CA1121975A - Crystalline silicates and method of preparing the same - Google Patents
Crystalline silicates and method of preparing the sameInfo
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- CA1121975A CA1121975A CA000297955A CA297955A CA1121975A CA 1121975 A CA1121975 A CA 1121975A CA 000297955 A CA000297955 A CA 000297955A CA 297955 A CA297955 A CA 297955A CA 1121975 A CA1121975 A CA 1121975A
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Abstract
CRYSTALLINE SILICATES AND METHOD
OF PREPARING THE SAME
Abstract of the Disclosure A novel synthetic crystalline silicate composition is described which is essentially free of Group IIIA metals, e.g. aluminum and /or gallium, and is particularly useful in catalytic cracking of hydrocarbons. It possesses an X-ray diffraction pattern manifesting substantially the d-spacing set out in Table I below:
OF PREPARING THE SAME
Abstract of the Disclosure A novel synthetic crystalline silicate composition is described which is essentially free of Group IIIA metals, e.g. aluminum and /or gallium, and is particularly useful in catalytic cracking of hydrocarbons. It possesses an X-ray diffraction pattern manifesting substantially the d-spacing set out in Table I below:
Description
This invention relates to novel crystalline silicates and to methods for their preparation and to organic com-pound conversion, especially hydrocarbon conversion therewith.
Zeolitic materials, both natural and synthetic, have been known in the past to have catalytic capability for various types of hydrocarbon conversion reactions. Certain of these zeolitic materials comprising ordered porous crystalline aluminosilicates have a definite crystalline structure, as determined by X-ray diffraction, within which there are a number of small cavities which are intercon-nected by a number of still smaller channels. These cavities and channels are precisely uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption purposes molecules of cer-tain dimensions while rejecting those of larger dimensions, these materials have commonly been known to be "molecular sieves" and are utilized in a variety of ways to take ad-vantage of the adsorptive properties of these compositions.
~hese molecular sieves include a wide variety of positive ion containing crystalline aluminosilicates, both natural and synthetic. These aluminosilicates can be described as a rigid three-dimensional network of SiO4 and ~104 in which the tetrahedra are cross linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electro-valence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example, an a~kaline metal or alkaline earth cation. Thus, a uni-valent positive sodium cation balances one negatively charged aluminosilicate tetrahedra where an alkaline earth metal cation is employed in the crystal structure of an aluminosilicate, it balances two negatively charged tetrahedra because of its doubly positive valence. One type of cation may be exchanged either entirely or partially by another type of cation utilizing ion exchange techniques in a conventional manner. sy means of such cation exchange, it has been possible to vary the size of the pores in a given aluminosilicate by suitable selection of the parti-ular cation. The spaces between the tetrahedra are occupied by moleeules of water prior to dehydration.
One such group of crystalline aluminosilicates designated as those of the ZSM-5 type, have been known and are particularly described in U.S. Patent number 3,702,886. The ZSM-5 type crystalline aluminosilicates have been prepared, for example, from a solution containing a tetraalkyl ammonium hydroxide, sodium oxide, an oxide of aluminum or gallium, an oxide of silicon or germanium and water and have been found to be characterized by a specific X-ray diffraction pattern.
The above crystalline aluminosilicates, as previously noted, have been characterized by the presence of aluminum and silicon, the total of such atoms to oxyaen being 1:2.
The amount of alumina present appears directly related to aeidity characteristics of the resulting product. A low alumina content has been recognized as being advantageous in obtaining a low degree of acidity which in many catalytic reactions is translated into low coke making properties and low aging rates.
In accordance with the present invention there is provided a famlly of crystalline silicates which are essentially free of Group IIIA metals ~Sargent-l~elch periodic table~, i.e.
, 9t~5 aluminum and/or gaLlium. These silicates have surprisingly been found to be characteriz~d by an X-ray diffraction pattern characteristic of the above-noted ZSM-5 type cry-stalline aluminosilicates. Thus, the novel synthetic crystalline silicate of this invention can be defined as that which possesses an X-ray diffraction pattern manifes-ting substantially the d-spacing set out in Table 1 below:
. .
.. .. .. . . ~
Interplanar spacing d(A) Relative Intensity _ __ _ _ 11.1 + 0.2 s 10.0 + 0.2 s 7.4 + 0.15 w 7.1 + 0.15 w 6.3 + 0.1 w 6.04 + 0.1 w 5.97 5.56 + 0.1 w 5.01 + 0.1 w 4.60 + 0.0~ w 4.25 + 0.08 w 3.85 + 0.07 vs 3.71 + 0.05 s 3.04 + 0.03 w
Zeolitic materials, both natural and synthetic, have been known in the past to have catalytic capability for various types of hydrocarbon conversion reactions. Certain of these zeolitic materials comprising ordered porous crystalline aluminosilicates have a definite crystalline structure, as determined by X-ray diffraction, within which there are a number of small cavities which are intercon-nected by a number of still smaller channels. These cavities and channels are precisely uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption purposes molecules of cer-tain dimensions while rejecting those of larger dimensions, these materials have commonly been known to be "molecular sieves" and are utilized in a variety of ways to take ad-vantage of the adsorptive properties of these compositions.
~hese molecular sieves include a wide variety of positive ion containing crystalline aluminosilicates, both natural and synthetic. These aluminosilicates can be described as a rigid three-dimensional network of SiO4 and ~104 in which the tetrahedra are cross linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electro-valence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example, an a~kaline metal or alkaline earth cation. Thus, a uni-valent positive sodium cation balances one negatively charged aluminosilicate tetrahedra where an alkaline earth metal cation is employed in the crystal structure of an aluminosilicate, it balances two negatively charged tetrahedra because of its doubly positive valence. One type of cation may be exchanged either entirely or partially by another type of cation utilizing ion exchange techniques in a conventional manner. sy means of such cation exchange, it has been possible to vary the size of the pores in a given aluminosilicate by suitable selection of the parti-ular cation. The spaces between the tetrahedra are occupied by moleeules of water prior to dehydration.
One such group of crystalline aluminosilicates designated as those of the ZSM-5 type, have been known and are particularly described in U.S. Patent number 3,702,886. The ZSM-5 type crystalline aluminosilicates have been prepared, for example, from a solution containing a tetraalkyl ammonium hydroxide, sodium oxide, an oxide of aluminum or gallium, an oxide of silicon or germanium and water and have been found to be characterized by a specific X-ray diffraction pattern.
The above crystalline aluminosilicates, as previously noted, have been characterized by the presence of aluminum and silicon, the total of such atoms to oxyaen being 1:2.
The amount of alumina present appears directly related to aeidity characteristics of the resulting product. A low alumina content has been recognized as being advantageous in obtaining a low degree of acidity which in many catalytic reactions is translated into low coke making properties and low aging rates.
In accordance with the present invention there is provided a famlly of crystalline silicates which are essentially free of Group IIIA metals ~Sargent-l~elch periodic table~, i.e.
, 9t~5 aluminum and/or gaLlium. These silicates have surprisingly been found to be characteriz~d by an X-ray diffraction pattern characteristic of the above-noted ZSM-5 type cry-stalline aluminosilicates. Thus, the novel synthetic crystalline silicate of this invention can be defined as that which possesses an X-ray diffraction pattern manifes-ting substantially the d-spacing set out in Table 1 below:
. .
.. .. .. . . ~
Interplanar spacing d(A) Relative Intensity _ __ _ _ 11.1 + 0.2 s 10.0 + 0.2 s 7.4 + 0.15 w 7.1 + 0.15 w 6.3 + 0.1 w 6.04 + 0.1 w 5.97 5.56 + 0.1 w 5.01 + 0.1 w 4.60 + 0.0~ w 4.25 + 0.08 w 3.85 + 0.07 vs 3.71 + 0.05 s 3.04 + 0.03 w
2.99 + 0.02 w 2.94 + 0.02 w .. _ . ~ .
These values were determined by standard techniques.
The radiation was the K-alpha doublet of copper and a Geiger Counter Spectrometer with a strip chart pen record-er was used. The peak heights, I, and the position as a function of two times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these r the
These values were determined by standard techniques.
The radiation was the K-alpha doublet of copper and a Geiger Counter Spectrometer with a strip chart pen record-er was used. The peak heights, I, and the position as a function of two times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these r the
3~ relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak and d(obs.), the interplanar spacing in A, corresponding to the recorded lines were calculated. In Table 1, the relative intensities are given in terms of the symbols s = strong, w = weak and vs =
very strong.
The crystalline silicate of the present invention can be used either in the alkali metal form, e.g. the sodium form, other desired metal form, the ammonium form or the hydrogen form. Preferably, one or both of the last two forms is employed. They can also be used in intimate com-bination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be per-formed. Such component can suitably be impregnated on or physically intimately admixed with the crystalline silicate.
The above silicates as synthesized or after impregnation can be beneficially converted to another form by thermal treatment. This can be done by heating to a temperature in the range of 200~ to 600C. in an atmosphere such as air, nitrogen, etc., and at atmospheric or subatmospheric pressures for b~etween 1 and 48 hours. Dehydration may also be performed at lower temperatures merely by placing the silicate in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The crystalline silicates of the invention can be suit-ably synthesized by preparing a solution containing (R4N~2O2 sodium oxide, a silica, an oxide of a metal other than a metal of Group IIIA and water and having a comp-osition in terms of mole ratios of oxides falling within the following ranges:
sroad Preferred OH/ SiO4 .01 - 5 .05 - 1.0 R4N/ (R4N+ + Na) .05 - 1.0 .1 - .5 H2O / O~ 50 - 100050 - 500 SiO2 / A12O3 >1 >3 wherein R is an alkyl radical, preferably between 2 and 5 carbon atoms and M is total metal. Thereafter, the mixture is maintained until crystals of the silicate are formed. Preferably, crystallization is performed under pressure in an autoclave or static bomb reactor. The temperature ranges from 100C~ to 200C.
generally, but at lower temperatures, e.g. about 100 C., crystallization time is longer. Thereafter, the crystals are separated from the liquid and recovered. Typical reaction conditions consist of heatino the foregoing reaction mixture to a temperature from about 100C. to 175C. for a period of time of from about 6 hours to 60 days. The more preferred temperature range is from about 100 C. to 175C. with the amount of time at a temperature in such range being from about 12 hours to 30 days.
The treatment of the amorphous mixture is carried out until crystals form. The resulting crystalline product is separated from the reaction medium, as by cooling to room temperature, filtering and water washing. The product so obtained is dried, e.g. at 230F., for about 8 to 24 hours. If desired, milder conditions may be employed, e.g. room temperature under vacuum.
The desired crystalline silicate can be prepared utilizing materials wh ch supply the appropriate ~ 5 --oxide. Such compositions include sodium silicate, colloidal silica, silica hydrosol, silica gel, silicic acid, sodium hydroxide, compounds of the desired metal, other than a metal of Group IIIA and tetraalkylammonium compounds, e.g.
tetrapropylammonium bromide. In addition to tetrapropyl-ammonium com~ounds, it is contemplated that tetramethyl, tetraethyl or tetrabutyl ammonium compounds may similarly be er~lpioy-ed. It will be understood that each oxide com-ponent utilized in the reaction mixture for preparing the crystalline silicates of this invention can be supplied by one or more initial reactants and they can be mixed together in any order. For example, sodium o~ide can be supplied by an aqueous solution of sodium hydroxide or by an aqueous solution of sodium silicate; tetrapropylammonium can be supplied in the form of its hydroxide as can the other tetraalkylammonium radicals noted hereinabove. The reaction mixture can be prepared either batchwise or continuously.
Crystal size and crystalliæation time of the crystalline metal silicate composition will vary with the nature of the reaction mixture employed.
m e crystalline silicates described herein are sub-stantially free of alumina, but may contain very minor amounts of such oxide attributable primarily to the presence of aluminum impurities in the reactants and/or equipment employed. Thus, the molar ratio of th~ alumina to silica will be in the range of O to less than 0.005 A1203 to more than 1 mole of SiO2 Generally, the latter may range from >1 SiO2 up to 500 or more.
The crystalline silicates as synthesi~ed can have any cations present replaced by a wide ~ariety of others accord-ing tc techniques ~iell known in the art. Typical replacing L9~75 components would include hydrogen, ammonium, alkyl ammonium and aryl ammonium and metals, other than metals of Group IIIA, including mixtures of the same. The hydrogen form may be prepared, for example, by substitution of original sodium with ammonium. The composition is then calcined at a temperature of, say, l,000F., causing evolution of ammonia and retention of hydrogen in the composition. Of the replacing metals, preference is accorded to metals of Groups II, IV and VIII of the Periodic TablP.
The crystalline silicates are then preferably washed with water and dried at a temperature ranging from 150F.
to about 600F. and thereafter calcined in air or other inert gas to temperatures ranging from 500F. to 1,500F.
for periods of time ranging from l to 48 hours or more.
Regardless of the synthesized form of the silicate, the spatial arrangement of atoms which form the basic crystal lattices remain essentially unchanged by the described replacement of sodium or other alkali metal or by the presence in the initial reaction mixture of metals in addition to sodium, as determined by an X-ray powder diffraction pattern of the resulting silicate. The X-ray diffraction of such products are essentially the same as those set forth in Table 1 above.
The crystalline silicates prepared in accordance with the instant invention are formed in a wide variety of particular sizes. Generally the particles can be in the form of powder, a granule or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh ITyler) screen and be maintained on a 400 mesh ITyler) screen in cases where the catalyst is molded such as by extrusion. The silicate can be ~xtruded before dxying or dried or partially dried and then extruded.
In the case of many catalysts, it is desired to in-corporate the new crystalline silicate with anotner material resistant to the temperatures and other conditions employed in organic processes. Such materials include active and inactive materials and synthetic and naturally occuring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occuring or in the form of gelatinous pre-cipitates or gels including mixtures of silica and metal oxides. Use of the material in conjunction with the new crystalline alumina silicate, i.e. combined therewith which is activç, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes.
Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that pro-ducts can be obtained economically and in an orderly manner without employing other means for controlling the rate of reaction. Normally, crystalline materials have been in-corporated into naturally occurring clays, e.g. bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These materials, i.e. clays, oxides etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in a petroleum refinery the catalyst is often subjected to rough handling which tends to break the catalyst down into powder like materials which cause problems in processing~ These clay binders have been employed for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the crystalline silicate described herein include the montmorillonite and kaolin family, which families include the sub-bentonites and the kaolins known commonly as nixie~ McNamee, Georgia and Florida or others in which the main constituent is halloysite, kaolinite, dickite, nacrite or anau~ite. Such clays can be used in the raw state as originally mined or initially subjected to calcinationt acid treatment or chemical modification.
In addition to the foregoing materials, the crystalline silicate may be composed with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a co-gel. The relative proportions of finally divided crystalline silicate and inorganic oxide gel matrix can vary widely with the crystalline silicate congent ranging from about 1 to 90 percent by weight and more usually in the range of about 2 to about 50 percent by weight of the composite.
Employing the catalyst of this invention, containing a hydrogenation component, heavy petroleum residual stocks, - cycle stocks, and other hydrocrackable charge stocks can be hydrocracked at temperatures between 400F. and 825F.
using molar ratios of hydrogen to hydrocarbon charge in the range of between 2 and 80. The pressure employed will vary between 10 and 2,500 psig and the liquid hourly space velo-city between 0.1 and 10.
Employing the catalyst of this invention for catalytic cracking/ hydrocarbon cracking stocks can be craoked at a liquid hourly space velocity between about 0.5 and 50, a temperature between about 550F. and 1100F, and a pressure between subatmospheric and several hundred atmospheres.
Employing a catalytically active form of silicate of this invention containing a hydrogenation component, reforming stocks can be reformed employing a temperature between 700~F.
and 1000F. The pressure can be between lQ0 and 1000 psig., but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0.1 and 10, pre-ferably between 0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20, preferably between
very strong.
The crystalline silicate of the present invention can be used either in the alkali metal form, e.g. the sodium form, other desired metal form, the ammonium form or the hydrogen form. Preferably, one or both of the last two forms is employed. They can also be used in intimate com-bination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be per-formed. Such component can suitably be impregnated on or physically intimately admixed with the crystalline silicate.
The above silicates as synthesized or after impregnation can be beneficially converted to another form by thermal treatment. This can be done by heating to a temperature in the range of 200~ to 600C. in an atmosphere such as air, nitrogen, etc., and at atmospheric or subatmospheric pressures for b~etween 1 and 48 hours. Dehydration may also be performed at lower temperatures merely by placing the silicate in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The crystalline silicates of the invention can be suit-ably synthesized by preparing a solution containing (R4N~2O2 sodium oxide, a silica, an oxide of a metal other than a metal of Group IIIA and water and having a comp-osition in terms of mole ratios of oxides falling within the following ranges:
sroad Preferred OH/ SiO4 .01 - 5 .05 - 1.0 R4N/ (R4N+ + Na) .05 - 1.0 .1 - .5 H2O / O~ 50 - 100050 - 500 SiO2 / A12O3 >1 >3 wherein R is an alkyl radical, preferably between 2 and 5 carbon atoms and M is total metal. Thereafter, the mixture is maintained until crystals of the silicate are formed. Preferably, crystallization is performed under pressure in an autoclave or static bomb reactor. The temperature ranges from 100C~ to 200C.
generally, but at lower temperatures, e.g. about 100 C., crystallization time is longer. Thereafter, the crystals are separated from the liquid and recovered. Typical reaction conditions consist of heatino the foregoing reaction mixture to a temperature from about 100C. to 175C. for a period of time of from about 6 hours to 60 days. The more preferred temperature range is from about 100 C. to 175C. with the amount of time at a temperature in such range being from about 12 hours to 30 days.
The treatment of the amorphous mixture is carried out until crystals form. The resulting crystalline product is separated from the reaction medium, as by cooling to room temperature, filtering and water washing. The product so obtained is dried, e.g. at 230F., for about 8 to 24 hours. If desired, milder conditions may be employed, e.g. room temperature under vacuum.
The desired crystalline silicate can be prepared utilizing materials wh ch supply the appropriate ~ 5 --oxide. Such compositions include sodium silicate, colloidal silica, silica hydrosol, silica gel, silicic acid, sodium hydroxide, compounds of the desired metal, other than a metal of Group IIIA and tetraalkylammonium compounds, e.g.
tetrapropylammonium bromide. In addition to tetrapropyl-ammonium com~ounds, it is contemplated that tetramethyl, tetraethyl or tetrabutyl ammonium compounds may similarly be er~lpioy-ed. It will be understood that each oxide com-ponent utilized in the reaction mixture for preparing the crystalline silicates of this invention can be supplied by one or more initial reactants and they can be mixed together in any order. For example, sodium o~ide can be supplied by an aqueous solution of sodium hydroxide or by an aqueous solution of sodium silicate; tetrapropylammonium can be supplied in the form of its hydroxide as can the other tetraalkylammonium radicals noted hereinabove. The reaction mixture can be prepared either batchwise or continuously.
Crystal size and crystalliæation time of the crystalline metal silicate composition will vary with the nature of the reaction mixture employed.
m e crystalline silicates described herein are sub-stantially free of alumina, but may contain very minor amounts of such oxide attributable primarily to the presence of aluminum impurities in the reactants and/or equipment employed. Thus, the molar ratio of th~ alumina to silica will be in the range of O to less than 0.005 A1203 to more than 1 mole of SiO2 Generally, the latter may range from >1 SiO2 up to 500 or more.
The crystalline silicates as synthesi~ed can have any cations present replaced by a wide ~ariety of others accord-ing tc techniques ~iell known in the art. Typical replacing L9~75 components would include hydrogen, ammonium, alkyl ammonium and aryl ammonium and metals, other than metals of Group IIIA, including mixtures of the same. The hydrogen form may be prepared, for example, by substitution of original sodium with ammonium. The composition is then calcined at a temperature of, say, l,000F., causing evolution of ammonia and retention of hydrogen in the composition. Of the replacing metals, preference is accorded to metals of Groups II, IV and VIII of the Periodic TablP.
The crystalline silicates are then preferably washed with water and dried at a temperature ranging from 150F.
to about 600F. and thereafter calcined in air or other inert gas to temperatures ranging from 500F. to 1,500F.
for periods of time ranging from l to 48 hours or more.
Regardless of the synthesized form of the silicate, the spatial arrangement of atoms which form the basic crystal lattices remain essentially unchanged by the described replacement of sodium or other alkali metal or by the presence in the initial reaction mixture of metals in addition to sodium, as determined by an X-ray powder diffraction pattern of the resulting silicate. The X-ray diffraction of such products are essentially the same as those set forth in Table 1 above.
The crystalline silicates prepared in accordance with the instant invention are formed in a wide variety of particular sizes. Generally the particles can be in the form of powder, a granule or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh ITyler) screen and be maintained on a 400 mesh ITyler) screen in cases where the catalyst is molded such as by extrusion. The silicate can be ~xtruded before dxying or dried or partially dried and then extruded.
In the case of many catalysts, it is desired to in-corporate the new crystalline silicate with anotner material resistant to the temperatures and other conditions employed in organic processes. Such materials include active and inactive materials and synthetic and naturally occuring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occuring or in the form of gelatinous pre-cipitates or gels including mixtures of silica and metal oxides. Use of the material in conjunction with the new crystalline alumina silicate, i.e. combined therewith which is activç, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes.
Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that pro-ducts can be obtained economically and in an orderly manner without employing other means for controlling the rate of reaction. Normally, crystalline materials have been in-corporated into naturally occurring clays, e.g. bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These materials, i.e. clays, oxides etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in a petroleum refinery the catalyst is often subjected to rough handling which tends to break the catalyst down into powder like materials which cause problems in processing~ These clay binders have been employed for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the crystalline silicate described herein include the montmorillonite and kaolin family, which families include the sub-bentonites and the kaolins known commonly as nixie~ McNamee, Georgia and Florida or others in which the main constituent is halloysite, kaolinite, dickite, nacrite or anau~ite. Such clays can be used in the raw state as originally mined or initially subjected to calcinationt acid treatment or chemical modification.
In addition to the foregoing materials, the crystalline silicate may be composed with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a co-gel. The relative proportions of finally divided crystalline silicate and inorganic oxide gel matrix can vary widely with the crystalline silicate congent ranging from about 1 to 90 percent by weight and more usually in the range of about 2 to about 50 percent by weight of the composite.
Employing the catalyst of this invention, containing a hydrogenation component, heavy petroleum residual stocks, - cycle stocks, and other hydrocrackable charge stocks can be hydrocracked at temperatures between 400F. and 825F.
using molar ratios of hydrogen to hydrocarbon charge in the range of between 2 and 80. The pressure employed will vary between 10 and 2,500 psig and the liquid hourly space velo-city between 0.1 and 10.
Employing the catalyst of this invention for catalytic cracking/ hydrocarbon cracking stocks can be craoked at a liquid hourly space velocity between about 0.5 and 50, a temperature between about 550F. and 1100F, and a pressure between subatmospheric and several hundred atmospheres.
Employing a catalytically active form of silicate of this invention containing a hydrogenation component, reforming stocks can be reformed employing a temperature between 700~F.
and 1000F. The pressure can be between lQ0 and 1000 psig., but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0.1 and 10, pre-ferably between 0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20, preferably between
4 and 12.
The catalyst can also be used for hydroisomerization of normal parafins when provided with a hydrogenation com-ponent, e.g. platinum. Hydroisomerization is carried out at a temperature between 200 and 700F., preferably 300 to 550F., with a li~luid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50 employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1. Additionally the catalyst can be used for olefin isomerization employing temperatures between 30F. and 500F.
In order to more fully illustrate the nature of the invention and the manner of practicing the same, the following examples are presented.
In examples which follow, whenever adsorption data are set forth, it was determined as follows:
A weighted sample of the material was contacted with the desired pure adsorbate vapor in an adsorption chamber at a pressure less than the vapor-liquid equilibrium pressure of the adsorbate at room temperature. This pressure was kept constant during the adsorption period which did not exceed about 8 hours. Adsorption was complete when a constant pressure in the adsorption chamber was reached, i.e. 12 mm. of mercury for water and 20 mm. of N-hexane and cyclohexane. The increasing weight was calculated as tne adsorption capacity of tl-le samlpie.
The alumina reported in some product analysis was present solely by virtue of having been a reagent impurity.
A crystalline silicate containing tin an~
sodium was synthesized from tetrapropyl ammonium bromide, colloidal silica, stannic chloride and sodium hydroxide.
A mixture ofl9.1 grams of colloidal silica ( 30 wt. %
SiO2), 15.6 grams of tetrapropylammonium bromide, 1.5 grams of NaOH, 1~0 gram of SnC14-5H2O and 100 grams of water was prepared. This mixture was placed in an auto-clave and maintained for 22 hours at 300F. and autogenous pressure. The product was removed, fil~ered, water washed and dried at 230F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table 1. The reaction composition and product analysis are shown below :
Reaction Composition Moles .
SiQ2 .095 ~(C3H8)4 N]2 .0294 H2O 6.3 Na2O .01875 SnO2 .0029 4 /R4N + Na .610 OE~- ~ SiO2 .395 H2O / OH- 168.3 SiO2 / ~l2/nO 4.38 where R is propyl and M is total metal.
Product Composition Weight percent ... _ .
A123 0.06 Na 3.1 SiO2 91 ( Approx.) Sn 6.1 .. .. _ _ . .. .
. .
A crystalline silicate containing sodium was produced from tetrapropylammonium bromide, colloidal silica and sodium hydroxide. A mixture of 19.1 grams of colloidal silica (30 wt.% SiO~), 15.6 grams tetra-propyl ammonium bromide, 1.0 gram NaOH and 100 grams of wa-ter w~s prepared. This mixture was placed in an auto-clave and maintained for 24 hours at 300F. and autogenous pressure. The product was removed,~filtered, water washed and dried at 230F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product anaylsis are 3~ shown below:
_ _ 9~5 _ .
Reaction Composition Moles ._ ..................................... . _ , Si2 .095 [(c3H8)4 N ]2 .0294 H2O 6.3 Na2O .0125 4 / R4N + Na .701 OH- /SiO 2 .263 H2O / OH 252.5 Product Composition Weight Percent 1 0 _ _ . _ _ . , 12O3 0.13 N 0.69 Na ~
sio2 9~ S
___ _ _~ _ __ . ~ . .. .
Adsorptlon Welght Percent _ _ .. _ . . __ .
Cyclohexene 2.4 ¦ Water 4.6 A crystalline silicate containing sodium was syn-thesized from sodium silicate, sodium hydroxide, sulfuric acid and tetrapropylammonium bromide. A mixture of 40 grams of sodium silicate "Q" brand (Na2O / SiO2 = 0.299 ), 31.2 grams or tetrapropylammonium bromide, 0.5 grams of NaOH, 4.6 grams H2SO4 and 200 grams of water was prepared. This mixture was maintained for 6 days at 212F. and atmospheric pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis established the product as being crystalline and having the l~Z~7S
X-ray diffraction pattern set forth in Table 1.
The reaction composition is shown below:
.
Reaction Composition Moles , ~ - --SiO2 .1896 ~(C3il8)4 N ]2 .0587 H2O 12.5 Na2O .0943 4 / R4N Na .884 OH / SiO2 .499 H2O / OH 137.1 . _ ,, _ . . _ After calcination for 16 hours at 1000F. in air, the product was used to effect selective separation of C8 aromatic isomers. As will be evident from the data shown in Table III, orthoxylene and m~taxylene are both very selectively excluded at 200C., while paraxylene and ethylbenzene are both sorbed.
TABLE III
2~ _ _ _ __ __ A. Pure Components Retention Time, Sec.
__ . __ . _ ._ _ __ .
Mesitylene 10 0 - xylene 11 m - xylene 11 p - xylene 394 Ethylbenzene 319 B. Cl - Aromatic Mixture Major SeparationNo Resolution Minor SeparationOX, MX/PX, EB
Number of Peaks 2 Resolution Excellent 3-~' Capacity ~ Q/g) 111 __ . . . . . _ .. . ~ _ ~xample 4 A erystalline silicate eontaining sodium was synthesized from sodium silicate, sulfurie acid, tetrapropylar~lonium bromide and water. A mixture of 80 grams Of sodium sili-cate ~ Na2O/SiO2= 0.299 ), 8 grams of sulfuric aeid, 60 grams of tetrapropylammonium bromide and 200 grams of water was prepared. This mixture was maintained at 212F. for 66 hours and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis established the produet as being ervstalline and having X-ray diffraetion pattern set forth in Table 1.
The reaetion eomposition and produet analysis are shown below:
Reaetion Composition Moles _ _ Si2 .379 [(C3H8)4 N] 2 .113 H2O 13.9 Na2O ~176 R4N / R4N + Na .391 OH- / SiO2 .498 H2O / OH 73.66 SiO2 2.15 Product Composition Wt. Pereent`
_ _ _ _ 23 0.18 N 0.78 Na 1.3 SiO 97 (approx.) ~.~ X1975 Example 5 A crystalline silicate containing sodium was synthesized from sodium silicate, sulfuric acid, sodium hydroxide, tetramethylammoniumchloride, tetrapropylammonium bromide and water. A mixture of 40 grams of sodium silicate Na2O / SiO2 = 0.299 ), 1.5 grams of sodium hydroxide, 3 grams of sulfuric acid, 6 grams of tetramethylammonium chloride, 6 grams of tetrapropylammonium bromide and 231 grams of water was prepared. This mixture was maintained for 113 hours at 320F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 25ûF. X-ray diffraction ànalysis showed the crystalline material to have the X-ray diffraction patterr.
set forth in Table 1.
The reaction composition is shown below:
. . ~
Reaction Compositlon Moles . _ . . _ __ . _ _ . .
SiO2 .1897 [(c3H8)4 N ]2 .0113 [(CH3)4 N ]2 .0274 H2O 14.2 Na2O .0755 R4N / R4N + Na 339 OH / SiO2 .~73 H2O / OH 138.1 SiO2 / M2/n o 2.313 . ~ _ . _ _ where R is propyl + methyl.
Example 6 A crystalline silicate containing sodium ~as synthesized 30 from sodium silicate, sodium hydroxide, sulfuric acid, tetrapropylammonium bromide and water. A mixture of 150 grams of sodium silicate ( Na2O / SiO2 = 0.299 ), . ~, 2 grams of sodium hydroxide, 18.4 grams of sulfuric acid, 124.8 grams of tetrapropylammonium bromide and 800 grams of water was prepared. This mixture was maintained for 40 hours at 212F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F.
X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction analysis set forth in Table 1.
The reaction composition and product analysis are shown below:
Reaction Composition Moles .... _ _ _ _ _ .
Si2 .759 [(c3H8)4 N ]2 .2347 H2O 50.02 I~a2O .2521 4 / 4 Na .482 OH / SiO2 .1696 H2O / OH- 383.7 _ _ _ 3.01 -----. . . . _. ~
Product Composition Weight Percent ._ .. _......... . .. _ _ .
23 0.202 Na 1.5 _. _ __ -- _ r . _ __ - _ _ ~
_ _ . . _ Example 7 A crystalline silicate containing zirconium and sodium was synthesized from colloidal silica, sodium hydroxide zirconium oxide (25% solution), tetrapropylammonium bromide and water. A mix~ure of 50 grams of colloidal silica (30 wt. % SiO2 ), 1 gram of sodium hydroxide, 25 grams of __ _ zirconium oxide ( 25~ solution), 20 grams of tetrapropyl-ammonium bromide and 50 grams of water was prepared. This mixture was maintained for 25 days at 300F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern in Table 1.
The reaction composition and product analysis are shown below:
Reaction Composition Moles _ _ . .. . .
SiO2 .2496 [( 3 8)4 N]2O .0376 H2O 5.76 Na2O .0125 Zr2 .0507 R4N / R4N + Na .750 H2O / OH 230.4 2 2/n 3.94 .~ .
_ . _ _ _ ___ _ . , Product Composition Weight Percent _ . _ _ _ _ __ _ _ . __ 2 3 <0.04 H 0.32 Na 0.24 Example 8 A crystalline silicate containing calcium and sodium was synthesized from colloidal silica, sodium hydroxide, calcium hydroxide, tetrapropylammonium bromide and water.
A mixture of 50 grams of colloidal silica ~ 30 wt. % of -- lS --ll~lg7~
SiO2 ), 1 gram of NaOH, 1 gram of Ca(OH)2, 20 grams of tetrapropylammonium bromide and 100 grams of water was prepared. The mixture was maintained for 16 days at 212F. and autogenous pressure.
The product was removed, filtered, water washed and dried at about 250F. X-ray analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
Reaction composition and product analysis are shown below:
. _ Reaction Composition Moles . . .. . . _ _ SiO2 .2496 [(C3H8)4 N]2O .0376 H2O 7.50 Na2O .0125 CaO .0135 R4N / R4N ~ Na .750 OH / SiO2 .100 SiO2 / M2/n _~
._ _ _ . _ _ _ .
Produ¢t Composition Weight Percent _ . ._ _ _ . _ . .. _ .
2 3 ~0.04 H 0.63 Na 0.66 SiO2 96 ( approx.
C2 2.9 ~ . . . _ _ .__ . .
Example 9 A crystalline silicate containing nickel and sodium was synthesized from colloidal silica, sodium hydroxide, nickel nitrate, tetrapropylammonium bromide and water.
A mixture of 50 grams of colloidal silica ( 30 ~t. ~ SiO21, 1.5 grams of NaOH, ~ grams of Ni (NO2) M 6H2O, 20 grams of tetrapropylammonium bromide and 60 grams of water was prepared. This mixture was maintained for 19 days at 212F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product analysis are shown below:
_ __ .__ _ .
Reaction Composition Moles . ._ __ .
SiO2 .2496 [(C3H8)~N]2O .0376 H2O 5.34 Na2O .0188 NiO .01376 4 / 4 Na .067 OH / SiO2 .150 H2O / OH 142.9 2 2/n 7.68 =_ _ _ = _ _ _ . . . _ . _ ._ .
Product CompositionWeight Percent _........ _. _ .. __ _ .. .
2 3 <0O04 H 0.15 Na 0.71 SiO2 92 (approx.) Ni 7-_ ~
Example 10 A crystalline silicate containing zinc and sodium was synthesized from colloidal silica, sodium hydroxide, zinc nitrate, tetrapropylammonium bromide and water. A mixture of 100 grams of colloidal silica, 4 grams NaOH, 4 grams ZN(N03)3 6~20, 25 grams of ~etrapropylammonium bromide and 100 grams of water was prepared. This mixture was maintained for 14 days at 212F. and autogenous pressure.
The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product analysis are shown below:
~ , Reaction Composition Moles SiO2 .4992 ( 3 8)4 ]2 .047 H20 9.53 Na2 03 ZnO .0059 4 / 4 Na .485 OH / SiO2 .200 H20 / OH 95.3 SiO2/ M2/nO 2.93 _ _ . . _ _ _ _ . . . _ . . . _ . Product Composition Weight Percent ___ _ _ A123 <0.04 H 0.69 SiO2 95 (approx.) ZnO 2.63 .. _ _ _. . _ .. _
The catalyst can also be used for hydroisomerization of normal parafins when provided with a hydrogenation com-ponent, e.g. platinum. Hydroisomerization is carried out at a temperature between 200 and 700F., preferably 300 to 550F., with a li~luid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50 employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1. Additionally the catalyst can be used for olefin isomerization employing temperatures between 30F. and 500F.
In order to more fully illustrate the nature of the invention and the manner of practicing the same, the following examples are presented.
In examples which follow, whenever adsorption data are set forth, it was determined as follows:
A weighted sample of the material was contacted with the desired pure adsorbate vapor in an adsorption chamber at a pressure less than the vapor-liquid equilibrium pressure of the adsorbate at room temperature. This pressure was kept constant during the adsorption period which did not exceed about 8 hours. Adsorption was complete when a constant pressure in the adsorption chamber was reached, i.e. 12 mm. of mercury for water and 20 mm. of N-hexane and cyclohexane. The increasing weight was calculated as tne adsorption capacity of tl-le samlpie.
The alumina reported in some product analysis was present solely by virtue of having been a reagent impurity.
A crystalline silicate containing tin an~
sodium was synthesized from tetrapropyl ammonium bromide, colloidal silica, stannic chloride and sodium hydroxide.
A mixture ofl9.1 grams of colloidal silica ( 30 wt. %
SiO2), 15.6 grams of tetrapropylammonium bromide, 1.5 grams of NaOH, 1~0 gram of SnC14-5H2O and 100 grams of water was prepared. This mixture was placed in an auto-clave and maintained for 22 hours at 300F. and autogenous pressure. The product was removed, fil~ered, water washed and dried at 230F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table 1. The reaction composition and product analysis are shown below :
Reaction Composition Moles .
SiQ2 .095 ~(C3H8)4 N]2 .0294 H2O 6.3 Na2O .01875 SnO2 .0029 4 /R4N + Na .610 OE~- ~ SiO2 .395 H2O / OH- 168.3 SiO2 / ~l2/nO 4.38 where R is propyl and M is total metal.
Product Composition Weight percent ... _ .
A123 0.06 Na 3.1 SiO2 91 ( Approx.) Sn 6.1 .. .. _ _ . .. .
. .
A crystalline silicate containing sodium was produced from tetrapropylammonium bromide, colloidal silica and sodium hydroxide. A mixture of 19.1 grams of colloidal silica (30 wt.% SiO~), 15.6 grams tetra-propyl ammonium bromide, 1.0 gram NaOH and 100 grams of wa-ter w~s prepared. This mixture was placed in an auto-clave and maintained for 24 hours at 300F. and autogenous pressure. The product was removed,~filtered, water washed and dried at 230F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product anaylsis are 3~ shown below:
_ _ 9~5 _ .
Reaction Composition Moles ._ ..................................... . _ , Si2 .095 [(c3H8)4 N ]2 .0294 H2O 6.3 Na2O .0125 4 / R4N + Na .701 OH- /SiO 2 .263 H2O / OH 252.5 Product Composition Weight Percent 1 0 _ _ . _ _ . , 12O3 0.13 N 0.69 Na ~
sio2 9~ S
___ _ _~ _ __ . ~ . .. .
Adsorptlon Welght Percent _ _ .. _ . . __ .
Cyclohexene 2.4 ¦ Water 4.6 A crystalline silicate containing sodium was syn-thesized from sodium silicate, sodium hydroxide, sulfuric acid and tetrapropylammonium bromide. A mixture of 40 grams of sodium silicate "Q" brand (Na2O / SiO2 = 0.299 ), 31.2 grams or tetrapropylammonium bromide, 0.5 grams of NaOH, 4.6 grams H2SO4 and 200 grams of water was prepared. This mixture was maintained for 6 days at 212F. and atmospheric pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis established the product as being crystalline and having the l~Z~7S
X-ray diffraction pattern set forth in Table 1.
The reaction composition is shown below:
.
Reaction Composition Moles , ~ - --SiO2 .1896 ~(C3il8)4 N ]2 .0587 H2O 12.5 Na2O .0943 4 / R4N Na .884 OH / SiO2 .499 H2O / OH 137.1 . _ ,, _ . . _ After calcination for 16 hours at 1000F. in air, the product was used to effect selective separation of C8 aromatic isomers. As will be evident from the data shown in Table III, orthoxylene and m~taxylene are both very selectively excluded at 200C., while paraxylene and ethylbenzene are both sorbed.
TABLE III
2~ _ _ _ __ __ A. Pure Components Retention Time, Sec.
__ . __ . _ ._ _ __ .
Mesitylene 10 0 - xylene 11 m - xylene 11 p - xylene 394 Ethylbenzene 319 B. Cl - Aromatic Mixture Major SeparationNo Resolution Minor SeparationOX, MX/PX, EB
Number of Peaks 2 Resolution Excellent 3-~' Capacity ~ Q/g) 111 __ . . . . . _ .. . ~ _ ~xample 4 A erystalline silicate eontaining sodium was synthesized from sodium silicate, sulfurie acid, tetrapropylar~lonium bromide and water. A mixture of 80 grams Of sodium sili-cate ~ Na2O/SiO2= 0.299 ), 8 grams of sulfuric aeid, 60 grams of tetrapropylammonium bromide and 200 grams of water was prepared. This mixture was maintained at 212F. for 66 hours and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis established the produet as being ervstalline and having X-ray diffraetion pattern set forth in Table 1.
The reaetion eomposition and produet analysis are shown below:
Reaetion Composition Moles _ _ Si2 .379 [(C3H8)4 N] 2 .113 H2O 13.9 Na2O ~176 R4N / R4N + Na .391 OH- / SiO2 .498 H2O / OH 73.66 SiO2 2.15 Product Composition Wt. Pereent`
_ _ _ _ 23 0.18 N 0.78 Na 1.3 SiO 97 (approx.) ~.~ X1975 Example 5 A crystalline silicate containing sodium was synthesized from sodium silicate, sulfuric acid, sodium hydroxide, tetramethylammoniumchloride, tetrapropylammonium bromide and water. A mixture of 40 grams of sodium silicate Na2O / SiO2 = 0.299 ), 1.5 grams of sodium hydroxide, 3 grams of sulfuric acid, 6 grams of tetramethylammonium chloride, 6 grams of tetrapropylammonium bromide and 231 grams of water was prepared. This mixture was maintained for 113 hours at 320F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 25ûF. X-ray diffraction ànalysis showed the crystalline material to have the X-ray diffraction patterr.
set forth in Table 1.
The reaction composition is shown below:
. . ~
Reaction Compositlon Moles . _ . . _ __ . _ _ . .
SiO2 .1897 [(c3H8)4 N ]2 .0113 [(CH3)4 N ]2 .0274 H2O 14.2 Na2O .0755 R4N / R4N + Na 339 OH / SiO2 .~73 H2O / OH 138.1 SiO2 / M2/n o 2.313 . ~ _ . _ _ where R is propyl + methyl.
Example 6 A crystalline silicate containing sodium ~as synthesized 30 from sodium silicate, sodium hydroxide, sulfuric acid, tetrapropylammonium bromide and water. A mixture of 150 grams of sodium silicate ( Na2O / SiO2 = 0.299 ), . ~, 2 grams of sodium hydroxide, 18.4 grams of sulfuric acid, 124.8 grams of tetrapropylammonium bromide and 800 grams of water was prepared. This mixture was maintained for 40 hours at 212F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F.
X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction analysis set forth in Table 1.
The reaction composition and product analysis are shown below:
Reaction Composition Moles .... _ _ _ _ _ .
Si2 .759 [(c3H8)4 N ]2 .2347 H2O 50.02 I~a2O .2521 4 / 4 Na .482 OH / SiO2 .1696 H2O / OH- 383.7 _ _ _ 3.01 -----. . . . _. ~
Product Composition Weight Percent ._ .. _......... . .. _ _ .
23 0.202 Na 1.5 _. _ __ -- _ r . _ __ - _ _ ~
_ _ . . _ Example 7 A crystalline silicate containing zirconium and sodium was synthesized from colloidal silica, sodium hydroxide zirconium oxide (25% solution), tetrapropylammonium bromide and water. A mix~ure of 50 grams of colloidal silica (30 wt. % SiO2 ), 1 gram of sodium hydroxide, 25 grams of __ _ zirconium oxide ( 25~ solution), 20 grams of tetrapropyl-ammonium bromide and 50 grams of water was prepared. This mixture was maintained for 25 days at 300F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern in Table 1.
The reaction composition and product analysis are shown below:
Reaction Composition Moles _ _ . .. . .
SiO2 .2496 [( 3 8)4 N]2O .0376 H2O 5.76 Na2O .0125 Zr2 .0507 R4N / R4N + Na .750 H2O / OH 230.4 2 2/n 3.94 .~ .
_ . _ _ _ ___ _ . , Product Composition Weight Percent _ . _ _ _ _ __ _ _ . __ 2 3 <0.04 H 0.32 Na 0.24 Example 8 A crystalline silicate containing calcium and sodium was synthesized from colloidal silica, sodium hydroxide, calcium hydroxide, tetrapropylammonium bromide and water.
A mixture of 50 grams of colloidal silica ~ 30 wt. % of -- lS --ll~lg7~
SiO2 ), 1 gram of NaOH, 1 gram of Ca(OH)2, 20 grams of tetrapropylammonium bromide and 100 grams of water was prepared. The mixture was maintained for 16 days at 212F. and autogenous pressure.
The product was removed, filtered, water washed and dried at about 250F. X-ray analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
Reaction composition and product analysis are shown below:
. _ Reaction Composition Moles . . .. . . _ _ SiO2 .2496 [(C3H8)4 N]2O .0376 H2O 7.50 Na2O .0125 CaO .0135 R4N / R4N ~ Na .750 OH / SiO2 .100 SiO2 / M2/n _~
._ _ _ . _ _ _ .
Produ¢t Composition Weight Percent _ . ._ _ _ . _ . .. _ .
2 3 ~0.04 H 0.63 Na 0.66 SiO2 96 ( approx.
C2 2.9 ~ . . . _ _ .__ . .
Example 9 A crystalline silicate containing nickel and sodium was synthesized from colloidal silica, sodium hydroxide, nickel nitrate, tetrapropylammonium bromide and water.
A mixture of 50 grams of colloidal silica ( 30 ~t. ~ SiO21, 1.5 grams of NaOH, ~ grams of Ni (NO2) M 6H2O, 20 grams of tetrapropylammonium bromide and 60 grams of water was prepared. This mixture was maintained for 19 days at 212F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product analysis are shown below:
_ __ .__ _ .
Reaction Composition Moles . ._ __ .
SiO2 .2496 [(C3H8)~N]2O .0376 H2O 5.34 Na2O .0188 NiO .01376 4 / 4 Na .067 OH / SiO2 .150 H2O / OH 142.9 2 2/n 7.68 =_ _ _ = _ _ _ . . . _ . _ ._ .
Product CompositionWeight Percent _........ _. _ .. __ _ .. .
2 3 <0O04 H 0.15 Na 0.71 SiO2 92 (approx.) Ni 7-_ ~
Example 10 A crystalline silicate containing zinc and sodium was synthesized from colloidal silica, sodium hydroxide, zinc nitrate, tetrapropylammonium bromide and water. A mixture of 100 grams of colloidal silica, 4 grams NaOH, 4 grams ZN(N03)3 6~20, 25 grams of ~etrapropylammonium bromide and 100 grams of water was prepared. This mixture was maintained for 14 days at 212F. and autogenous pressure.
The product was removed, filtered, water washed and dried at about 250F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table 1.
The reaction composition and product analysis are shown below:
~ , Reaction Composition Moles SiO2 .4992 ( 3 8)4 ]2 .047 H20 9.53 Na2 03 ZnO .0059 4 / 4 Na .485 OH / SiO2 .200 H20 / OH 95.3 SiO2/ M2/nO 2.93 _ _ . . _ _ _ _ . . . _ . . . _ . Product Composition Weight Percent ___ _ _ A123 <0.04 H 0.69 SiO2 95 (approx.) ZnO 2.63 .. _ _ _. . _ .. _
Claims (2)
1. A synthetic crystalline silicate composition which is essentially free of Group IIIA metals and which possesses an X-ray diffraction pattern manifesting substantially the d-spacing set out in Table I below:
2. A composition according to claim 1 which possesses base exchange capacity to the extent that it contains alumina present as an impurity in one or more of the components from which it was synthesized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000297955A CA1121975A (en) | 1978-03-01 | 1978-03-01 | Crystalline silicates and method of preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000297955A CA1121975A (en) | 1978-03-01 | 1978-03-01 | Crystalline silicates and method of preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121975A true CA1121975A (en) | 1982-04-20 |
Family
ID=4110889
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000297955A Expired CA1121975A (en) | 1978-03-01 | 1978-03-01 | Crystalline silicates and method of preparing the same |
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| Country | Link |
|---|---|
| CA (1) | CA1121975A (en) |
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|---|---|---|---|---|
| CN111298744A (en) * | 2019-11-15 | 2020-06-19 | 江苏隆昌化工有限公司 | Preparation method of active agent for improving aromatic hydrocarbon nitration efficiency |
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Cited By (2)
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| CN111298744A (en) * | 2019-11-15 | 2020-06-19 | 江苏隆昌化工有限公司 | Preparation method of active agent for improving aromatic hydrocarbon nitration efficiency |
| CN111298744B (en) * | 2019-11-15 | 2021-12-14 | 江苏隆昌化工有限公司 | Preparation method of active agent for improving aromatic hydrocarbon nitration efficiency |
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