operated with the complete naphtha fraction obtained from the coker or with part of the naphtha fraction obtained from the coker. The extensive analytical results of the composition of the coker naphtha and some of the characteristics of the coker naphtha are described in Pat. U.S. No. 4,711,968.

The hydrocarbon-containing fluid may be subjected to a contacting step, wherein such a hydrocarbon-containing fluid is contacted by any appropriate means, method (s) or form, with the zeolite catalyst composition., described herein, contained within a reaction zone, i.e., conversion zone. The contact stage can be operated as an intermittent process or, preferably, as a continuous process step. In the latter operation, a solid catalyst bed, or a moving catalyst bed or a fluidized catalyst bed may be employed. Any of these modes of operation have advantages and disadvantages, and those skilled in the art can select the most appropriate one for a particular fluid and catalyst.

In a preferred operational form, the hydrocarbon-containing fluid is subjected to a pre-treatment step, wherein such hydrocarbon-containing fluid is pre-treated within a pretreatment zone where it is contacted with a removal medium of Nitrogen, preferably ion exchange resin, before such a hydrocarbon containing fluid is passed to a conversion zone to be contacted with the zeolite catalyst composition. Suitable non-limiting examples of the ion exchange resin are Amberlyst-15, Amberlyst XN-1005, Amberlyst XN-1008, Amberlyst XN-1010, Amberlyst XN-1011, Amberlite 200, Amberli te-IR-120 and combinations thereof. . More preferably, the ion exchange resin is the ion exchange resin Amberli te-I R-120 (provided by Rohm &Haas Co.) or the ion exchange resin Amberli te 15 (also provided by Rohm &Haas Co. .).

The pre-treatment step can be done by any appropriate means, method (s) or form, known in the art to pre-treat a fluid containing hydrocarbons with a nitrogen removal medium such as, preferably, ion exchange resin. The pre-treatment step can be operated as an intermittent process or, preferably, as a continuous process step preferably preceding the contacting step. In a preferred operation, the pretreatment zone comprises a bed of solid ion exchange resin used before (ie, upstream of) a conversion zone comprising a bed of solid catalyst or bed of moving catalyst or bed of fluidized catalyst, which contains the composition of the zeolite catalyst. Any of these modes of operation have advantages and disadvantages, and those skilled in the art can select the most appropriate one for a particular fluid, nitrogen removal medium and the composition of the zeolite catalyst.

The pre-treatment step is preferably carried out under the pretreatment conditions which appropriately promote the reduction of the concentration of the nitrogen compounds, preferably the removal of the nitrogen compounds, from the fluid containing hydrocarbons. In this way, the resulting pretreated hydrocarbon containing fluid, which contains a reduced level of nitrogen compounds, can then be passed to a conversion zone to promote the formation of aromatics, preferably BTX, of at least a portion of the hydrocarbons of the fluid which contains hydrocarbons.

The pre-treatment conditions would include a pre-treatment temperature in the range of about O'C to about 550'C, more preferably in the range of about 10"C to about 200'C and, more preferably, in the range from 20'C to 150 ° C. The pre-treatment pressure may be in the range of below atmospheric pressure upwards of approximately 500 pounds per square inch absolute (psia), preferably, the pre-treatment pressure may be in the range of about atmospheric pressure to about 450 psia and, more preferably, the pre-treatment pressure may be from atmospheric pressure to 400 psia.

The flow rate at which the hydrocarbon containing fluid is charged to the pretreatment zone (ie, the pretreatment loading rate of the hydrocarbon containing fluid) is such as to provide a space velocity per hour by weight of pretreatment ("Pre-treatment WSHV") in the range exceeding 0 hour-1 upwards of approximately 1000 hours "1. The term" space velocity per hour by pre-treatment weight ", as used herein, shall mean the ratio number of the speed at which a fluid containing hydrocarbons is loaded into the pre-treatment zone in pounds per hour divided by the pounds of the nitrogen removal medium, preferably the ion exchange resin, contained in the pre-treatment zone. - treatment at which the hydrocarbon containing fluid is charged The preferred WHSV of pretreatment of the hydrocarbon containing fluid to the pre-treatment zone may be in the range of about 0.25 hour "1 to about 250 hour" 1, more preferably, in the range of 0.5 hour "1 to 100 hour" 1.

The contacting step is preferably carried out, within a conversion zone, where the zeolite catalyst composition is brought into contact and under the reaction conditions, ie, conversion conditions, which appropriately promote the formation of the catalyst. aromatics, preferably BTX, of at least a portion of the hydrocarbons of the hydrocarbon-containing fluid, preferably the fluid containing pre-treated hydrocarbons. In this way, the reaction product, i.e., the conversion product, includes aromatics.

Conversion conditions would include a reaction temperature of the contacting step, preferably in the range of about 400"C to about 800" C, more preferably in the range of about 450 'C to about 750"C and, more preferably, in the range of 500'C to 700'C.The contact pressure can be in the range of below atmospheric pressure up to above about 500 pounds per square inch absolute (psia), preferably, the contact pressure can be in the range of about atmospheric pressure to about 450 psia and, more preferably, the contact pressure may be in the range of atmospheric pressure to 400 psia.

The flow velocity at which the hydrocarbon-containing fluid is loaded into the conversion zone (ie, the contact loading velocity of the hydrocarbon-containing fluid is such to provide a space velocity per hour by weight of contact ("WHSV"). of contact ") in the range exceeding 0 hour" 1 upwards of approximately 1000 hours "1. The term" space velocity per hour by contact weight ", as used herein, shall mean the numerical relation of the speed at which a fluid containing hydrocarbons is charged to the conversion zone in pounds per hour divided by the pounds of the catalyst contained in the conversion zone to which the hydrocarbon-containing fluid is charged The preferred contact WHSV of the hydrocarbon-containing fluid the conversion zone may be in the range of about 0.25 hour -i about 250 hour "1 and, more preferably, in the range of 0.5 hour" 1 to 100 hour "1.

The process effluent, from the conversion zone, generally contains: a light gas fraction comprising hydrogen and methane, a C2-C3 fraction comprising ethylene, propylene, ethane and propane, an intermediate fraction comprising non-aromatic compounds having more than 3 carbon atoms, a BTX aromatic hydrocarbon fraction comprising benzene, toluene, ortho-xylene, meta-xylene, paraxylene and also ethylbenzene (ie, BTX aromatic hydrocarbons) and a C9 + fraction ("heavy") which contains aromatic compounds that have 9 or more carbon atoms per molecule In general, the process effluent can be separated into these main fractions by any known method, such as, for example, fractional distillation. Because the separation methods are known to one skilled in the art, the description of such separation methods is omitted here. The intermediate fraction can be fed to an aromatization reactor to be converted to aromatic hydrocarbons. Methane, ethane and propane can be used as a fuel gas or as a feed for other reactions such as, for example, in a thermal fractionation process, to produce ethylene and propylene. The olefins can be recovered and further separated into individual olefins by any method known to one skilled in the art. The individual olefins can then be recovered and marketed. The BTX fraction can be further separated into the individual C6 to C8 aromatic hydrocarbon fractions. Alternatively, the BTX fraction may then be subjected to one or more reactions either before or after separation to individual C6 to C8 hydrocarbons, to increase the content of the most desired BTX aromatics fraction. Suitable examples of such conversions of subsequent C6 to C8 aromatic hydrocarbons are the disproportionation of toluene (to form benzene and xylenes), the conversion of benzene and xylenes (to form toluene), and the isomerization of meta-xylene and / or ortho -xylene to para-xylene.

After the nitrogen removal medium has been deactid, preferably the ion exchange resin (ie, contaminated) by, for example, refinery feed contaminants, to a degree that the nitrogen removal capacity of the removal medium Nitrogen has become a factory, the nitrogen removal medium, preferably the ion exchange resin, could be replaced with new nitrogen removal medium or, preferably, reactid by any means or method (s) known to one skilled in the art. art, such as, for example, acid washing. The optimum temperatures and periods of time for the acid wash of the ion exchange resin depend, in general, on the types and amounts of the deactid deposits of such resin. These optimum temperatures and periods of time can be readily determined by those skilled in the art and are omitted here for the interest of brevity After the composition of the improved zeolite catalyst has been deactid, by, for example, the deposition of coke or feed contaminants, to a degree that the feed conversion and / or the selectivity has become unsuitable, the The composition of the improved zeolite catalyst (ie, inventive) can be reactid by any means or method known to one skilled in the art, such as, for example, calcination in air to burn the deposited coke and other carbonaceous materials, such as oligomers or polymers. , preferably, at a temperature in the range of about 400 ° C to about 1000 ° C. The optimum periods of time of the calcination depend, in general, on the types and amounts of deaction deposits in the zeolite catalyst composition and in the calcination temperatures.These optimal periods of time can be easily determined by ordinary experts in the art. and are omitted here for the interest of brevity.

The following examples are presented to further illustrate this invention and are not elaborated to unduly limit the scope of this invention.

EXAMPLE I This example illustrates the preparation of several catalysts that were subsequently tested as catalysts in the conversion of hydrocarbon containing fluids.

Catalyst of Zeolite ZSM-5 treated with acid A commercially available zeolite ZSM-5 catalyst (provided by United Catalysts Inc., Louisville, KY, under the designation of commercial product "t-4480" obtained as 1/16 inch extruded) was acid treated. To treat the catalyst with acid, the catalyst was rinsed in an aqueous solution of hydrochloric acid (HCl), having a concentration of 19 weight percent HCl (about 6N), for two hours at a constant temperature of about 90 * C. After rinsing, the catalyst was separated from the acid solution and washed thoroughly with water and dried. The acid rinsed, washed and dried catalyst was calcined in air at a temperature of about 525 ° C for four hours.

Catalyst A (Control An amount of 10 grams of the acid-treated zeolite catalyst ZSM-5, described above, (commercially available "T-4480" treated with acid, as described above) was impregnated, by an incipient moisture impregnation technique (ie, essentially completely filling the pores of the substrate material with a solution of the incorporation elements), with a solution containing 1.08 grams of hydrated zinc nitrate (Zn (N03) 2 • 6H20), 0.45 grams of boric acid (H3B03) and 8.47 grams of deionized water. This impregnated, acid-treated zeolite was then dried in air at 125 ° C for 16 hours.The dried, impregnated, acid-treated zeolite was then treated in a steam atmosphere for 6 hours at 650 ° C with a flow rate of H20 of 20 ml / hr followed by calcination in helium for 2 hours at 538 ° C with a helium flow rate of 50 ml / min.We obtained a final product weighing 10.26 grams.The final product contained a boron concentration (B) of 0.77 percent of the total weight of the final product (ie, 0.77 weight percent of B). The final product also contained a zinc (Zn) concentration of 2.31 percent of the total weight of the final product (i.e., 2.31 weight percent Zn). The final product had an atomic ratio of boron to zinc of 2: 1.

Catalyst B (Control) An amount of 100 grams of the zeolite ZSM-5 commercially available Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 25 grams of bentonite to form a mixture. A sufficient amount of deionized water was then added to the mixture to provide an extrudable paste which was extruded. The extrudate was then dried at room temperature (approximately 20 * C to approximately 25'C) and atmospheric pressure (approximately 14.7 pounds per square inch absolute) for approximately 2 hours and then calcined in air for 3 hours at 500 ° C. An amount of 500 grams of this extruded The dried and calcined zeolite was impregnated, by an incipient moisture technique (ie, essentially completely filling the pores of the substrate material with a solution of the incorporation elements), with a solution containing 10.8 grams of nitrate. of hydrated zinc (Zn (N03) 2 • 6H20), 4.5 grams of boric acid (H3B03) and 84.7 grams of deionized water, this extruded on impregnated zeolite was then dried at 125 ° C and atmospheric pressure ( i.e., approximately 14.7 pounds per square inch absolute) for about 3 hours.An amount of 25 grams of the extruded zeolite-bentonite impregnated, dried in this manner, then calcined in air for 3 hours at a temperature of 500'C. The impregnated zeolite-bentonite extrude, calcined in this way, was then treated in a vapor atmosphere for 8 hours at 650 ° C with a flow rate of 20 ml / hr and a helium flow rate of 500 cc. / min. A final product was obtained by weighing approximately 25 grams. The final product contained a boron concentration (B) of 0.62 percent of the total weight of the final product (i.e., 0.62 weight percent of B). The final product also contained a zinc (Zn) concentration of 1.88 weight percent of the total weight of the final product (i.e., 1.88 weight percent Zn).

Catalyst C (Invention) An amount of 20 grams of the commercially available zeolite ZSM-5 Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 5 grams of bentonite and 2 grams of Zn2B6011 • 7H20 (dizinc heptahydrate hexaborate, provided by Alfa AESAR, Ward Hill, MA under the product designation, zinc hexaborate, 98%) to form a mixture. An amount of 39 ml of deionized water was then added to the mixture to provide an extrudable paste which was extruded. The extrudate was then dried at about 125 ° C and atmospheric pressure (about 14.7 pounds per square inch absolute) for about 3 hours. The extrude of zeol i ta-bent oni t-borate zinc dried in this way, was then treated in a steam atmosphere for 4 hours at 650 ° C, with a flow rate of H20 of 20 ml / hr and a helium flow rate of 500 cc / min. A final product was obtained by weighing approximately 25 grams. The final product contained 0.26 grams of boron (B) resulting in a boron concentration of 1.0 percent of the total weight of the final product (i.e., 1.0 percent by weight of B). The final product also contained 0.53 grams of zinc (Zn) resulting in a zinc concentration of 2.1 percent of the total weight of the final product (i.e., 2.1 percent by weight of Zn).

Catalyst D (Invention) An amount of 20 grams of the commercially available zeolite ZSM-5 Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 5 grams of bentonite and 2 grams of Zn2B409 # 5H20 (trizinc tetrahydrate pentahydrate, provided by Pfaltz & Bauer, Inc., Waterbury, CT under the product designation, zinc borate) to form a mixture. An amount of 22 ml of deionized water was then added to the mixture to provide an extrudable paste which was extruded. The extrudate was then dried at about 125 ° C and atmospheric pressure (about 14.7 pounds per square inch absolute) for about 3 hours. The extruded zinc zeolite ta-bent oni t-borate dried in this way, then treated in a vapor atmosphere for 4 hours at 650 ° C, with an H20 flow rate of 20 ml / hr and a helium flow rate of 500 cc / min. A final product was obtained by weighing approximately 25 grams. The final product contained 0.18 grams of boron (B) resulting in a boron concentration of 0.7 percent of the total weight of the final product (i.e., 0.7 percent by weight of B). The final product also contained 0.83 grams of zinc (Zn) resulting in a zinc concentration of 3.3 percent of the total weight of the final product (i.e., 3.3 percent by weight of Zn).

Catalyst E (Invention) An amount of 20 grams of the commercially available zeolite ZSM-5 Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 5 grams of bentonite and 2 grams of Zn2B6Ou • 7H20 (dizinc hexaborate heptahydrate, provided by Alfa AESAR, Ward Hill, MA under the product designation, zinc hexaborate, 98%) to form a mixture. An amount of 21 ml of deionized water was then added to the mixture to provide an extrudable paste that was extruded. The extrudate was then dried at about 125 ° C and atmospheric pressure (about 14.7 pounds per square inch absolute) for about 3 hours. The extrude of zinc ze-ta-bent oni t-borate zinc dried in this way, then calcined in air for 3 hours at a temperature of 500'C. The calcination was done in place of a steam treatment. A final product was obtained by weighing approximately 25 grams. The final product contained 0.26 grams of boron (B) resulting in a boron concentration of 1.04 percent of the total weight of the final product (i.e., 1.04 weight percent of B). The final product also contained 0.53 grams of zinc (Zn) resulting in a zinc concentration of 2.12 percent of the total weight of the final product (i.e., 2.12 percent by weight of Zn).

Catalyst F (Invention) An amount of 28 grams of the zeolite ZSM-5 commercially available Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 1.4 grams of Zn2B60u • 7 H20 (dizinc hexaborate heptahydrate, provided by Alfa AESAR, Ward Hill, MA under the product designation, zinc hexaborate, 98%) and 30 grams of colloidal silica (provided by Aldrich Chemical Company, Inc., Milwaukee, Wl, under the designation of the product of "LUDOX AS-40" (suspension at 40% weight of silica in water)) to form a paste. The pulp was then dried at about 125 * C and atmospheric pressure (about 14.7 pounds per square inch absolute) for about 3 hours. The zeolite-tin-zinc borate paste dried in this manner, was then finely ground and screened to a particle size (ie, granulate) of between 12 and 20 mesh. The granulate of zeolite-1 ice- zinc borate dried in this manner, then treated in a vapor atmosphere for 4 hours at 650 ° C with a flow rate of 20 ml / hr H20 flow rate and a helium flow rate of 500 cc / min. a final product weighing approximately 22.8 grams The final product contained 0.1 grams of boron (B) resulting in a boron concentration of 0.44 percent of the total weight of the final product (ie, 0.44 percent by weight of B). it also contained 0.2 grams of zinc (Zn) resulting in a zinc concentration of 0.89 percent of the total weight of the final product (ie, 0.89 percent by weight of Zn).

Catalyst G (Invention An amount of 28 grams of the commercially available zeolite ZSM-5 Zeocat PZ2 / 50H powder (provided by Chemie Uetikon) was mixed with 2.8 grams of Zn2B6011 • 7H20 (dizinc heptahydrate heptahydrate, provided by Alfa AESAR, Ward Hill, MA under product designation, zinc hexaborate, 98%) and 25 ml colloidal silica (provided by Aldrich Chemical Company, Inc., Milwaukee, Wl, under the product designation of "LUDOX AS-40" (suspension at 40% weight of silica in water)) to form a paste. The pulp was then dried at -about 125"C and atmospheric pressure (approximately 14.7 pounds per square inch absolute) for about 3 hours. The zeolite-zinc paste itself was dried in this manner, then finely ground and screened to a particle size (ie, granulate) of between 12 and 20 mesh. The duplication preparation procedure was then repeated. the amount of the zeolitic granules as a result of zinc drying in this manner.

The granulate of zeolite t a-s i 1 i zinc ce-borate dried in this way, then treated in a vapor atmosphere for 4 hours at 650 ° C with an H20 flow rate of 20 ml / hr and a helium flow rate of 500 cc / min. A final product was obtained weighing approximately 22.8 grams. The final product contained 0.2 grams of boron (B) resulting in a boron concentration of 0.88 percent of the total weight of the final product (i.e., 0.88 weight percent of B). The final product also contained 0.4 grams of zinc (Zn) resulting in a zinc concentration of 1.78 percent of the total weight of the final product (i.e., 1.78 weight percent Zn).

EXAMPLE II This example illustrates the use of the catalysts described in Example I as catalysts in the conversion of a fluid in the boiling range of catalytically fractionated gasoline to light olefins (such as ethylene and propylene) and aromatics (such as benzene). , toluene and xylene, ie, BTX).

For each of these test runs, a 5.0 g sample of each catalyst material described in Example I was placed in a stainless steel tube reactor (length: about 18 inches, internal diameter: about 0.5 inches). Fluid in the boiling range of gasoline from a refinery catalytic fractionation unit was passed through the reactor at a flow rate of approximately 14 ml / hour, at a temperature of approximately 600 ° C, and at atmospheric pressure (approximately 0 pounds per square inch calibrated). The reaction product formed was taken out of the reactor tube and passed through several ice-cooled traps. The liquid portion was kept in these traps and weighed, while the volume of the gaseous portion that came out of the traps was measured in a "wet test meter". The samples of the liquid and gaseous product (collected at intervals per hour) were analyzed by means of a gas chromatograph. The results of the test runs for Catalyst A (Control), B (Control), C (Invention) and D (Invention) are summarized in Table I. All results were obtained after 8 hours in series. f Extruded zinc zeolite-bentonite-tetraborate dried and vaporized (the zeolite was not leached with acid).

The results of the test presented in Table 1 clearly show that the catalysts of the invention C and D exhibited considerably less coking than the control catalysts A and B. The catalyst of the invention D also exhibited an improved olefin to BTX ratio when was compared to the control catalysts A and B. The catalyst of the invention C exhibited an improved olefin to BTX ratio (ie, higher) when compared to the control catalyst B. Improvement in catalyst development is believed to be it is due to the new process for the elaboration of the inventive catalyst by drying and vaporizing an extrude of zeolite zinc bentonite or extruded zeolite-bentonite-tet raborat or zinc. The improvement in catalyst development is also significant given the fact that the catalysts of the invention C and D use a zeolite that has not been treated with acid or leached with acid.

The difference in the development between the catalysts of the invention and the control catalysts is certainly unexpected. It would be expected that the drying and steaming of an extruded zinc zeolite-bentonite ta-hexaborate would not be leached with acid, or the extruded zeolite ta-bentonite a-tet zinc borer would not be leached with acid instead of impregnated with a zeolite leaching with acid with zinc nitrate and boric acid would improve the development of the final inventive zeolite catalyst compositions. Nor would it be expected to dry and vaporize an extruded zinc zeolite ta-bentoni ta-hexaborate not leached with acid or extruded zeolite-bentonite or zinc trapezole not leached with acid, instead of impregnating an extruded of zeolite-bentonite not acid-lixiviated with zinc nitrate and boric acid, would improve the development of the final inventive zeolite catalyst compositions.

The results demonstrate that the catalysts of the invention, in which an extrude of zinc zeolite ta-benthic ta-hexaborate not acid-leased or extruded from zinc zeolite a-bentonium t-tetraborate unleaxed with acid, rather than impregnating an acid leached zeolite or extruded zeolite-bentonite not leached with acid, with zinc nitrate and boric acid, gives a catalyst that is significantly superior to the control catalysts.

EXAMPLE III This example illustrates that the catalysts of the invention described in Example I can be used to modify the yields of aromatics (such as, BTX) and light olefins (such as ethylene and propylene) in the conversion of a fluid in the boiling range of catalytically fractionated gasoline. Each test run was carried out in the same manner as described above for Example II. The results of the test runs for catalysts B (control), C (invention) and E (invention) are summarized in Table II. All test results were obtained after 8 hours in series.

Extruded zeolite ta-bent onite-zinc hexaborate, dried and calcined (the zeolite was not leached with acid).

The results of the test presented in Table II clearly show that the new methods for preparing the catalysts of the invention can have an impact on the yield of light aromatics and olefins. Catalyst C of the invention, made by the new vaporization process of an extrude of zinc zeolite ta-bentonite zinc hexaborate, exhibited superior yields of light olefins and lower aromatic yields than the calcined catalyst E of the invention. Catalyst E of the invention, made by the new calcination process, the vaporization site, an extrude of zinc zeolite ta-bentonite, hexaproate, produced an unexpected and opposite result of lower yields of light olefins and higher yields of aromatics than the vaporized catalyst C of the invention.

The results of the test indicate that the octane levels of the lower octane streams can be maximized by increasing the aromatics yield and minimizing the yield of light olefins using the catalyst E of the invention. The opposite result, of minimizing the yield of aromatics and maximizing the yield of light olefins, can be obtained using catalyst C of the invention.

In addition, catalyst E of the invention that exhibited considerably less coking than control catalyst B had an improved (ie, higher) olefin to BTX ratio when compared to control catalyst B, and had a BTX aromatic yield similar to control catalyst B. Also, as set forth above in Example II, catalyst C of the invention exhibited considerably less coking than control catalyst B and had an improved (ie, higher) olefin to BTX ratio when compared to control catalyst B .

The results demonstrate that the catalysts of the invention, in which an extruded zinc zeolite-bentonite-hexaborate is extruded and calcined, do not leach with acid or dry and vaporize, rather than impregnate a non-leached zeolite-bentonite extrude with acid with zinc nitrate and boric acid, gives a catalyst that is essentially superior to the control catalyst.

EXAMPLE IV This example illustrates that the catalysts of the invention described in Example I can be used to increase the concentration of benzene in the BTX fraction of the reaction product produced in the conversion of a fluid in the boiling range of the catalytically fractionated gasoline. Each test run was carried out in the same manner as described above for Example II. The results of the test runs for catalysts C and E of the invention are summarized in Table III. All test results were obtained after 8 hours in series.

The test results presented in Table III clearly show that the new methods for preparing the catalysts of the invention can have an impact on the increase of the higher value component, benzene, of the aromatic hydrocarbons (such as, BTX, ie, benzene, toluene and xylene) produced in the conversion of a fluid from the boiling range of catalytically fractionated gasoline. The catalyst E of the invention, made by the new calcination process of an extruded zinc zeolite-bentonite-hexaborate, produced a BTX fraction of the reaction product having a higher concentration of benzene, compared to the catalyst C of the invention, made by the new process of vaporization, instead of calcination, an extruded zinc zeolite-bentonite-hexaborate. The results of the test in Table III indicate that the concentration of benzene in the BTX fraction of the reaction product can be maximized using catalyst E of the invention.

In addition, the test results in Table III indicate that the increase in BTX yield using catalyst E of the invention (calcined extrudate) (BTX yield = 47.7% by weight) as compared to catalyst C of the invention (extruded vaporized) (BTX yield = 42.1% by weight), is a result of an increase in benzene concentration in the BTX fraction of the reaction product. It is also significant that catalyst E of the invention increased the concentration of benzene in the BTX fraction of the reaction product without affecting the concentration of the other aromatics (such as toluene and xylenes) in the BTX fraction of the reaction product.

EXAMPLE V This example illustrates that catalyst F of the invention described in Example I, can be used in the improvement of coker naphtha (a fluid containing thermally fractionated hydrocarbons in the boiling range of gasoline), in a single process step to reduce the levels of, or preferably remove, low olefinic and diolefinic materials (such as olefins and C5 + diolefins) from such a coker naphtha to produce a product containing high value petrochemicals, such as aromatics (such as BTX, ie, benzene, toluene and xylene) and light olefins (such as ethylene and propylene). The sample from the coker naphtha had been produced in a commercial coker unit.

Each test run was carried out in the same manner as described above for Example II, except that the coker naphtha of a commercial coker unit of a refinery was used in place of the boiling range fluid of a gasoline. catalytic fractionation unit of a refinery that was used in Example II. The properties of the coker naphtha used in this example are shown in Table IV below. The results of the test run for the catalyst F of the invention are summarized in Table V. All test results were obtained after 8 hours in series.

The results of the test presented in the Table V clearly shows that the new preparation methods produce inventive catalysts which can be used in the improvement of naphtha of the coker to produce a product containing high-value petrochemicals, such as aromatics (such as BTX, ie, benzene, toluene and xylene). ) and light olefins (such as ethylene and propylene). The test results also show that the catalyst F of the invention improved the coker naphtha, which initially contained only about 4 weight percent of high value pet chemicals (BTX and light olefins) before raising the grade, to about 56 Percent by weight of high-value petrochemicals (BTX and light olefins) after raising the grade.

The development of the catalyst of the invention is certainly unexpected. It would not be expected that the vaporization of a zeolite-zinc oxide borate granulate would produce a final inventive zeolite catalyst composition that produces such a high amount of high-value petrochemicals during the use of such a composition in the improvement of coke naphtha.

EXAMPLE VI This example illustrates that catalyst G of the invention described in Example I, can be used in the improvement of coker naphtha (a fluid containing thermally fractionated hydrocarbons in the boiling range of gasoline) to produce a product containing a high concentration of aromatics (such as BTX, ie, benzene, toluene and xylene). The naphtha sample from the coker had been produced in a commercial coker unit.

This example also illustrates that the activity (in terms of BTX performance) and stability (in terms of BTX throughput over time) of the catalyst G of the invention can be maintained for long periods of time when used in the improvement of naphtha. of the coker, when such naphtha of the coker is pre-treated with a nitrogen removal medium, such as the ion exchange resin Amberlyst 15 (provided by Rohm &Haas, Co.) or the ion exchange resin Amberli te-IR -120 (also provided by Rohm &Haas, Co.).

Three test runs were carried out. Run 1 was carried out in the same manner as described above for Example II, except that the coker naphtha of a commercial coker unit of a refinery was used instead of the boiling range fluid of a gasoline. catalytic fractionation unit of a refinery, which was used in Example II. The coker naphtha used in this example was the same as the coker naphtha used in Example V above. The properties of the coker naphtha, used in this example and Example V, are shown in Table IV above.

Run II was carried out in the same manner as run I, except that the coker naphtha was passed through a stainless steel tube reactor (length: about 12 inches; inner diameter: about 0.5 inches) which contained 15 grams (ie, 20 ml) of the ion exchange resin Amberl i te-IR-120 (provided by Rohm &Haas, Co.) at a flow rate of about 14 ml / hour, at a temperature of about 550"C, and at atmospheric pressure (approximately 0 pounds per square inch calibrated), before such coker naphtha was passed through the reactor containing the catalyst." Run III was carried out in the same manner as run II, except that the ion exchange resin Amberlyst 15 (provided by Rohm &Haas, Co.) was used in place of the ion exchange resin Amberli te-IR-120. The results of the three runs for the catalyst G of the invention they res umen in Table VI below.

The results of the test in Table VI illustrate a time period of 8 hours in series in 1 hour segments. The results were obtained starting with the second hour. The results in Table VI are plotted in FIGURE.

In addition, the amount of nitrogen, in parts per million (ppm), which remains in the coker naphtha after 8 hours in series during Runs I and III is summarized in Table VII below.

The results in Table VI, such results are plotted in the FIGURE, clearly demonstrate that the catalyst G of the invention can be used in the improvement of the coker naphtha to produce a high octane liquid product, which contains a high concentration of aromatics (such as BTX, ie, benzene, toluene and xylene).

The results in Table VI also demonstrate that the improvement of the coker naphtha (in terms of BTX yield) using the catalyst G of the invention did not decrease over time, when the coker naphtha was pre-treated with a coke resin. ion exchange (Runs II and III), as compared to the improvement of coker naphtha that was not pre-treated (Run I). The results show that the activity (in terms of BTX yield) and the stability (in terms of the BTX yield over time) of the catalyst G of the invention, can be maintained for long periods of time when used in the naphtha breeding. of the coker, when such coker naphtha is pre-treated with an ion exchange resin, such as Amberlyst 15 (provided by Rohm &Haas, Co.) or Amberli te-I R-120 (also provided by Rohm &Haas , Co.).

The results in Table VII demonstrate that more nitrogen was removed from the coker naphtha when such coker naphtha is pre-treated with an ion exchange resin, such as Amberlyst 15 (provided by Rohm &Haas, Co.). The results in Table VII combined with the results in Table VI demonstrate that the pretreatment of such coker naphtha with a nitrogen removal medium, such as the ion exchange resin, during the improvement of such coker naphtha helps to increase the activity and stability of the catalyst G of the invention (in terms of BTX yield and BTX yield over time) (Run III), as compared to the improvement of coker naphtha which was not pre-treated ( Run I), due to the removal of additional nitrogen by the ion exchange resin.

The results shown in the previous examples clearly demonstrate that the present invention is well suited to carry out the objectives and achieve the aforementioned objectives and advantages as well as those inherent herein.

Reasonable variations, modifications and adaptations may be made within the scope of the description and the appended claims, without departing from the scope of the invention.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims

1. A process for making a catalyst composition for use in the conversion of hydrocarbons into a conversion product including light and aromatic olefins, characterized in that the process essentially consists of: (a) mixing a zeolite, a binder and a zinc borate compound to provide a mixture, (b) treating the mixture to provide a formed agglomerate, and (c) treating the agglomerate formed by calcination or vaporization to provide the catalyst composition.

2. A process according to claim 1, characterized in that the treatment step (c) comprises calcining the agglomerate formed to provide the catalyst composition, wherein the calcination comprises exposing the agglomerate formed to: an atmosphere of air, at a temperature in the range of about 100'C to about 1500 * C, at a pressure in the range of about 7 pounds per square inch absolute (psia) to about 750 psia, and for a time in the range of approximately 1 hour to approximately 30 hours.

3. A process according to claim 1, characterized in that the treatment step (c) comprises vaporizing the agglomerate formed to provide the catalyst composition, wherein the vaporization comprises exposing the formed agglomerate to: a vapor atmosphere, which has a vapor concentration that exceeds approximately 90 mole percent, at a temperature in the range of about 100 ° C to about 1500 ° C, at a pressure in the range of below atmospheric upwards of about 3000 pounds per square inch absolute (psia), and for a period of time in the range of about 0.1 hour to about 30 hours.

4. A process according to claim 1, characterized in that the amount of zeolite in the agglomerate is in the range of about 40 weight percent of the agglomerate (on a weight basis of total agglomerate) to about 99.5 weight percent of the agglomerate (on a total agglomerate weight basis) wherein the amount of the binder in the agglomerate is in the range of about 5 weight percent of the agglomerate (on a weight basis of total agglomerate) to about 40 weight percent. weight of the agglomerate (on a total agglomerate weight basis), and wherein the amount of the zinc borate compound in the agglomerate is in the range of about 0.5 percent by weight of the agglomerate (on a weight basis of total agglomerate) ) at about 30 weight percent of the agglomerate (on a weight basis of total agglomerate).

5. A process for the conversion of hydrocarbons, characterized in that it comprises contacting under conversion conditions, a reaction mixture consisting essentially of (1) a fluid containing hydrocarbons with (2) a catalyst composition made by the process according to any of the preceding claims, to produce a conversion product that includes light olefins and toxic odors.

6. A process according to claim 5, characterized in that the fluid containing hydrocarbons is a gasoline from a catalytic thermofraction process of petroleum, a pyrolysis gasoline from a hydrocarbon thermocracking process, a naphtha, a diesel, a reformed, a Direct distillation gasoline or a combination of any two or more of the fluids containing hydrocarbons.

7. A process according to claim 5, characterized in that it further comprises passing the hydrocarbon-containing fluid through a pre-treatment zone where a nitrogen removal medium is contained before the hydrocarbon-containing fluid is subjected to contact , under conversion conditions, with the composition of the catalyst.

8. A process according to claim 5, characterized in that the amount of zeolite in the catalyst composition is in the range of about 40 weight percent of the catalyst composition (on a weight basis of the total catalyst composition) to about 95 weight percent of the catalyst composition (on a weight basis of the total catalyst composition), wherein the amount of the binder in the catalyst composition is in the range of about 5 percent by weight of the catalyst composition (on a weight basis of the total catalyst composition) to about 50 weight percent of the catalyst composition (on a weight basis of the total catalyst composition), and wherein the amount of the zinc borate compound in the composition of the catalyst is in the range of about 0.5 percent by weight of the catalyst composition (on a weight basis of the total catalyst composition) to about 30 percent by weight of the catalyst composition (on a of weight of the total catalyst composition).

9. A composition for use in the conversion of hydrocarbons, characterized in that it consists essentially of a zeolite, a binder and a zinc borate compound.

10. A process according to claim 9, characterized in that the amount of zeolite in the composition is in the range of about 40 weight percent of the composition (on a weight basis of the total composition) to about 95 weight percent of the composition (on a weight basis of the total composition), and wherein the amount of the binder in the composition is in the range of about 5 weight percent of the composition (on a weight basis of the composition total) to about 50 weight percent of the composition (on a weight basis of the total composition). A COMPOSITION FOR USE IN THE CONVERSION OF J HYDROCARBONS, ITS PREPARATION AND USE SUMMARY OF THE INVENTION A novel zeolite catalyst composition comprising a mixture of a zeolite, a binder and a zinc borate compound, wherein said mixture is calcined or steam treated. Preferably, the zeolite has not been treated with an acid. Also provided is a process for making such a composition, a product by such a process, and the use thereof in the conversion of a fluid containing hydrocarbons, such as a fluid in the boiling range of gasoline or coker naphtha. The use of such a zeolite in the conversion of a hydrocarbon-containing fluid also includes the pre-treatment of such hydrocarbon-containing fluid with a nitrogen removal medium, such as an ion exchange resin.