CA1127134A - Crystalline zeolite composition - Google Patents
Crystalline zeolite compositionInfo
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Abstract
CRYSTALLINE ZEOLITE COMPOSITION
ABSTRACT OF THE DISCLOSURE
The invention provides a crystalline aluminosilicate zeolite composition related to the family of ZSM-5 zeolites.
The zeolite contains a metal selected from the rare earth metals, chromium, vanadium, molybdenum, indium, boron, mercury, tellurium, silver and one of the platinum group metals. The invention also provides a process for converting an organic charge with the zeolite and a method for preparing it.
ABSTRACT OF THE DISCLOSURE
The invention provides a crystalline aluminosilicate zeolite composition related to the family of ZSM-5 zeolites.
The zeolite contains a metal selected from the rare earth metals, chromium, vanadium, molybdenum, indium, boron, mercury, tellurium, silver and one of the platinum group metals. The invention also provides a process for converting an organic charge with the zeolite and a method for preparing it.
Description
~1~7134 BACK~RO~ D OF T~E I~JEN~IO~I
~ield of the~lnvention The invention relates to crystalline aluminosilicate zeolite composltions. More parti~ularly, it relates to crystal-line zeolites that are crystallized in the presence of certain metals or metal compounds. It relates further to hydrocarbon conversion with such catalysts.
Description of the Prior Art Zeolitlc materials, both natural and synthetic, have been demonstrated in the past to have catalytic capabillties for various types of hydrocarbon conversion. Certain zeolitic - materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure within which there are a large number of small ca~ities which are interconnected by a number of still smaller channels. These cavities and channels are pre-cisely uniform in size. Since the dimensions o~ these pores are such as to accept for adsorption molecules of certain dimensions, while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
Such molecular sieves lnclude a wide variety of posi-tlve ion-contalnlng crystalline aluminosilicates~ both natural and synthetlc. These alumlnosilicates can be described as a rlgid three-dimenslonal network of SiO4 and A104 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 electrovalence of the tetrahedra-containing
~ield of the~lnvention The invention relates to crystalline aluminosilicate zeolite composltions. More parti~ularly, it relates to crystal-line zeolites that are crystallized in the presence of certain metals or metal compounds. It relates further to hydrocarbon conversion with such catalysts.
Description of the Prior Art Zeolitlc materials, both natural and synthetic, have been demonstrated in the past to have catalytic capabillties for various types of hydrocarbon conversion. Certain zeolitic - materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure within which there are a large number of small ca~ities which are interconnected by a number of still smaller channels. These cavities and channels are pre-cisely uniform in size. Since the dimensions o~ these pores are such as to accept for adsorption molecules of certain dimensions, while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
Such molecular sieves lnclude a wide variety of posi-tlve ion-contalnlng crystalline aluminosilicates~ both natural and synthetlc. These alumlnosilicates can be described as a rlgid three-dimenslonal network of SiO4 and A104 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 electrovalence of the tetrahedra-containing
- 2 -' ~
aluminum is balanced by the inclusion in the crystal of a cation, for e~ample, an alkali metal or an alkaline earth metal cation. This can be expressed by lormula ~herein the ratio o~ Al to the number of the various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of catlon has been exchanged elther ln entirety or partially by another type of cation utilizin~ ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the size of the pores in the given aluminosilicate by suitable selection of the particular cation.
` The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
U.S. 3,941,871 discloses and claims a crystalllne metal organosilicate ha~ing a high silica-to-alumina ratio and contalnlng, in additlon to sodium, calcium1 nlckel or zinc.
Other prior art techniques have resulted in the ~ormation of a great ~ariety of synthetic crystalline alumino-silicates. These aluminosilicates have come to be designated by letter or other con~enient symbol, as lllustrated by zeolite A (U.S. 2,882,243), zeolite X (U.S. 2,882,244), zeolite ZSM-5 (U.S, 3,702,886), zeolite ZSM-ll (U.S~ 3,709,979), ZSM~12 ~U.S. 3,832,449) and zeolite ZSM-35 ~U.S. 4,016,245), merely to name a ~ew.
SUMMARY OF T~E INVENTION
The pre9ent inventlon relates to stable synthetic crystalline aluminosilicate æeolite compositions, toa m~hod for t he ir preparation and to hydrocarbon con~ersion processes conducted therewith. These composltions, as synthesized, have .
~ ::
aluminum is balanced by the inclusion in the crystal of a cation, for e~ample, an alkali metal or an alkaline earth metal cation. This can be expressed by lormula ~herein the ratio o~ Al to the number of the various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of catlon has been exchanged elther ln entirety or partially by another type of cation utilizin~ ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the size of the pores in the given aluminosilicate by suitable selection of the particular cation.
` The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
U.S. 3,941,871 discloses and claims a crystalllne metal organosilicate ha~ing a high silica-to-alumina ratio and contalnlng, in additlon to sodium, calcium1 nlckel or zinc.
Other prior art techniques have resulted in the ~ormation of a great ~ariety of synthetic crystalline alumino-silicates. These aluminosilicates have come to be designated by letter or other con~enient symbol, as lllustrated by zeolite A (U.S. 2,882,243), zeolite X (U.S. 2,882,244), zeolite ZSM-5 (U.S, 3,702,886), zeolite ZSM-ll (U.S~ 3,709,979), ZSM~12 ~U.S. 3,832,449) and zeolite ZSM-35 ~U.S. 4,016,245), merely to name a ~ew.
SUMMARY OF T~E INVENTION
The pre9ent inventlon relates to stable synthetic crystalline aluminosilicate æeolite compositions, toa m~hod for t he ir preparation and to hydrocarbon con~ersion processes conducted therewith. These composltions, as synthesized, have .
~ ::
3~
a definite x-ray diffraction pattern, characteristic of the ZSM-5 zeolites and shows the significant lines set forth in Table 1.
Interplanar spacing d(A~: Relevant Intensitx 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
a definite x-ray diffraction pattern, characteristic of the ZSM-5 zeolites and shows the significant lines set forth in Table 1.
Interplanar spacing d(A~: Relevant Intensitx 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 + 0.08 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 technique~.
The radlatlon was the K-alpha doublet of copper, and a sclntilla-tlon counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from X
.
1127i;~4 the spectrometer chart. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d (obs.l, 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. It should be understood that this X-ray diffraction pattern is characteristic of all the species of the present compositions. Ion exchange of the sodium ion with cations reveals substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample and the extent of thermal conditioning.
The anhydrous composition can also be identified, in terms of mole ratios of oxides, as follows:
2 ~W : ~A120~ X : ~sio2Jy : ~M" 0 2 n wherein W~X is from ~0.5 to <3, Y/X is ~20 and Z/X is from >zero to ~ ~ 100, R is a nitrogen containing cation. R may include primary amines containing 2 to 10 carbon atoms and ammonium cations, preferably the tetraalkylammonium cation in which the alkyl contains from 2 to 5 carbon atoms, M' is a metal from Group IA of the Periodic Table, ammonium, hydrogen or mixtures thereof, and n is the valence of M' or M". With respect to M", the pre-ferred metals are those selected from the rare earth metals, (i.e.
metals having atomic numbers from 57 to 71), chromium, vanadium, molybdenum, indium, boron, mercury, tellurium, silver and one of the platinum group metals, which latter group includes platinum, palladium and ruthenium.
It is not known whether the M" is present as a metal or as a metal compound. The above formula will be understood to take into account the presence in any of the M" various states and also to allow for varying amounts thereof. For example, if it is present in the occluded state, then its concentration relative to aluminum in the zeolite as synthe-sized can range up to but less than about 100.
DESCRIPTION OF SPECIFIC EMBODIMEMTS
A reaction mixture containing sources of the tetra-propylammonium cation tas from the hydroxide), sodium oxide, silica, water, and sources of, for example, indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, mercury, tellurium, silver, palladium, molybdenum and, optionally, alumina, will yield a ZSM-5 zeolite, but having unexpectedly improved properties. The content of indium, boron, etc. listed above can range in the final product from about 0.005~ by weight to 5.0% by weight.
The crystalline aluminosilicates prepared by the ~ method of the present invention have high thermal stability and `~ ~ 20 exhibit superior catalytic performance.
~ The original alkali metal can be replaced, at least in :
part, in accordance with techniques well-known in the art by lon exchange wlth other cations. Pre~erred replaciny cations include metal ions, ammonium ions, hydrogen ions, and mixtures of the same. Particularly preferred cations are those which render the zeolite catalytically active, especially for hydrocarbon conversion. These ir,clude hydrogen, metals of Group II and VIII of the Periodic Table and manganese.
~' ~lZ7~,34 In a preferred embodiment of the zeolite, the silica/alumina mole ratio is yreater than 35 and ranges up to about 3000.
The present zeolites have a high degree of thermal stability thereby rendering them particularly effective for use in processes involving elevated temperatures.
The composit~on can be prepared utilizing materials which supply the appropriate components of the zeolite. Such components include, for an aluminosilicate, sodium aluminate, alumina, sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide and a tetrapropylammonium compound, e.g.
tetrapropylammonium hydroxide. It will be understood that each component utilized in the reaction mixture for preparing the zeolite can be supplied by one or more initial reactants and they can be mixed together in any order. For example, sodium can be supplied by an aqueous solution of sodium hydroxide, or by an aqueous solution of sodium silicate; tetrapropylammonium cation can be supplied by the bromide salt. The reaction mix-~ture can be prepared either batchwise or continuously. Crystal ^~ 20 size and crystallization time of the composition will vary with the nature of the reaction mixture employed. It will be further understood that in the very high silica-to-alumina ratios, which , ~
can ln this invention preferably range from greater than 35 to about 3000 or more, and more preferably about 70 to about 500, 1t may not be necessary to add a source of alumlna to the reaction mixture since residual amounts in other reactants may suffice.
, The zeolite can be prepared from a reaction mixture having a composition, in terms of mole ratios of oxides or in ~ of total moles of oxides, falling within the fcllowing ranges:
llZ7134 ~ABLE 2 ~ost Broad Preferred Preferred OH-~SiO2 0.07-1.0 0.1-0,8 0.2-0.75 R4N ~R4N~ + Na+l 0.2-0.95 0.3-0.9 0.4-0.9 H20~0E 10-300 10-300 10-300 sio2/A123 50-3000 70-1000 70-500 Other metal (% of total oxides) lx10 -1-0 lx10 -0.1 lx10-5-0 01 R is as deflned hereinabove in the Summary.
.
Typlcal reaction conditions consist of heating the foregoing reaction mixture to a temperature of from about 95C
to 175C for a period of tlme of from about six hours to 120 days.
A more preferred temperature range is from about 100C to 175C
~: wlth the amount of time at a temperature in such range being from about 12 hours to 8 days.
` ~ The digestion of the gel particles is carried out -~ untll crystals form. The solid product is separated from the 2~ reaction medium, as by cooling the whole to room temperature~
filtering and water washing.
The ~oregoing product ls dried, e,g~ at 230F, for ~,, from about 8 to 24 hours. Of course, milder conditions may be `~ employed i~ deslred, e.g room temperature under vacuum.
:
2~ The zeolite can have the alkali metal associated therewith replaced by a wide variety of other cations according ; to technlques well-known in the art. Typical replaclng cations would lnclude hydrogen, ammonium and metal cations includlng - mixtures of the same. Of the replacing metallic cations, par-ticular preference is given to cation of metals such as rare earth metal, manganese and calcium, a~ well as metals of Groups II and VIII of the Periodic Table, e~g,~ zinc or platinum, _ 8 -~i27~34 Typical ion exchange techniques include contacting the zeolite with a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
Representative ion exchange techniques are disclosed in a wide variety of patents including United States 3,140,249;
United States 3,140,251; and United States 3,140,253.
Following contact with the salt solution of the desired replacing cations, the zeolites are then preferably washed wlth water and dried at a temperature ranging from 150F
to about 600F and thereafter calcined in air or other inert gas at temperatures ranging from about 500F to 1500F for periods of time ranging from 1 minute to ~8 hours or more.
Regardless of the cations replacing the sodium in its synthesized form, the spatial arrangement of the aluminum, silicon and oxygen atoms which form the basic crystal lattices of the zeolite remains essentially unchanged by the described .~:
replacement of sodium or other alkali metal as determined by taking an X-ray powder diffraction pattern of the ion-exchanged materials. Such X-ray diffraction pattern of the ion-exchanged -~ product reveals a pattern substantially the same as that set forth in Table 1 above.
The aluminosilicates prepared by the instant invention are formed in a wide variety of particular sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size - sufficient to pass through a 2 mesh (Tyler) screen and be ;
retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the aluminosilicate can be extruded before drying or dried or partially dried and then extruded.
~127~34 As in the case of many catalysts, it is desired to incorporate the zeolites with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter ~ay be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of an active material in conjuctiDn with the present composition, i.~., combined therewith, 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 products can be obtained economically ~nd in orderly manner without employing other means for controlling the rate or reaction. Normally, zeolite materials have been incorporated 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 which can be composited with the catalyst include the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite ~12~134 kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined, or they can be initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the catalyst can be composited with a porous matrix material such as silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, 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 cogel.
The relative proportions of finely divided crystalline alumino-silicate and inorganic oxide gel matrix vary widely, with the crystalline aluminosilicate content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 50 percent by weight of the composite.
While the catalyst is useful in cracking and hydro-cracking, it is outstandingly useful in other petroleum refining processes, indicating again the unique catalytic characteristics of these zeolites. The latter processes include isomerization of n-paraffins and naphthenes, polymerization o~ compounds con-talning an olefinic or acetylenic carbon-to-carbon linkage such as isobutylene and butene-l, reformlng, alkylation, isomerlzation `, of polyalkyl substituted aromatics, e.g. ortho-xylene, and disproportionation of aromatics, such as toluene, to provide a mixture of benzene, xylenes and higher methylbenzenes. The catalysts have exceptional high selectivity and, under the conditions of hydrocarbon conversion, provide a high percentage of desired products relative to total products compared with known zeolite hydrocarbon conversion catalysts.
AS indicated above, the zeolite is also useful in other catalytic processes, such as catalytic cracking of hydrocarbons and hydrocrac~ing. In addition to the thermal stability of this family of zeolites under these conditions, they provide conversion of the cracked oil to materials having lower molecular weights and boiling points, which are of greater economic value. The ability to be physically stable under high temperatures and/or in the presence of high tempera-ture steam is extremely important for a cracking catalyst.During catalytic conversion, the reaction which takes place is essentially a cracking to produce hydrocarbons. However, this cracking is accompanied by a number of complex side reactions such as aromatization, polymerization, alkylation and the li~e.
As a result of these complex reactions, a carbonaceous deposit is laid down on the catalyst which is referred to by petroleum engineers as "coke". The deposit of coke on the catalyst tends to seriously impair the catalyst efficiency for the principal reaction desired and to substantially decrease the rate of conversion and/or the selectivity of the process. Thus, lt is common to remove the catalyst after coke has been deposited thereon and to regenerate it by burning the coke in a stream of oxidizing gas. The regenerated catalyst is returned to the converslon stage of the process cycle. The thermal ~tabllity of the 2eolite is advantageous in this re~ard.
~ he products can be used either in the alkali metal form, e.g., the sodium form, in the ammonium form, the hydrogen form, or another univalent or multivalent cationic form.
Preferably, one or the other of the last two forms is employed.
They can also be used in intimate combination with a hydro-genating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation dehydrogena-tion functlon is to be performed. Suah component can be exchanged 7~34 into the composition, impregnat~d therein or physically intim-ately admiYed therewith. Such component can be impregnated in or onto the zeolite, such as, for example, by, in the case of platinum, treating the zeolite with a platinum metal-containing ion. Thus, suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum ammine complex.
The compounds of the useful platinum or other metals can be divided into compounds in which the metal is present in the cation of the compound and compounds in which it is present in the anion of the compound. Both types of compounds which contain the metal in the ionic state can be used. A solution in which platinum metals are in the form of a cation or cationic complex, e.g. Pt(NH3)6C14 is particularly useful. For some hydrocarbon conversion processes, this noble metal form of the catalyst is unnecessary such as in low temperature, liquid phase ortho-xylene isomerization.
When it is employed either as an adsorbent or as a catalyst in one of the aforementioned processes, the catalyst should be at least partially dehydrated. 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 between 1 minute and 48 hours~
Dehydration can also be performed at lower temperautres merely by placing the catalyst in a vacuum, but a lon~er time is required to obtain a sufficient amount of dehydration.
The following examples will illustrate the invention~
'~r ;.r ~127~34 E~AMPLE 1 Solution 1 Q Brand Silicate240 gms Distilled ~20 300 Solution 2 Distilled H20~10 gms Tetrapropyl Ammonlum Bromide 30 ~; Conc. H2S04 20 CrK(S04)2~l2H2012,25 Q Brand ls a Phlladelphia Quartz Co. commercial brand of sodium sllicate. Typlcal Analysis: 8.9% Na20, 28.7 S102, 62.4% H20.
Solutlon 1 was placed into a 4-neck 2 1. flask wlth overhead stirrer. Solution 2 was added wlth stirring. The solutlon became very gelatlnous, A small amount of X-ZSM-5 (about O.lg) was added for seeding. Heating was begun and the solutlon was allowed to heat to about 205F~ The variac ; ~ setting was the only control on the temperature so it varied 20 ~ + 3C depending on voltage variations during the day. After a few days, the solutlon lost lts gelatinous character and became more ohalX-like. Crystallization~ as determined by X-ray, took 5-6 days. The catalyst was flltered and washed with about 4 llters of distilled H20. The yield was 60-70 gms of catalyst.
The catalyst was dried at 70C and calcined in a crucible in a muffle furnace at 75 to 1000F for 12 hours.
The catalyst was placed in a 200 ml flask with 100 cc f H20 and 10 gm of NH4N03 and refluxed at 100C for 1 hour, The catalyst was filtered, washed and NX4~03 e~changed reoeatedly for 5 hours. The catalyst was again filtered, washed and , exchanged re~eatedly for about' 16 hours. ~he catalyst was ~_l'erec, -~as'r.ed thoroughly and drie~ -~ 70C ~or ebou~ ~
hours. The catalyst was calcined again in a muffle furnace at 75 to 1000F for 6 hours.
X-ray powder diffraction patterns of the crystalline product, both in the as-synthesized form and after the treat-ments descrlbed a bove, are given in Table 3~
While this Example illustrates the use of the ammonium cation, other cations such as alkyl ammonium, metals and hydrogen may be used.
As set forth in Table 3, minor differences are observed between the X-ray diffraction patterns of the as-synthe-sized zeolite and the same zeolite after ion exchange and thermal treatments. These differences are changes from singlets to doublets and other doublets to singlets between the two patterns resulting ~rom mlnor shiPts in interplanar spacings and varla-tlons in relatlve lntensities. These observed differences reflect minor variations ln lattice parameters and crystal symmetry.
~127134 ~ABLE 3 ~s Syn~hesize~ ~inished O~t21 ~st 2~ d(A)I/I(0) 2e d(A) I/I(0) 7.89 11.20 367 ' 85 11.26 100 8 78 10.07 26 8.75 10.11 59 9 01 9.81 9 9.05 9.77 14 9.84 8.9g 3 9.80 -9.02 10.98 8. o6 1 10.95 8.08 11.88 7.45 11 11.85 7.47 12.49 7.09 5 12.50 7.08 13.15 6.73 6 13.17 6.72 8 13.89 6.38 14 13.88 6.38 11 14.60 6.07 9~
! 14.72 6.02 17 14.79 5 - 99 10 ~ 14.90 5.95 2 15.48 5.72 9 15.50 5.72 8 15.89 5.58 11 15.85 5.59 11 16.46 5.39 3 16.50 5.37 3 17.25 5.14 ~ 17.23 5.15 2 17.65 5.02 2 17.60 5,04 4 17.75 5~00 4 17.76 4.99 5 18.13 4.89 - 18.80 4.72 19.25 4.61 9 19.21 4.62 4 19.90 4.46 3 19.85 4.47 20.35 4.36 11 20.32 4.37 6 20.85 4.26 12 20.82 4.27 8 21.75 4.09 2 21.75 4.09 3 22.19 4.01 8 22.16 4.01 4 23.15 3.84 100 23.13 3.85 65 23.25 3.83 28 23.67 3.76 24 23.63 3.76 16 23.~2 3.72 45 23,90 3.72 30 ~-24.30 3.66 8 24.38 3.65 30 ~ 24.52 3.63 8 ;~ ~ 24 75 3.60 2 25 55 3.49 4 25.50 3.49 3 25.90 3.44 12 25.84 3,45 5 26.35 3.38 2 26.15 3.41 2 26 68 3.34 7 26.53 3.36 5 26 95 3.31 9 26.92 3.31 7 ~27.38 3.26 3 27 - 45 3.25 3 ~7.63 3.23 28.05 3.18 2 28.13 3.17 28.45 3 - 14 3~28 40 3; 146 13 29.25 3.05 11~29.35 3.04 3 ~29.85 2~99 12 29.~5 2.98 12 ~30.18 2.96 5 30.35 2.94 6 30,52 2.93 31.23 2,86 2 31.20 2 ~ 87 2 31.50 2 ~84 32 15 2.78 1 32.12 2 ~7~ 1 32 80 2.73 3 32.71 2.7~ 2 ~127134 TABLE 3 ( CO~TT ' D ) 33.45 2.68 1 33,36 2.69 33.80 2.65 1 33.69 2,66 34.38 2,61 4 34.33 2.61 2 34.71 2.58 - 1 34.55 2.60 2 34.95 2.57 - 1 35, o6 2,56 2 35.18 2.55 35.75 2.51 3 35,63 2,52 2 ~36, o4 2.49 3 36.10 2.49 5 (36,28 2,48 2 36.72 2.45 1 36,58 2.46 37.11 2.42 3 37,18 2,42 2 37.53 2.4~ 4 37,56 2,39 2 38.31 2.35 38.79 2,32 39.17 2,30 40,39 2,23 1~
40,45 2,23 40.62 2.22 1 40.99 2,20 1 40,99 2.20 41.45 2.18 1 41,43 2.18 41 78 2 16 1 41.80 2,16 42 50 2 13 1 42,48 2.13 42,88 2,11 ^ 1 42,83 2,11 43 24 2,09 1 43.13 2.10 43 56 2,08 1 43.53 2,08 43,81 2.07 45.15 2.01 9 45.02 2.01 6 45.48 1.99 9 45.50 1.99 5 46.25 1.96 46 51 1.95 3 46.50 1.95 2 47 50 1.91 3 47,42 1.92 2 48.44 1.88 2 48.60 1.87 4 ~48.83 1.86 49.48 1.84 1 49.53 1,84 49,78 1.83 1 49,92 1.83 50.18 1.82 1 5~,27 1,81 50,87 1,79 51 40 1,78 1 51,27 1,78 51 60 1.77 2 51,66 1.77 51,90 1,76 52 25 1 75 53.21 1,72 1 53,17 1.72 53.50 1.71 54 23 1 7619 54.93 1.67 2 54.92 1.67 55.25 1.66 3 55.05 1,67 55.55 1.65 1 55.70 1.65 55.92 1.64 1 56.19 1.64 56.69 1.62 1 56.55 1,63 56.90 1.62 ~1 57.19 1.61 58'25 1 6518 59.04 1,56 1 58.96 1.57 .
:, , , :~
In the rollowing Examples (i.e. Examples 2-8) x-ray diffraction pattern for the catalytic form of the respecti~e .-~a.erials is shown ~n .he table followlng t;~e Example.
- Same as Example 1 with the e~ception that 5 gm o~
RuC13.3~20 and 35 gm of HCl were used in place o~ the chromium compound and the sul~urlc acid.
X-ray dlr~raction patterns for this material show subs~antially all the characterlstic lines for the ZSM-5 zeolites as shown in Table 1. As in the ~irst e~ample, treat-ments of the zeolltes o~ this and the six following examples byi~n~exchange~ thermal conditlonln~ or other treatments lead to slmilar ~inor varlations in lnterplanar spacings, lattice symmetry, and relative lntensity.
- 15 . TABLE 4 d(A) ~sO
7.90 11.2 100 8.79 lo.0 57 9.07 9.7 11 9.81 9.0 10.95 8.08 11.8~ 7.46 : 12.4~ 7.0g 13.20 6.71 8 13.90 6.3t11 4.75 6.0118 14.92 5.94 3 ls.52 5.71 9 : ~5.88 5.5812 16.50 5.37 3 17.27 5.13 3 1~.61 5.04 5 17.81 4.~8 6 18.1S 4.89 18.83 4.71 19.23 4.62 4 19.87 4.47 20.35 4.36 20.84 4.25 8 21.79 4.08 2 22.18 4.01 3 il27134 TABLE 4 CONTD~
23 . 083 . 85 66 - 23.28 3.8232 23 . 6s3 . 76 16 23.92 3 . 72 36 24.29 3.66 9 24.53 3.63 9 24.78 3.59 3 24.54 3.49 3 25.85 3.45 5 26.18 3.40 2 26.52 3.36 4 26.92 3.31 6 2~.38 3.26 3 27.63 3.23 28.04 3.18 7 28.43 3.14 2 29.22 ~.06 2 29.30 3.05 2 29.87 2.99 9 30.20 2.96 6 30.55 2.93 31.23 2.86 2 31.55 2.84 a 32.15 2.~8 32.?~3 2.?4~ 2 33.37 2.69 33.75 2.66 ~ ~ .
, 34.30 2.61 2 34.60 2.59 2 35.04 2.56 6 35.63 2.52 2 36 09 2.49 3 '36 33 2.47 2 36.60 2.46 37.18 2.42 2 37.54 2.40 2 :
~Z~34 ~ABLE 4 CON~D.
2~ t " I/
40.99 2.20 41.45 2.18 41.73 2.16 42.50 2.13<1 - 42.88 2.11 43.14 2.10` ` 1 43.53 2.08 -1 45.04 2.~1 7 4S.52 1.99 5 46.48 1.95 2 47.40 1.92 2 48.47 1.88 2 48.83 1.86 49.50 1 . 84 49.83 1.83 ;50.23 1.82<1 -go 1.7S <1 51.24 1.78 51.74 1.77 52.05 1.76 52.33 1.75 53.15 1.72 - <1 53.65 1.7t <1 54.30 1.6~ 3 ~54.98 1.67 3 55.30 1.66 55.75 1.65 `56.05 1.64 <1 56.55 1.63 57.20 1.61 ; 59.03 1.56 llZ7134 EXAMæLE 3 S-ame as Example 1 except that 2 gm of H2PtC16.nH20 was used instead of the chromium compound. Also 35 gm of HCl replaced the H2S04.
2e - d(A~ / o 7.90 11.2 100 8.80 10.0 60 9.10 9.7 14 9.85 9.0 2 11.02 8.03 11.92 7.42 2 12.53 7.06 13.23 6.69 8 13.93 6.3612 14.77 6.0018 15.04 5.89 3 15.54 5.7010 15.89 5.5~313 16.54 5.36 4 17.27 5.13 2 17.58 5.04 5 17.80 4.98 6 18.20 4.87 18.80 4.72 19.25 4.61 5 19.90 4.46 2 ; 20.37 4.36 7 20.85 4.2610 21.80 4.08 3 22.21 4.00 5 22.50 3.95 3 23.10 3.8565 23.34 3.8135 23.72 3.7522 23.95 3.7239 24.33 3.6614 24.57 3.6213 24.86 3.58 3 25.53 3.49 3 25.87 3.44 6 26.13 3.41 3 26.57 3.35 5 26.97 3.31 8 27.42 3.25 4 27.62 3.23 28.08 3.18 28.44 3.14 X
1127~34 ~ E C ~
29.17 3.06 2 29.40 3.04 4 29.90 2.99 13 30.22 2.96 7 30.55 2.93 1 31.23 2.86 2 31.58 2.83 32 lS 2 ~8 33.47 2.68 33.79 2.65 .
34.37 2.61 2 35.70 2.52 3 36.12 2.49 4 36.25 2.48 2 36.~0 2.45 37.23 2.42 2 38.72 2.33 39.20 2.30 39 ~5 2 2~ 2 40.62 2.22 41.03 2.20 41.48 2.18 41.81 2.16 42.50 2.`13 <1 42.95 2.11 43.20 2.10 43.53 2.08 45 13 2.01 a 45 60 1.99 46.13 1.97 2 46.55 1.95 3 47.45 1.92 2 48.51 1.88 2 48.83 1.86 2 49.55 l.B4 49.85 1.63 50.20 l.a2 ~1 so.a8 l.~o <1 51.18 1.7~ <1 51.70 1.77 <1 51.98 1.76 52.27 1.75 53.25 1.72 <1 53.63 1.71 <1 ;
:
~ ~ ~ 5 C Gt~TI~ .
-2a ~L / c 54 . 93 1 . 67 3 55 . 18 1 . 66 2 55.65 1.65 55.93 1.64 <1 56.50 1.6~ 1 56.90 1.6.2 <1 S~.20 1.61 58.30 1.58 a 58.98 1.5 7 ; ~
:: ~
.
. . ...
EXAMPLE` 4 Same as Example 1 except 6~3 gm of In2(S04~3 was used in place of the chromium potassium sulfate.
TAB~E 6 2e d~A) I/Io 7.90 11.2 100 8.80 10.0 41 9.05 9.8 13 9.85 9.0 10.98 8.06 11.85 7.47 12.50 7.08 13.22 6.70 8 13.92 6.36 12 14.75 6.01 13 14.90 5.95 2 15.53 5.71 8 15.91 5.57 11 16.52 5.37 3 17.25 5.14 2 17.63 5.03 4 17.82 4.98 5 18.18 4.88 18.83 4.71 19.27 4.61 4 19.93 4.45 20.40 4.35 6 20.88 4.25 8 : ~
21.83 4.07 2 22.22 4.00 4 23.10 3.85 75 23.30 3.82 40 23.68 3.76 17 23.95 3.72 30 24 30 3.66 8 24 55 3.63 8 25.57 3.48 2 25.90 3.44 5 26~22 3.40 2 26.57 3.35 4 26.97 3.31 7 27.40 3.26 3 ; 27.65 3.23 28.08 3.18 28.45 3.14 ~,, :`
~` 24 ~:
' X~
, :: ::
~, 1~27~34 md~LE ~, A?l`!LD `
29.23 3.06 2 29.33 3.05 2 29.90 2.99 8 30.18 2.96 5 30.50 2.93 31.25 2.86 2 31.53 2.84 32.1~ 2.~8 32.~8 2.~3 2 33.43 2.68 33.73 2.66 .:
34.33 2.61 2 34.60 2.59 35.10 2.56 35.68 2.52 2 36.10 2.49 3 36 30 2.47 36 62 2.45 .:
~ 3~.24 2.41 2 ; ~ 3~.57 2.39 2 . .
, -,~
' . ' . ' :
.
1127~34 Co,~`,Tr .
40.50 2.23 <
41.03 2.20 41.50 2.18 41.80 2.16 <1 42.50 2.13 42.95 2.
43.25 2.10 43.63 2.07 45.05 2.01 5 45.53 1.99 4 46.53 l.9S 2 47.47 1.92 2 48.50 1.8~ 2 48.88 1.86 49.53 1.84 49.90 1.83 50.38 1.81 <1 50.90 1.~9 <1 51.29 1.7a <1 51.75 1.77 52.03 1.76 52.37 1.75 53.20 1.72 a 53.65 1.7~ <
54.20 1.69 <1 S4.g9 1.67 2 55.30 1.66 55.75 1.6 56.10 1.6 56.60 1.63 57.20 1.61 58.35 1.58 <1 59.08 1.56 _ 2~ -i 127134 .
.
EXA~PLE 5 Same as Example 1 except that 5,8 gm of Ce(S04~2 plus 3.7 o. A12(S04)3.14X20 were used~ 'ne former to repl~ce ~he chromium compound.
TA~LE 7 29 drAl _ `
7.91 11.2 100 8.83 10.0 60 9.10 9.7 21 9.80 9.0 2 11.02 8.03 ll.gl 7.43 2 12.50 ~.08 13.23 6.69 15 13.92 6.36 17 14.80 5.9920 15.03 5.89 4 15.55 5.7012 15.93 5.5614 16.54 5.36 4 17.30 5.13 3 17.68 5.02 5 ~.86 4.97 9 18.22 4.8~ 1 18.85 4.71 19.38 4.58 6 19.93 4.45 2 20.40 4.3510 20.88 4.2513 21.80 4.08 4 22.19 4.01 7 22.60 3.93 3 23.09 3 8582 23.33 3 8138 23.70 3.7524 23.98 3.7147 24.35 3.6614 24.58 3.6213 24.85 3.58 3 25.59 3.48 3 25.91 3.44 8 ' ~127134 m.~ E 7 ~ T3 ~
26.34 3.38 3 26.60 3.35 5 26.98 3.30 11 27.42 3.2~ 4 27.58 3.23 28.12 3.17 2 28.47 3.14 2 29.23 3.05 5 29.43 3.04 5 29.92 2.99 15 30.25 2.95 8 30.54 2. g3 2 31.25 2.86 3 31.60 2.83 32.19 2.7~ 2 -32.79 2.73 4 _ _ _ 33.42 2.68 2 33.74 2.66 2 33.99 2.64 }
34.37 2.61 3 34.68 2.59 2 35.13 2.55 2 35.71 2.51 3 36.12 2.49 5 36.33 2.47 3 36.64 2.45 37.20 2.42 3 37,56 2.39 3 38.32 2.35 38.77 2.32 ', ,~
2 ~ -:, ~Z71;~4 - 3 __ C ~ ~3 ~
29 d ( ~ ) 40.54 2.23 41.03 2.2~ 1 41.47 2.18 42.54 2.13 42.93 2.11 2 43.58 2.08 45.11 2.01 9 4S.58 1.99 9 46.03 1.97 46.55 1.95 3 47.49 1.92 3 48.51 1.88 2 48.88 1.86 2 49.50 1.84 49.98 1.82 50.37 1.81 50.88 l.~o 51.30 1.7~ 1 51.71 1.77 52.00 1.76 52.33 1.75 .
54.93 1.67 2 55.i8 1.66 2 ~ 55.55 1.65 - 55.82 1.65 56.S5 1.63 <1 56.98 1.62 <1 ~ 57.25 1.61 a `` ~ 58.35 1.58 <1 ~ 59.00 1.57 , .
:`
EX~MP~E 6 Same as Example 1 except that 2~23 gm of V205 was used in place of the chromium compo~nd.
_Z~ ~(A~ /Io ` 7.85 11.3 100 8_76 10.1 55 9.03 9.8 14 9.75 9.1 2 10.908.12 11.807.50 12.477.10 13.236.69 7 13.856.39 9 14.716.02 17 15.005.91 3 15.485.72 7 15.835.60 11 16.485.38 3 17.205.16 2 17.555.05 5 17.764.99 5 18.104.90 18.804.72 19.204.62 4 19.904.46 20.304.37 6 20.794.27 7 21.714.09 2 22.134.02 3 22.493.95 2 23.023.86 60 23.253.83 31 23.623.77 14 23.883.73 34 24.233.67 8 24.473.64 8 24.723.60 2 25.503.49 3 25.803.45 5 ~' .,' ~.
.~
,, , .
: ~r ~, , . :
~1~27134 I''BLE ~ 5C`~?~.
25. 13 3 .41 2 26.51 3.36 S
26.88 3.32 6 27.33 3.26 2 27.58 3.23 28.09 3.18 28.38 3.14 29.13 3.06 4 29.33 3.05 3 29.82 2.99 10 30.11 2.97 7 30.47 2.93 31.1S 2.87 31.63 2.83 32.19 2.78 32.~1 2.74 2 33.36 2.69 33.69 2.66 33.92 2.64 2 34.30 2.61 34.59 2.59 2 35.00 2.56 2 35.63 2.52 2 36.00 2.49 3 36.23 2.48 2 36.61 2.45 :
:
` 3~.18 2.42 2 ` 3~.50 2.40 2 38.20 2.36 38.65 2.33 '~
~13~
.. .. ..
23 d ( A) 40.43 2.23 40.97 2.20 41.40 2.18 41.72 2.16 - 42.50 2.13<1 42.8s 2.11 43.20 2. lo 43.61 2.08 4s .02 2.016 45.48 l . gS 5 4s .92 1.9~1 46.44 1.96 47.35 1.92 2 48.43 l.B8 48.80 1.87 49.s2 1.84<1 49.82 1.83 ` 50.20 l.a~<1 50.90 1.~9<1 51.24 1.78C
51.62 1.77 - 51.93 1.76 52.20 1.75 ` 53.25 1.72<1 53.65 1.~11 54.9B 1.673 55.25 1.66 ` ss.so 1.66 " ss.~5 1.65 6.5s 1.63 56.90 1.6<~
` s7.22 1.61 ; s8.45 1.58<1 -- 59.00 1.57 , . .
~ :' ., .
~, ~
,, ~, ~., _ 3~ ~
~127~;~4 Same as Example 1 except that 1.5 gm of Zn2B6011 and 25 gm of tetraet~ylammonium bromide were used to replace the chromium compound and the tetrapropylammonium bromide, respectiv-ely.
2e d~A) I/Io 7.91 11.2 100 8.78 10.1 54 : 9.05 9.8 17 9.80 9.0 10.97 8.07 11.85 7.47 12.47 7.10 <1 13.18 6.72 4 13.92 6.36 6 14.74 6.01 10 14.95 5.93 15 50 5.72 4 15 87 5~58 16.42 5.40 16.59 5.34 17.25 5.14 17.60 5.04 3 17.80 4.98 3 18.15 4.89 18.80 4.72 19.21 4.62 2 :~ : 20 33 4 37 3 ~; 20.83 4.26 5 ~27134 ~ 3 _ _ _ _ _ 21.74 4.09 22.23 4.00 2 22.58 3.94 23.05 3.86 77 23.30 3.82 23 23.70 ~ .75 14 23.94 3.72 36 24.32 3.66 10 24.53 3.63 10 24.75 3.60 3-25.50 3.49 5 25.76 3.46 5 25.92 3.44 5 26.18 3.40 2 26.53 3.36 5 26.94 3.31 5 27.37 3.26 3 2~.58 3.23 28.08 3.18 28.33 3.15 3 28.53 3.13 29.18 3.06 5 29.36 3.04 5 29.87 2.99 13 30.18 2.96 6 30.53 2.93 31.18 2.87 2 31.43 2.85 31.70 2.82 32.10 2.79 32.73 2. ~4 3 . ~ ~
. !
.
:
;' ~lZ7~34 . ~ ., g C ~ .
d ( A ) / o 33 . 3a 2 . 6a 1 -33.72 2.~6 33.92 2.64 34. 30 2.612 34.55 2.60 2 SS.05 2.56 2 35.64 2.52 3 36.08 2.49 3 36.28 2.48 36.55 2.46 36.?9 2.44 37.17 2.42 2 37.38 2.41 37.58 2.3g 38.20 2.36 38.63 2.33 38.83 2.32 39.17 2.30 40.38 2.23 40.58 2.22 41.02 2.20 41. 37 2.18 41.65 2.17 42.43 2.13 42.82 2.11 43.11 2.10 43.53 2.08 45.02 2.018 45.53 1.99S
45.95 1.9~1 46.39 1.9b 46.65 1.95 49.90 1.83 50.30 1.81~1 50.95 1.?9 51 2B 1.78 Sl ~0 1.77
The radlatlon was the K-alpha doublet of copper, and a sclntilla-tlon counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from X
.
1127i;~4 the spectrometer chart. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d (obs.l, 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. It should be understood that this X-ray diffraction pattern is characteristic of all the species of the present compositions. Ion exchange of the sodium ion with cations reveals substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample and the extent of thermal conditioning.
The anhydrous composition can also be identified, in terms of mole ratios of oxides, as follows:
2 ~W : ~A120~ X : ~sio2Jy : ~M" 0 2 n wherein W~X is from ~0.5 to <3, Y/X is ~20 and Z/X is from >zero to ~ ~ 100, R is a nitrogen containing cation. R may include primary amines containing 2 to 10 carbon atoms and ammonium cations, preferably the tetraalkylammonium cation in which the alkyl contains from 2 to 5 carbon atoms, M' is a metal from Group IA of the Periodic Table, ammonium, hydrogen or mixtures thereof, and n is the valence of M' or M". With respect to M", the pre-ferred metals are those selected from the rare earth metals, (i.e.
metals having atomic numbers from 57 to 71), chromium, vanadium, molybdenum, indium, boron, mercury, tellurium, silver and one of the platinum group metals, which latter group includes platinum, palladium and ruthenium.
It is not known whether the M" is present as a metal or as a metal compound. The above formula will be understood to take into account the presence in any of the M" various states and also to allow for varying amounts thereof. For example, if it is present in the occluded state, then its concentration relative to aluminum in the zeolite as synthe-sized can range up to but less than about 100.
DESCRIPTION OF SPECIFIC EMBODIMEMTS
A reaction mixture containing sources of the tetra-propylammonium cation tas from the hydroxide), sodium oxide, silica, water, and sources of, for example, indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, mercury, tellurium, silver, palladium, molybdenum and, optionally, alumina, will yield a ZSM-5 zeolite, but having unexpectedly improved properties. The content of indium, boron, etc. listed above can range in the final product from about 0.005~ by weight to 5.0% by weight.
The crystalline aluminosilicates prepared by the ~ method of the present invention have high thermal stability and `~ ~ 20 exhibit superior catalytic performance.
~ The original alkali metal can be replaced, at least in :
part, in accordance with techniques well-known in the art by lon exchange wlth other cations. Pre~erred replaciny cations include metal ions, ammonium ions, hydrogen ions, and mixtures of the same. Particularly preferred cations are those which render the zeolite catalytically active, especially for hydrocarbon conversion. These ir,clude hydrogen, metals of Group II and VIII of the Periodic Table and manganese.
~' ~lZ7~,34 In a preferred embodiment of the zeolite, the silica/alumina mole ratio is yreater than 35 and ranges up to about 3000.
The present zeolites have a high degree of thermal stability thereby rendering them particularly effective for use in processes involving elevated temperatures.
The composit~on can be prepared utilizing materials which supply the appropriate components of the zeolite. Such components include, for an aluminosilicate, sodium aluminate, alumina, sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide and a tetrapropylammonium compound, e.g.
tetrapropylammonium hydroxide. It will be understood that each component utilized in the reaction mixture for preparing the zeolite can be supplied by one or more initial reactants and they can be mixed together in any order. For example, sodium can be supplied by an aqueous solution of sodium hydroxide, or by an aqueous solution of sodium silicate; tetrapropylammonium cation can be supplied by the bromide salt. The reaction mix-~ture can be prepared either batchwise or continuously. Crystal ^~ 20 size and crystallization time of the composition will vary with the nature of the reaction mixture employed. It will be further understood that in the very high silica-to-alumina ratios, which , ~
can ln this invention preferably range from greater than 35 to about 3000 or more, and more preferably about 70 to about 500, 1t may not be necessary to add a source of alumlna to the reaction mixture since residual amounts in other reactants may suffice.
, The zeolite can be prepared from a reaction mixture having a composition, in terms of mole ratios of oxides or in ~ of total moles of oxides, falling within the fcllowing ranges:
llZ7134 ~ABLE 2 ~ost Broad Preferred Preferred OH-~SiO2 0.07-1.0 0.1-0,8 0.2-0.75 R4N ~R4N~ + Na+l 0.2-0.95 0.3-0.9 0.4-0.9 H20~0E 10-300 10-300 10-300 sio2/A123 50-3000 70-1000 70-500 Other metal (% of total oxides) lx10 -1-0 lx10 -0.1 lx10-5-0 01 R is as deflned hereinabove in the Summary.
.
Typlcal reaction conditions consist of heating the foregoing reaction mixture to a temperature of from about 95C
to 175C for a period of tlme of from about six hours to 120 days.
A more preferred temperature range is from about 100C to 175C
~: wlth the amount of time at a temperature in such range being from about 12 hours to 8 days.
` ~ The digestion of the gel particles is carried out -~ untll crystals form. The solid product is separated from the 2~ reaction medium, as by cooling the whole to room temperature~
filtering and water washing.
The ~oregoing product ls dried, e,g~ at 230F, for ~,, from about 8 to 24 hours. Of course, milder conditions may be `~ employed i~ deslred, e.g room temperature under vacuum.
:
2~ The zeolite can have the alkali metal associated therewith replaced by a wide variety of other cations according ; to technlques well-known in the art. Typical replaclng cations would lnclude hydrogen, ammonium and metal cations includlng - mixtures of the same. Of the replacing metallic cations, par-ticular preference is given to cation of metals such as rare earth metal, manganese and calcium, a~ well as metals of Groups II and VIII of the Periodic Table, e~g,~ zinc or platinum, _ 8 -~i27~34 Typical ion exchange techniques include contacting the zeolite with a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
Representative ion exchange techniques are disclosed in a wide variety of patents including United States 3,140,249;
United States 3,140,251; and United States 3,140,253.
Following contact with the salt solution of the desired replacing cations, the zeolites are then preferably washed wlth water and dried at a temperature ranging from 150F
to about 600F and thereafter calcined in air or other inert gas at temperatures ranging from about 500F to 1500F for periods of time ranging from 1 minute to ~8 hours or more.
Regardless of the cations replacing the sodium in its synthesized form, the spatial arrangement of the aluminum, silicon and oxygen atoms which form the basic crystal lattices of the zeolite remains essentially unchanged by the described .~:
replacement of sodium or other alkali metal as determined by taking an X-ray powder diffraction pattern of the ion-exchanged materials. Such X-ray diffraction pattern of the ion-exchanged -~ product reveals a pattern substantially the same as that set forth in Table 1 above.
The aluminosilicates prepared by the instant invention are formed in a wide variety of particular sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size - sufficient to pass through a 2 mesh (Tyler) screen and be ;
retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the aluminosilicate can be extruded before drying or dried or partially dried and then extruded.
~127~34 As in the case of many catalysts, it is desired to incorporate the zeolites with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter ~ay be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of an active material in conjuctiDn with the present composition, i.~., combined therewith, 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 products can be obtained economically ~nd in orderly manner without employing other means for controlling the rate or reaction. Normally, zeolite materials have been incorporated 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 which can be composited with the catalyst include the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite ~12~134 kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined, or they can be initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the catalyst can be composited with a porous matrix material such as silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, 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 cogel.
The relative proportions of finely divided crystalline alumino-silicate and inorganic oxide gel matrix vary widely, with the crystalline aluminosilicate content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 50 percent by weight of the composite.
While the catalyst is useful in cracking and hydro-cracking, it is outstandingly useful in other petroleum refining processes, indicating again the unique catalytic characteristics of these zeolites. The latter processes include isomerization of n-paraffins and naphthenes, polymerization o~ compounds con-talning an olefinic or acetylenic carbon-to-carbon linkage such as isobutylene and butene-l, reformlng, alkylation, isomerlzation `, of polyalkyl substituted aromatics, e.g. ortho-xylene, and disproportionation of aromatics, such as toluene, to provide a mixture of benzene, xylenes and higher methylbenzenes. The catalysts have exceptional high selectivity and, under the conditions of hydrocarbon conversion, provide a high percentage of desired products relative to total products compared with known zeolite hydrocarbon conversion catalysts.
AS indicated above, the zeolite is also useful in other catalytic processes, such as catalytic cracking of hydrocarbons and hydrocrac~ing. In addition to the thermal stability of this family of zeolites under these conditions, they provide conversion of the cracked oil to materials having lower molecular weights and boiling points, which are of greater economic value. The ability to be physically stable under high temperatures and/or in the presence of high tempera-ture steam is extremely important for a cracking catalyst.During catalytic conversion, the reaction which takes place is essentially a cracking to produce hydrocarbons. However, this cracking is accompanied by a number of complex side reactions such as aromatization, polymerization, alkylation and the li~e.
As a result of these complex reactions, a carbonaceous deposit is laid down on the catalyst which is referred to by petroleum engineers as "coke". The deposit of coke on the catalyst tends to seriously impair the catalyst efficiency for the principal reaction desired and to substantially decrease the rate of conversion and/or the selectivity of the process. Thus, lt is common to remove the catalyst after coke has been deposited thereon and to regenerate it by burning the coke in a stream of oxidizing gas. The regenerated catalyst is returned to the converslon stage of the process cycle. The thermal ~tabllity of the 2eolite is advantageous in this re~ard.
~ he products can be used either in the alkali metal form, e.g., the sodium form, in the ammonium form, the hydrogen form, or another univalent or multivalent cationic form.
Preferably, one or the other of the last two forms is employed.
They can also be used in intimate combination with a hydro-genating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation dehydrogena-tion functlon is to be performed. Suah component can be exchanged 7~34 into the composition, impregnat~d therein or physically intim-ately admiYed therewith. Such component can be impregnated in or onto the zeolite, such as, for example, by, in the case of platinum, treating the zeolite with a platinum metal-containing ion. Thus, suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum ammine complex.
The compounds of the useful platinum or other metals can be divided into compounds in which the metal is present in the cation of the compound and compounds in which it is present in the anion of the compound. Both types of compounds which contain the metal in the ionic state can be used. A solution in which platinum metals are in the form of a cation or cationic complex, e.g. Pt(NH3)6C14 is particularly useful. For some hydrocarbon conversion processes, this noble metal form of the catalyst is unnecessary such as in low temperature, liquid phase ortho-xylene isomerization.
When it is employed either as an adsorbent or as a catalyst in one of the aforementioned processes, the catalyst should be at least partially dehydrated. 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 between 1 minute and 48 hours~
Dehydration can also be performed at lower temperautres merely by placing the catalyst in a vacuum, but a lon~er time is required to obtain a sufficient amount of dehydration.
The following examples will illustrate the invention~
'~r ;.r ~127~34 E~AMPLE 1 Solution 1 Q Brand Silicate240 gms Distilled ~20 300 Solution 2 Distilled H20~10 gms Tetrapropyl Ammonlum Bromide 30 ~; Conc. H2S04 20 CrK(S04)2~l2H2012,25 Q Brand ls a Phlladelphia Quartz Co. commercial brand of sodium sllicate. Typlcal Analysis: 8.9% Na20, 28.7 S102, 62.4% H20.
Solutlon 1 was placed into a 4-neck 2 1. flask wlth overhead stirrer. Solution 2 was added wlth stirring. The solutlon became very gelatlnous, A small amount of X-ZSM-5 (about O.lg) was added for seeding. Heating was begun and the solutlon was allowed to heat to about 205F~ The variac ; ~ setting was the only control on the temperature so it varied 20 ~ + 3C depending on voltage variations during the day. After a few days, the solutlon lost lts gelatinous character and became more ohalX-like. Crystallization~ as determined by X-ray, took 5-6 days. The catalyst was flltered and washed with about 4 llters of distilled H20. The yield was 60-70 gms of catalyst.
The catalyst was dried at 70C and calcined in a crucible in a muffle furnace at 75 to 1000F for 12 hours.
The catalyst was placed in a 200 ml flask with 100 cc f H20 and 10 gm of NH4N03 and refluxed at 100C for 1 hour, The catalyst was filtered, washed and NX4~03 e~changed reoeatedly for 5 hours. The catalyst was again filtered, washed and , exchanged re~eatedly for about' 16 hours. ~he catalyst was ~_l'erec, -~as'r.ed thoroughly and drie~ -~ 70C ~or ebou~ ~
hours. The catalyst was calcined again in a muffle furnace at 75 to 1000F for 6 hours.
X-ray powder diffraction patterns of the crystalline product, both in the as-synthesized form and after the treat-ments descrlbed a bove, are given in Table 3~
While this Example illustrates the use of the ammonium cation, other cations such as alkyl ammonium, metals and hydrogen may be used.
As set forth in Table 3, minor differences are observed between the X-ray diffraction patterns of the as-synthe-sized zeolite and the same zeolite after ion exchange and thermal treatments. These differences are changes from singlets to doublets and other doublets to singlets between the two patterns resulting ~rom mlnor shiPts in interplanar spacings and varla-tlons in relatlve lntensities. These observed differences reflect minor variations ln lattice parameters and crystal symmetry.
~127134 ~ABLE 3 ~s Syn~hesize~ ~inished O~t21 ~st 2~ d(A)I/I(0) 2e d(A) I/I(0) 7.89 11.20 367 ' 85 11.26 100 8 78 10.07 26 8.75 10.11 59 9 01 9.81 9 9.05 9.77 14 9.84 8.9g 3 9.80 -9.02 10.98 8. o6 1 10.95 8.08 11.88 7.45 11 11.85 7.47 12.49 7.09 5 12.50 7.08 13.15 6.73 6 13.17 6.72 8 13.89 6.38 14 13.88 6.38 11 14.60 6.07 9~
! 14.72 6.02 17 14.79 5 - 99 10 ~ 14.90 5.95 2 15.48 5.72 9 15.50 5.72 8 15.89 5.58 11 15.85 5.59 11 16.46 5.39 3 16.50 5.37 3 17.25 5.14 ~ 17.23 5.15 2 17.65 5.02 2 17.60 5,04 4 17.75 5~00 4 17.76 4.99 5 18.13 4.89 - 18.80 4.72 19.25 4.61 9 19.21 4.62 4 19.90 4.46 3 19.85 4.47 20.35 4.36 11 20.32 4.37 6 20.85 4.26 12 20.82 4.27 8 21.75 4.09 2 21.75 4.09 3 22.19 4.01 8 22.16 4.01 4 23.15 3.84 100 23.13 3.85 65 23.25 3.83 28 23.67 3.76 24 23.63 3.76 16 23.~2 3.72 45 23,90 3.72 30 ~-24.30 3.66 8 24.38 3.65 30 ~ 24.52 3.63 8 ;~ ~ 24 75 3.60 2 25 55 3.49 4 25.50 3.49 3 25.90 3.44 12 25.84 3,45 5 26.35 3.38 2 26.15 3.41 2 26 68 3.34 7 26.53 3.36 5 26 95 3.31 9 26.92 3.31 7 ~27.38 3.26 3 27 - 45 3.25 3 ~7.63 3.23 28.05 3.18 2 28.13 3.17 28.45 3 - 14 3~28 40 3; 146 13 29.25 3.05 11~29.35 3.04 3 ~29.85 2~99 12 29.~5 2.98 12 ~30.18 2.96 5 30.35 2.94 6 30,52 2.93 31.23 2,86 2 31.20 2 ~ 87 2 31.50 2 ~84 32 15 2.78 1 32.12 2 ~7~ 1 32 80 2.73 3 32.71 2.7~ 2 ~127134 TABLE 3 ( CO~TT ' D ) 33.45 2.68 1 33,36 2.69 33.80 2.65 1 33.69 2,66 34.38 2,61 4 34.33 2.61 2 34.71 2.58 - 1 34.55 2.60 2 34.95 2.57 - 1 35, o6 2,56 2 35.18 2.55 35.75 2.51 3 35,63 2,52 2 ~36, o4 2.49 3 36.10 2.49 5 (36,28 2,48 2 36.72 2.45 1 36,58 2.46 37.11 2.42 3 37,18 2,42 2 37.53 2.4~ 4 37,56 2,39 2 38.31 2.35 38.79 2,32 39.17 2,30 40,39 2,23 1~
40,45 2,23 40.62 2.22 1 40.99 2,20 1 40,99 2.20 41.45 2.18 1 41,43 2.18 41 78 2 16 1 41.80 2,16 42 50 2 13 1 42,48 2.13 42,88 2,11 ^ 1 42,83 2,11 43 24 2,09 1 43.13 2.10 43 56 2,08 1 43.53 2,08 43,81 2.07 45.15 2.01 9 45.02 2.01 6 45.48 1.99 9 45.50 1.99 5 46.25 1.96 46 51 1.95 3 46.50 1.95 2 47 50 1.91 3 47,42 1.92 2 48.44 1.88 2 48.60 1.87 4 ~48.83 1.86 49.48 1.84 1 49.53 1,84 49,78 1.83 1 49,92 1.83 50.18 1.82 1 5~,27 1,81 50,87 1,79 51 40 1,78 1 51,27 1,78 51 60 1.77 2 51,66 1.77 51,90 1,76 52 25 1 75 53.21 1,72 1 53,17 1.72 53.50 1.71 54 23 1 7619 54.93 1.67 2 54.92 1.67 55.25 1.66 3 55.05 1,67 55.55 1.65 1 55.70 1.65 55.92 1.64 1 56.19 1.64 56.69 1.62 1 56.55 1,63 56.90 1.62 ~1 57.19 1.61 58'25 1 6518 59.04 1,56 1 58.96 1.57 .
:, , , :~
In the rollowing Examples (i.e. Examples 2-8) x-ray diffraction pattern for the catalytic form of the respecti~e .-~a.erials is shown ~n .he table followlng t;~e Example.
- Same as Example 1 with the e~ception that 5 gm o~
RuC13.3~20 and 35 gm of HCl were used in place o~ the chromium compound and the sul~urlc acid.
X-ray dlr~raction patterns for this material show subs~antially all the characterlstic lines for the ZSM-5 zeolites as shown in Table 1. As in the ~irst e~ample, treat-ments of the zeolltes o~ this and the six following examples byi~n~exchange~ thermal conditlonln~ or other treatments lead to slmilar ~inor varlations in lnterplanar spacings, lattice symmetry, and relative lntensity.
- 15 . TABLE 4 d(A) ~sO
7.90 11.2 100 8.79 lo.0 57 9.07 9.7 11 9.81 9.0 10.95 8.08 11.8~ 7.46 : 12.4~ 7.0g 13.20 6.71 8 13.90 6.3t11 4.75 6.0118 14.92 5.94 3 ls.52 5.71 9 : ~5.88 5.5812 16.50 5.37 3 17.27 5.13 3 1~.61 5.04 5 17.81 4.~8 6 18.1S 4.89 18.83 4.71 19.23 4.62 4 19.87 4.47 20.35 4.36 20.84 4.25 8 21.79 4.08 2 22.18 4.01 3 il27134 TABLE 4 CONTD~
23 . 083 . 85 66 - 23.28 3.8232 23 . 6s3 . 76 16 23.92 3 . 72 36 24.29 3.66 9 24.53 3.63 9 24.78 3.59 3 24.54 3.49 3 25.85 3.45 5 26.18 3.40 2 26.52 3.36 4 26.92 3.31 6 2~.38 3.26 3 27.63 3.23 28.04 3.18 7 28.43 3.14 2 29.22 ~.06 2 29.30 3.05 2 29.87 2.99 9 30.20 2.96 6 30.55 2.93 31.23 2.86 2 31.55 2.84 a 32.15 2.~8 32.?~3 2.?4~ 2 33.37 2.69 33.75 2.66 ~ ~ .
, 34.30 2.61 2 34.60 2.59 2 35.04 2.56 6 35.63 2.52 2 36 09 2.49 3 '36 33 2.47 2 36.60 2.46 37.18 2.42 2 37.54 2.40 2 :
~Z~34 ~ABLE 4 CON~D.
2~ t " I/
40.99 2.20 41.45 2.18 41.73 2.16 42.50 2.13<1 - 42.88 2.11 43.14 2.10` ` 1 43.53 2.08 -1 45.04 2.~1 7 4S.52 1.99 5 46.48 1.95 2 47.40 1.92 2 48.47 1.88 2 48.83 1.86 49.50 1 . 84 49.83 1.83 ;50.23 1.82<1 -go 1.7S <1 51.24 1.78 51.74 1.77 52.05 1.76 52.33 1.75 53.15 1.72 - <1 53.65 1.7t <1 54.30 1.6~ 3 ~54.98 1.67 3 55.30 1.66 55.75 1.65 `56.05 1.64 <1 56.55 1.63 57.20 1.61 ; 59.03 1.56 llZ7134 EXAMæLE 3 S-ame as Example 1 except that 2 gm of H2PtC16.nH20 was used instead of the chromium compound. Also 35 gm of HCl replaced the H2S04.
2e - d(A~ / o 7.90 11.2 100 8.80 10.0 60 9.10 9.7 14 9.85 9.0 2 11.02 8.03 11.92 7.42 2 12.53 7.06 13.23 6.69 8 13.93 6.3612 14.77 6.0018 15.04 5.89 3 15.54 5.7010 15.89 5.5~313 16.54 5.36 4 17.27 5.13 2 17.58 5.04 5 17.80 4.98 6 18.20 4.87 18.80 4.72 19.25 4.61 5 19.90 4.46 2 ; 20.37 4.36 7 20.85 4.2610 21.80 4.08 3 22.21 4.00 5 22.50 3.95 3 23.10 3.8565 23.34 3.8135 23.72 3.7522 23.95 3.7239 24.33 3.6614 24.57 3.6213 24.86 3.58 3 25.53 3.49 3 25.87 3.44 6 26.13 3.41 3 26.57 3.35 5 26.97 3.31 8 27.42 3.25 4 27.62 3.23 28.08 3.18 28.44 3.14 X
1127~34 ~ E C ~
29.17 3.06 2 29.40 3.04 4 29.90 2.99 13 30.22 2.96 7 30.55 2.93 1 31.23 2.86 2 31.58 2.83 32 lS 2 ~8 33.47 2.68 33.79 2.65 .
34.37 2.61 2 35.70 2.52 3 36.12 2.49 4 36.25 2.48 2 36.~0 2.45 37.23 2.42 2 38.72 2.33 39.20 2.30 39 ~5 2 2~ 2 40.62 2.22 41.03 2.20 41.48 2.18 41.81 2.16 42.50 2.`13 <1 42.95 2.11 43.20 2.10 43.53 2.08 45 13 2.01 a 45 60 1.99 46.13 1.97 2 46.55 1.95 3 47.45 1.92 2 48.51 1.88 2 48.83 1.86 2 49.55 l.B4 49.85 1.63 50.20 l.a2 ~1 so.a8 l.~o <1 51.18 1.7~ <1 51.70 1.77 <1 51.98 1.76 52.27 1.75 53.25 1.72 <1 53.63 1.71 <1 ;
:
~ ~ ~ 5 C Gt~TI~ .
-2a ~L / c 54 . 93 1 . 67 3 55 . 18 1 . 66 2 55.65 1.65 55.93 1.64 <1 56.50 1.6~ 1 56.90 1.6.2 <1 S~.20 1.61 58.30 1.58 a 58.98 1.5 7 ; ~
:: ~
.
. . ...
EXAMPLE` 4 Same as Example 1 except 6~3 gm of In2(S04~3 was used in place of the chromium potassium sulfate.
TAB~E 6 2e d~A) I/Io 7.90 11.2 100 8.80 10.0 41 9.05 9.8 13 9.85 9.0 10.98 8.06 11.85 7.47 12.50 7.08 13.22 6.70 8 13.92 6.36 12 14.75 6.01 13 14.90 5.95 2 15.53 5.71 8 15.91 5.57 11 16.52 5.37 3 17.25 5.14 2 17.63 5.03 4 17.82 4.98 5 18.18 4.88 18.83 4.71 19.27 4.61 4 19.93 4.45 20.40 4.35 6 20.88 4.25 8 : ~
21.83 4.07 2 22.22 4.00 4 23.10 3.85 75 23.30 3.82 40 23.68 3.76 17 23.95 3.72 30 24 30 3.66 8 24 55 3.63 8 25.57 3.48 2 25.90 3.44 5 26~22 3.40 2 26.57 3.35 4 26.97 3.31 7 27.40 3.26 3 ; 27.65 3.23 28.08 3.18 28.45 3.14 ~,, :`
~` 24 ~:
' X~
, :: ::
~, 1~27~34 md~LE ~, A?l`!LD `
29.23 3.06 2 29.33 3.05 2 29.90 2.99 8 30.18 2.96 5 30.50 2.93 31.25 2.86 2 31.53 2.84 32.1~ 2.~8 32.~8 2.~3 2 33.43 2.68 33.73 2.66 .:
34.33 2.61 2 34.60 2.59 35.10 2.56 35.68 2.52 2 36.10 2.49 3 36 30 2.47 36 62 2.45 .:
~ 3~.24 2.41 2 ; ~ 3~.57 2.39 2 . .
, -,~
' . ' . ' :
.
1127~34 Co,~`,Tr .
40.50 2.23 <
41.03 2.20 41.50 2.18 41.80 2.16 <1 42.50 2.13 42.95 2.
43.25 2.10 43.63 2.07 45.05 2.01 5 45.53 1.99 4 46.53 l.9S 2 47.47 1.92 2 48.50 1.8~ 2 48.88 1.86 49.53 1.84 49.90 1.83 50.38 1.81 <1 50.90 1.~9 <1 51.29 1.7a <1 51.75 1.77 52.03 1.76 52.37 1.75 53.20 1.72 a 53.65 1.7~ <
54.20 1.69 <1 S4.g9 1.67 2 55.30 1.66 55.75 1.6 56.10 1.6 56.60 1.63 57.20 1.61 58.35 1.58 <1 59.08 1.56 _ 2~ -i 127134 .
.
EXA~PLE 5 Same as Example 1 except that 5,8 gm of Ce(S04~2 plus 3.7 o. A12(S04)3.14X20 were used~ 'ne former to repl~ce ~he chromium compound.
TA~LE 7 29 drAl _ `
7.91 11.2 100 8.83 10.0 60 9.10 9.7 21 9.80 9.0 2 11.02 8.03 ll.gl 7.43 2 12.50 ~.08 13.23 6.69 15 13.92 6.36 17 14.80 5.9920 15.03 5.89 4 15.55 5.7012 15.93 5.5614 16.54 5.36 4 17.30 5.13 3 17.68 5.02 5 ~.86 4.97 9 18.22 4.8~ 1 18.85 4.71 19.38 4.58 6 19.93 4.45 2 20.40 4.3510 20.88 4.2513 21.80 4.08 4 22.19 4.01 7 22.60 3.93 3 23.09 3 8582 23.33 3 8138 23.70 3.7524 23.98 3.7147 24.35 3.6614 24.58 3.6213 24.85 3.58 3 25.59 3.48 3 25.91 3.44 8 ' ~127134 m.~ E 7 ~ T3 ~
26.34 3.38 3 26.60 3.35 5 26.98 3.30 11 27.42 3.2~ 4 27.58 3.23 28.12 3.17 2 28.47 3.14 2 29.23 3.05 5 29.43 3.04 5 29.92 2.99 15 30.25 2.95 8 30.54 2. g3 2 31.25 2.86 3 31.60 2.83 32.19 2.7~ 2 -32.79 2.73 4 _ _ _ 33.42 2.68 2 33.74 2.66 2 33.99 2.64 }
34.37 2.61 3 34.68 2.59 2 35.13 2.55 2 35.71 2.51 3 36.12 2.49 5 36.33 2.47 3 36.64 2.45 37.20 2.42 3 37,56 2.39 3 38.32 2.35 38.77 2.32 ', ,~
2 ~ -:, ~Z71;~4 - 3 __ C ~ ~3 ~
29 d ( ~ ) 40.54 2.23 41.03 2.2~ 1 41.47 2.18 42.54 2.13 42.93 2.11 2 43.58 2.08 45.11 2.01 9 4S.58 1.99 9 46.03 1.97 46.55 1.95 3 47.49 1.92 3 48.51 1.88 2 48.88 1.86 2 49.50 1.84 49.98 1.82 50.37 1.81 50.88 l.~o 51.30 1.7~ 1 51.71 1.77 52.00 1.76 52.33 1.75 .
54.93 1.67 2 55.i8 1.66 2 ~ 55.55 1.65 - 55.82 1.65 56.S5 1.63 <1 56.98 1.62 <1 ~ 57.25 1.61 a `` ~ 58.35 1.58 <1 ~ 59.00 1.57 , .
:`
EX~MP~E 6 Same as Example 1 except that 2~23 gm of V205 was used in place of the chromium compo~nd.
_Z~ ~(A~ /Io ` 7.85 11.3 100 8_76 10.1 55 9.03 9.8 14 9.75 9.1 2 10.908.12 11.807.50 12.477.10 13.236.69 7 13.856.39 9 14.716.02 17 15.005.91 3 15.485.72 7 15.835.60 11 16.485.38 3 17.205.16 2 17.555.05 5 17.764.99 5 18.104.90 18.804.72 19.204.62 4 19.904.46 20.304.37 6 20.794.27 7 21.714.09 2 22.134.02 3 22.493.95 2 23.023.86 60 23.253.83 31 23.623.77 14 23.883.73 34 24.233.67 8 24.473.64 8 24.723.60 2 25.503.49 3 25.803.45 5 ~' .,' ~.
.~
,, , .
: ~r ~, , . :
~1~27134 I''BLE ~ 5C`~?~.
25. 13 3 .41 2 26.51 3.36 S
26.88 3.32 6 27.33 3.26 2 27.58 3.23 28.09 3.18 28.38 3.14 29.13 3.06 4 29.33 3.05 3 29.82 2.99 10 30.11 2.97 7 30.47 2.93 31.1S 2.87 31.63 2.83 32.19 2.78 32.~1 2.74 2 33.36 2.69 33.69 2.66 33.92 2.64 2 34.30 2.61 34.59 2.59 2 35.00 2.56 2 35.63 2.52 2 36.00 2.49 3 36.23 2.48 2 36.61 2.45 :
:
` 3~.18 2.42 2 ` 3~.50 2.40 2 38.20 2.36 38.65 2.33 '~
~13~
.. .. ..
23 d ( A) 40.43 2.23 40.97 2.20 41.40 2.18 41.72 2.16 - 42.50 2.13<1 42.8s 2.11 43.20 2. lo 43.61 2.08 4s .02 2.016 45.48 l . gS 5 4s .92 1.9~1 46.44 1.96 47.35 1.92 2 48.43 l.B8 48.80 1.87 49.s2 1.84<1 49.82 1.83 ` 50.20 l.a~<1 50.90 1.~9<1 51.24 1.78C
51.62 1.77 - 51.93 1.76 52.20 1.75 ` 53.25 1.72<1 53.65 1.~11 54.9B 1.673 55.25 1.66 ` ss.so 1.66 " ss.~5 1.65 6.5s 1.63 56.90 1.6<~
` s7.22 1.61 ; s8.45 1.58<1 -- 59.00 1.57 , . .
~ :' ., .
~, ~
,, ~, ~., _ 3~ ~
~127~;~4 Same as Example 1 except that 1.5 gm of Zn2B6011 and 25 gm of tetraet~ylammonium bromide were used to replace the chromium compound and the tetrapropylammonium bromide, respectiv-ely.
2e d~A) I/Io 7.91 11.2 100 8.78 10.1 54 : 9.05 9.8 17 9.80 9.0 10.97 8.07 11.85 7.47 12.47 7.10 <1 13.18 6.72 4 13.92 6.36 6 14.74 6.01 10 14.95 5.93 15 50 5.72 4 15 87 5~58 16.42 5.40 16.59 5.34 17.25 5.14 17.60 5.04 3 17.80 4.98 3 18.15 4.89 18.80 4.72 19.21 4.62 2 :~ : 20 33 4 37 3 ~; 20.83 4.26 5 ~27134 ~ 3 _ _ _ _ _ 21.74 4.09 22.23 4.00 2 22.58 3.94 23.05 3.86 77 23.30 3.82 23 23.70 ~ .75 14 23.94 3.72 36 24.32 3.66 10 24.53 3.63 10 24.75 3.60 3-25.50 3.49 5 25.76 3.46 5 25.92 3.44 5 26.18 3.40 2 26.53 3.36 5 26.94 3.31 5 27.37 3.26 3 2~.58 3.23 28.08 3.18 28.33 3.15 3 28.53 3.13 29.18 3.06 5 29.36 3.04 5 29.87 2.99 13 30.18 2.96 6 30.53 2.93 31.18 2.87 2 31.43 2.85 31.70 2.82 32.10 2.79 32.73 2. ~4 3 . ~ ~
. !
.
:
;' ~lZ7~34 . ~ ., g C ~ .
d ( A ) / o 33 . 3a 2 . 6a 1 -33.72 2.~6 33.92 2.64 34. 30 2.612 34.55 2.60 2 SS.05 2.56 2 35.64 2.52 3 36.08 2.49 3 36.28 2.48 36.55 2.46 36.?9 2.44 37.17 2.42 2 37.38 2.41 37.58 2.3g 38.20 2.36 38.63 2.33 38.83 2.32 39.17 2.30 40.38 2.23 40.58 2.22 41.02 2.20 41. 37 2.18 41.65 2.17 42.43 2.13 42.82 2.11 43.11 2.10 43.53 2.08 45.02 2.018 45.53 1.99S
45.95 1.9~1 46.39 1.9b 46.65 1.95 49.90 1.83 50.30 1.81~1 50.95 1.?9 51 2B 1.78 Sl ~0 1.77
5~.95 1.76 52.26 1.75 ~4.92 1.67 4 55.13 1.67 2 55.73 1.6S
56.52 1.63 56.61 1.62 57.25 1.6) 58.40 1.58 59.03 1.56 ~127134 Same as Example 1, but usiny 3~97 gm of molybdic acid ~H2MoO4~ to replace the chr~mium compound.
2e d(A~ / o 7.90 11.2 100 8.79 10.1 55 9.10 9.7 12 9.83 9.0 11.02 a.03 11.80 7.50 12.50 7.08 13.20 6.71 7 13.90 6.3710 14.78 5.9917 15.08 5.87 2 15.52 5.71 7 15.90 5.5711 16.50 5.37 3 17.25 5.14 2 17.60 5.04 5 17.82 4.98 5 18.13 4.89 i 18.90 4.70 i 19.22 4.62 4 19.87 4.47 20.38 4.36 7 20.83 4.26 7 21.25 4.18 21.78 4.08 3 22.17 4.01 4 22.69 3.92 3 23.07 3.8657 23.35 3.8125 23.68 3.7617 23.92 3.7234 24.30 3.6611 24.51 3.6310 24.77 3.59 4 25.53 3.~7 4 25.79 3T45 5 .~
~.
1~27134 _ 10 ''O~Tr_.
2S.203.40 3 26 573.35 4 26.913.31 6 27.373.26 3 27.693.22 28.103.1a 2a.393.14 29.203.06 3 29.413.04 3 29.882.99 10 30.182.96 5 30.522.93 31.212.87 31.602.83 <1 32.1~2.78 32.~72.73 2 33.42 2.68 33.72 2.66 34.32 2.6~ 2 34.68 2.59 35.07 2.56 2 35.67 2.52 2 36.08 2.49 3 36.33 2.47 2 36.65 2.45 3~.20 2.42 2 3?.55 2.40 <1 38.32 2.35 38.63 2.33 ~1 39.26 2.29 2 40.50 2.23 40.g3 2.20 41.25 2.19 41.60 2.17 42.51 2.13 <1 42.gO 2.11 <1 43.20 2.10 43 57 2 oa 45.53 1.99 5 46.50 1.95 2 .~, ..... .
, - llZ7134 2~
47.48 l .9Z 2 48.53 1.88 2 48.89 1.86 49.62 1.84 49.97 1.82 50.35 1.81 <1 50.90 1.79 a 51.33 1.78 <1 51.61 1.~7 Sl.90 1.76 52.27 1.75 53.35 1.~2 <1 53.68 1.~ <1 54.25 1.69 54.92 1.6~ 2 55.20 1.66 2 55.~3 1.65 56.10 1.6~ <1 56.55 1.63 56.85 1.62 <1 57.25 1.61 a 58.45 1.58 a 59.09 1.56 a ~:
llZ7~34 EXAMPLE g This wzs ~.ace si . ~ l e-ly t~ -x2:~01~ 1, e~cseo~, t"a~
5 gm of silver acetate replaced the chromium compound~ The x-ray analysis showed it to have a pattern similar to the prevlous Examples.
Thls was made as shown ln Example 1 except that ~` 35 gm of HC1 was used instead o~ sul~uric acid and 5 gm o~ HgC12 was used instead o~ the chromium compound. The x-ray analysis showed it to have a pattern similar to the previous Examples.
This was also made like Example 1, except that 5 gm of H6TeO6was used instead o~ the chromium compound. The x-ray analysis showed it to have a pattern similar to the previous Examples.
Employing the catalyst o~ 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 ~25F using 2Q molar ratios of hydrogen to hydrocarbon charge in the ran~e between 2 and 80. The pressure employed wlll vary between 10 and 2,500 psig and the liquid hourly space velocity between 0.1 and 10.
Employing the catalyst of this invention ~or catalytic cracking, hydrocarbon crackin~ stocks can be cracked at a liquid hourly space velocity between about 0.5 and 50, a temperzture between about 550F and 1100F, a pressure between about sub-atmospherlc ~nd sever_l hur.dred atmospheres.
- 39 ~
Employing a catalytically active form of the zeolites of this invention cont~ining a hydrogenation component, reform-ing stocks can ~e reformed employing a temperature between 700F
and 1000F. The pressure can be ~etween lOO and 1000 psig, but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0,1 and lO, preferably 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 paraf~ins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 200 and 700F, preferably 300 to 550F, with a liquid 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 l:l and 5:1. Additionally, the catalyst can be used for olefin isomerization employing temperatures between 30F and 500F. and for methanol and dimethylether conversion.
Other reactions which can be accomplished employing the catalyst of this invention containing a metal, e.g. platinum include hydrogenation-dehydrogenation reactions and desulfuriza-tion and hydrocarbon oxidation reactions.
The products were tested in several o~ the conversion processes mentioned above. The result follow:
EVALUATION OF PRODUCTS
_ .
Toluene DisProportionation Table 11 summarizes data obtained using various samples of the hydrogen form of the zeolite in toluene conversion. The runs were made at 600 psig, 3~5 WHSV and a H2-hydrocarbon (H2/HC) ratiO of 2/l, except where different conditions are noted. The hydrogen form was obtained by the procedure of Example 1.
~lZ7134 .
TA3LE ,1 ?letal Used in T;lt. ,; Tolusne Synthesis_ Temp., FConve~sion _ Pt (Example 2) 850 31.8 5 V (Example 6) goo 14.0 Mo ~Example 8~ 900 14.7 ; Cr (Example 1) 1100 (10 WHSV) 16.9 - Hydrocracking Table12 shows the results obtained in convertinC
; 10 224F - 365F Buffalo Naphtha using the hydrogen form of the zeolite at 900 and 1000F. Conversion was at 100 psig, 5 ~HSV and a H2~HC o~ 3/1. The naphtha had the characteristics shown in the table. The hydrogen form of the zeolite was obtained as per the description hereinabove.
~;
.
~ 41 -~127~1 34 .
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u~ O L~
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.. . . ..
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~ I
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rl 0 50 ~J
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~ r-l ::: 3 V
~ ~ .
*. ~e ~: P tn o L~
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:: Ir~ 3 ~1, ~1 3 .~
. ~ ~
O O O O Z c~ O
. ~ ~ O O O o o O O O ~ ~i ~ O~
E~ ,~1 ~
u~ m .
~_1 ~ a~ a~
O ~ ~
u~ S LS~ ~) ~ h D ~ ~0 U~ h ¢
¢ + +
:~ ~ ~V H O ~O ~ O C~
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4 -- -- .
.. .
"~
. .
~12'7134 Reaction of Methanol Yaporized methanol was passed over the hydrogen form of the zeolite prepared using platinum~ The conditions and results are shown in Table 13.
, ` :~
~;
::
, ' llZ7134 .
.
o a~
o o a~
C) ,, ,, .
~,, X~
I U~ 5 l~
Il C~
~1 ~
O
' ~
:~ , a.
~` 3~1 5 t_ .
: , ¢
, ~ + I O ~
5 a-,V
,':
O
~ o ~n , ~ ~ U~
+
0 0~ O ~ ' C
'' : , :' ~ ' ~ I
U~ I~
. '~ IL~
~ ~1 ~
:, . ~ ~ O
t_ .
.
1~27134 Xylene Isomerization The same zeolite used for the test su~m2rized in Table ~ was tested for xylene isomeriza~ion activity. Table 14 summarizes the conditiol~s and results.
~ -~AB~E 14 680F, 200 psig, 5 ~SV And 4/1 H~/HC
Fractions Obtained ~lt. % % Xylene Charge Cl-C5 0 . 1 Benzene 2.1 0.1 Toluene 0.2 0.1 EB 16.1 20.9 p-Xyl. 19.1 24.5 2.8 m_Xyl. 41.6 53.3 51.3 o-Xyl. 17.4 22.2 24.5 Cgl Ar 3.4 0.3 The charge set ~orth in Tablel5 was passed over the same catalyst used as per Tables 13and 14at the conditions speci~led. A summary of results is shown in the table.
l~Z7134 TA~LE 1 Temp, F 100ûF
WHSV
Charge -Light Product Woodhaven Dist ribut ion, Wt . % Re format e Cl 3.6 C2 s .13 . 8 C3's . 19.2 C4's 4.9 Cs's 0 0.2 C6's 0.5 25.9 ; 15 C~' 0.2 25.1 C6H6 11. 8 8 . 6 Cg~s 0 7.6 Tol 33 5 32 .1 CgAr 9 . 6 0 . 5 ~' 20 Cg~Ar 2.9 New Aromatics Make, g/lOOg Charge 16.6 Wt. ~ of Aromatlcs Made/Conv . 28 . 7 '' .
56.52 1.63 56.61 1.62 57.25 1.6) 58.40 1.58 59.03 1.56 ~127134 Same as Example 1, but usiny 3~97 gm of molybdic acid ~H2MoO4~ to replace the chr~mium compound.
2e d(A~ / o 7.90 11.2 100 8.79 10.1 55 9.10 9.7 12 9.83 9.0 11.02 a.03 11.80 7.50 12.50 7.08 13.20 6.71 7 13.90 6.3710 14.78 5.9917 15.08 5.87 2 15.52 5.71 7 15.90 5.5711 16.50 5.37 3 17.25 5.14 2 17.60 5.04 5 17.82 4.98 5 18.13 4.89 i 18.90 4.70 i 19.22 4.62 4 19.87 4.47 20.38 4.36 7 20.83 4.26 7 21.25 4.18 21.78 4.08 3 22.17 4.01 4 22.69 3.92 3 23.07 3.8657 23.35 3.8125 23.68 3.7617 23.92 3.7234 24.30 3.6611 24.51 3.6310 24.77 3.59 4 25.53 3.~7 4 25.79 3T45 5 .~
~.
1~27134 _ 10 ''O~Tr_.
2S.203.40 3 26 573.35 4 26.913.31 6 27.373.26 3 27.693.22 28.103.1a 2a.393.14 29.203.06 3 29.413.04 3 29.882.99 10 30.182.96 5 30.522.93 31.212.87 31.602.83 <1 32.1~2.78 32.~72.73 2 33.42 2.68 33.72 2.66 34.32 2.6~ 2 34.68 2.59 35.07 2.56 2 35.67 2.52 2 36.08 2.49 3 36.33 2.47 2 36.65 2.45 3~.20 2.42 2 3?.55 2.40 <1 38.32 2.35 38.63 2.33 ~1 39.26 2.29 2 40.50 2.23 40.g3 2.20 41.25 2.19 41.60 2.17 42.51 2.13 <1 42.gO 2.11 <1 43.20 2.10 43 57 2 oa 45.53 1.99 5 46.50 1.95 2 .~, ..... .
, - llZ7134 2~
47.48 l .9Z 2 48.53 1.88 2 48.89 1.86 49.62 1.84 49.97 1.82 50.35 1.81 <1 50.90 1.79 a 51.33 1.78 <1 51.61 1.~7 Sl.90 1.76 52.27 1.75 53.35 1.~2 <1 53.68 1.~ <1 54.25 1.69 54.92 1.6~ 2 55.20 1.66 2 55.~3 1.65 56.10 1.6~ <1 56.55 1.63 56.85 1.62 <1 57.25 1.61 a 58.45 1.58 a 59.09 1.56 a ~:
llZ7~34 EXAMPLE g This wzs ~.ace si . ~ l e-ly t~ -x2:~01~ 1, e~cseo~, t"a~
5 gm of silver acetate replaced the chromium compound~ The x-ray analysis showed it to have a pattern similar to the prevlous Examples.
Thls was made as shown ln Example 1 except that ~` 35 gm of HC1 was used instead o~ sul~uric acid and 5 gm o~ HgC12 was used instead o~ the chromium compound. The x-ray analysis showed it to have a pattern similar to the previous Examples.
This was also made like Example 1, except that 5 gm of H6TeO6was used instead o~ the chromium compound. The x-ray analysis showed it to have a pattern similar to the previous Examples.
Employing the catalyst o~ 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 ~25F using 2Q molar ratios of hydrogen to hydrocarbon charge in the ran~e between 2 and 80. The pressure employed wlll vary between 10 and 2,500 psig and the liquid hourly space velocity between 0.1 and 10.
Employing the catalyst of this invention ~or catalytic cracking, hydrocarbon crackin~ stocks can be cracked at a liquid hourly space velocity between about 0.5 and 50, a temperzture between about 550F and 1100F, a pressure between about sub-atmospherlc ~nd sever_l hur.dred atmospheres.
- 39 ~
Employing a catalytically active form of the zeolites of this invention cont~ining a hydrogenation component, reform-ing stocks can ~e reformed employing a temperature between 700F
and 1000F. The pressure can be ~etween lOO and 1000 psig, but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0,1 and lO, preferably 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 paraf~ins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 200 and 700F, preferably 300 to 550F, with a liquid 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 l:l and 5:1. Additionally, the catalyst can be used for olefin isomerization employing temperatures between 30F and 500F. and for methanol and dimethylether conversion.
Other reactions which can be accomplished employing the catalyst of this invention containing a metal, e.g. platinum include hydrogenation-dehydrogenation reactions and desulfuriza-tion and hydrocarbon oxidation reactions.
The products were tested in several o~ the conversion processes mentioned above. The result follow:
EVALUATION OF PRODUCTS
_ .
Toluene DisProportionation Table 11 summarizes data obtained using various samples of the hydrogen form of the zeolite in toluene conversion. The runs were made at 600 psig, 3~5 WHSV and a H2-hydrocarbon (H2/HC) ratiO of 2/l, except where different conditions are noted. The hydrogen form was obtained by the procedure of Example 1.
~lZ7134 .
TA3LE ,1 ?letal Used in T;lt. ,; Tolusne Synthesis_ Temp., FConve~sion _ Pt (Example 2) 850 31.8 5 V (Example 6) goo 14.0 Mo ~Example 8~ 900 14.7 ; Cr (Example 1) 1100 (10 WHSV) 16.9 - Hydrocracking Table12 shows the results obtained in convertinC
; 10 224F - 365F Buffalo Naphtha using the hydrogen form of the zeolite at 900 and 1000F. Conversion was at 100 psig, 5 ~HSV and a H2~HC o~ 3/1. The naphtha had the characteristics shown in the table. The hydrogen form of the zeolite was obtained as per the description hereinabove.
~;
.
~ 41 -~127~1 34 .
a~
u~ O L~
C~
.,, . oo,, o ~ :~ ~Itr~ ~ 3 Eo~ O
~' ~ ~ ~ ~ CO ' : V O
I V 1~ ~O~D 3 _I
` .
.. . . ..
~S~ .
~dS
2~V
~ I
C~ ~
rl 0 50 ~J
J~ O .-1 ~1 ~0 ~1 . ' ~ O
~q ) ~a~
V
I ~ I N
~ r-l ::: 3 V
~ ~ .
*. ~e ~: P tn o L~
O t--~ U~ ~ ~
:: Ir~ 3 ~1, ~1 3 .~
. ~ ~
O O O O Z c~ O
. ~ ~ O O O o o O O O ~ ~i ~ O~
E~ ,~1 ~
u~ m .
~_1 ~ a~ a~
O ~ ~
u~ S LS~ ~) ~ h D ~ ~0 U~ h ¢
¢ + +
:~ ~ ~V H O ~O ~ O C~
C~J
4 -- -- .
.. .
"~
. .
~12'7134 Reaction of Methanol Yaporized methanol was passed over the hydrogen form of the zeolite prepared using platinum~ The conditions and results are shown in Table 13.
, ` :~
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, ' llZ7134 .
.
o a~
o o a~
C) ,, ,, .
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: , ¢
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O
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+
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'' : , :' ~ ' ~ I
U~ I~
. '~ IL~
~ ~1 ~
:, . ~ ~ O
t_ .
.
1~27134 Xylene Isomerization The same zeolite used for the test su~m2rized in Table ~ was tested for xylene isomeriza~ion activity. Table 14 summarizes the conditiol~s and results.
~ -~AB~E 14 680F, 200 psig, 5 ~SV And 4/1 H~/HC
Fractions Obtained ~lt. % % Xylene Charge Cl-C5 0 . 1 Benzene 2.1 0.1 Toluene 0.2 0.1 EB 16.1 20.9 p-Xyl. 19.1 24.5 2.8 m_Xyl. 41.6 53.3 51.3 o-Xyl. 17.4 22.2 24.5 Cgl Ar 3.4 0.3 The charge set ~orth in Tablel5 was passed over the same catalyst used as per Tables 13and 14at the conditions speci~led. A summary of results is shown in the table.
l~Z7134 TA~LE 1 Temp, F 100ûF
WHSV
Charge -Light Product Woodhaven Dist ribut ion, Wt . % Re format e Cl 3.6 C2 s .13 . 8 C3's . 19.2 C4's 4.9 Cs's 0 0.2 C6's 0.5 25.9 ; 15 C~' 0.2 25.1 C6H6 11. 8 8 . 6 Cg~s 0 7.6 Tol 33 5 32 .1 CgAr 9 . 6 0 . 5 ~' 20 Cg~Ar 2.9 New Aromatics Make, g/lOOg Charge 16.6 Wt. ~ of Aromatlcs Made/Conv . 28 . 7 '' .
Claims (50)
1. A crystalline aluminosilicate zeolite composition having, in the anhydrous state, a formula in terms of mole ratios of oxides as follows:
wherein W/X is from > 0.5 to < 3, Y/X is > 20 and Z/X is from > zero to < ~100, R is a nitrogen containing cation, M' is a metal from Group IA of the Periodic Table, M" is a metal selected from the group consisting of indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, palladium, molybdenum, mercury, tellurium, silver and a mixture of such metals, and n is the valence of the metal, said composition having the X-ray diffraction pattern substantially as set forth in Table 1 below:
wherein W/X is from > 0.5 to < 3, Y/X is > 20 and Z/X is from > zero to < ~100, R is a nitrogen containing cation, M' is a metal from Group IA of the Periodic Table, M" is a metal selected from the group consisting of indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, palladium, molybdenum, mercury, tellurium, silver and a mixture of such metals, and n is the valence of the metal, said composition having the X-ray diffraction pattern substantially as set forth in Table 1 below:
2. The composition of claim 1 wherein R is a tetra-alkylammonium cation in which the alkyl contains from 2 to 5 carbon atoms.
3. The composition of claim 1 wherein R and/or M' has been replaced by cations selected from the group consisting of alkylammonium, metal, ammonium, hydrogen and mixtures thereof.
4. The product resulting from thermally treating the composition of claim 3 at a temperature above 500°F.
5. The composition of claim 1 wherein M' is sodium.
6. The composition of claim 1 wherein M" is selected from the group consisting of chromium, ruthenium, platinum, indium, cerium, vanadium, boron, molybdenum, mercury, tellurium and silver.
7. The composition of claim 6 wherein M" is chromium.
8. The composition of claim 6 wherein M" is ruthenium.
9. The composition of claim 6 wherein M" is platinum.
10. The composition of claim 6 wherein M" is indium.
11. The composition of claim 6 wherein M" is cerium.
12. The composition of claim 6 wherein M" is vanadium.
13. The composition of claim 6 wherein M" is boron.
14. The composition of claim 6 wherein M" is molybdenum.
15. The composition of claim 6 wherein M" is mercury.
16. The composition of claim 6 wherein M" is tellurium.
17. The composition of claim 6 wherein M" is silver.
18. The composition of claim 1 in which the SiO2 to Al2O3 ratio is from greater than about 35 to about 3000.
19. A process for converting an organic charge under conversion conditions comprising passing said charge over a crystalline aluminosilicate zeolite composition having, in the anhydrous state, a formula in terms of mole ratios of oxides as follows:
wherein W/X is from > 0.5 to < 3, Y/Z is > 20 and Z/X is from > zero to < ~100, R is a nitrogen cation, M' is a metal from Group IA of the Periodic Table, M" is a metal selected from the group consisting of indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, palladium, molybdenum, mercury, tellurium, silver and a mixture of such metals, and n is the valence of the metal, said composition having the X-ray diffraction pattern substantially as set forth in Table 1 below:
wherein W/X is from > 0.5 to < 3, Y/Z is > 20 and Z/X is from > zero to < ~100, R is a nitrogen cation, M' is a metal from Group IA of the Periodic Table, M" is a metal selected from the group consisting of indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, palladium, molybdenum, mercury, tellurium, silver and a mixture of such metals, and n is the valence of the metal, said composition having the X-ray diffraction pattern substantially as set forth in Table 1 below:
20. The process of claim 19 wherein in the composition R
is a tetraalkylammonium cation, the alkyl containing 2 to 5 carbon atoms.
is a tetraalkylammonium cation, the alkyl containing 2 to 5 carbon atoms.
21. The process of claim 19 in which the composition used has been thermally treated.
22. The process of claim 19 wherein the composition used is the product resulting from replacing R and/or M' by cations selected from the group consisting of alkylammon-ium, metal, ammonium, hydrogen and mixtures thereof and thermally treating the material at a temperature above 500°F.
23. The process of claim 19 wherein in said composition M' is sodium.
24. The process of claim 19 wherein said composition M"
is selected from the group consisting of chromium, ruthenium, platinum, indium, cerium, vanadium, boron, molybdenum, mercury, tellurium, and silver.
is selected from the group consisting of chromium, ruthenium, platinum, indium, cerium, vanadium, boron, molybdenum, mercury, tellurium, and silver.
25. The process of claim 24 wherein said composition M"
is chromium.
is chromium.
26. The process of claim 24 wherein in said composition M"
is ruthenium.
is ruthenium.
27. The process of claim 24 wherein in said composition M"
is platinum.
is platinum.
28. The process of claim 24 wherein in said composition M"
is indium.
is indium.
29. The process of claim 24 wherein in said composition M"
is cerium.
is cerium.
30. The process of claim 24 wherein in said composition M"
is vanadium.
is vanadium.
31. The process of claim 24 wherein in said composition M"
is boron.
is boron.
32. The process of claim 24 wherein in said composition M"
is molybdenum.
is molybdenum.
33. The process of claim 24 wherein in said composition M"
is mercury.
is mercury.
34. The process of claim 24 wherein in said composition M"
is tellurium.
is tellurium.
35. The process of claim 24 wherein in said composition M"
is silver.
is silver.
36. The process of claim 19 in which the SiO2 to A12O3 ratio in said zeolite is from greater than about 35 to about 3000.
37. A method of preparing a crystalline aluminosilicate zeolite as defined in claim 1 which comprises preparing a reaction mixture comprising sources of tetraalkylammonium compound, silica, alumina, alkali metal and M", the mixture having the following mole ratios of oxides or % of total moles of oxides:
OH-/SiO2 0.07-1.0 R4N+/(R4N+ + Na+) 0.2-0.95 SiO2/A12O3 50-3000 Other metal Oxide (% of total oxides) 1x10-6-1.0 wherein R is a nitrogen cation, heating the mixture until crystals having the characteristic X-ray diffraction pattern of ZSM-5, as set forth in Table 1 in claim 1, are formed and ion exchanging and calcining same.
OH-/SiO2 0.07-1.0 R4N+/(R4N+ + Na+) 0.2-0.95 SiO2/A12O3 50-3000 Other metal Oxide (% of total oxides) 1x10-6-1.0 wherein R is a nitrogen cation, heating the mixture until crystals having the characteristic X-ray diffraction pattern of ZSM-5, as set forth in Table 1 in claim 1, are formed and ion exchanging and calcining same.
38. The method of claim 37 wherein the mole ratios of oxides or % of total moles of oxides are:
OH-/SiO2 0.1-0.8 R4N+/(R4N+ + Na+) 0.3-0.9 SiO2/A12O3 70-1000 Other metal Oxide (% of total oxides) 1x10-5-0.1.
OH-/SiO2 0.1-0.8 R4N+/(R4N+ + Na+) 0.3-0.9 SiO2/A12O3 70-1000 Other metal Oxide (% of total oxides) 1x10-5-0.1.
39. The method of claim 37 wherein the mole ratios of oxides or % of total moles of oxides are:
OH-/SiO2 0.2-0.75 R4N+/(R4N+ + Na+) 0.4-0.9 SiO2/Al2O3 70-500 Other metal Oxide (% of total oxides) 1x10-5-0.01.
OH-/SiO2 0.2-0.75 R4N+/(R4N+ + Na+) 0.4-0.9 SiO2/Al2O3 70-500 Other metal Oxide (% of total oxides) 1x10-5-0.01.
40. The method of claim 37, 38 or 39 wherein M" is chromium.
41. The method of claim 37, 38 or 39 wherein M" is ruthenium.
42. The method of claim 37, 38 or 39 wherein M" is platinum.
43. The method of claim 37, 38 or 39 wherein M" is indium.
44. The method of claim 37, 38 or 39 wherein M" is cerium.
45. The method of claim 37, 38 or 39 wherein M" is vanadium.
46. The method of claim 37, 38 or 39 wherein M" is boron.
47. The method of claim 37, 38 or 39 wherein M" is molybdenum.
48. The method of claim 37, 38 or 39 wherein M" is mercury.
49. The method of claim 37, 38 or 39 wherein M" is tellurium.
50. The method of claim 37, 38 or 39 wherein M" is silver.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA315,748A CA1127134A (en) | 1978-11-02 | 1978-11-02 | Crystalline zeolite composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA315,748A CA1127134A (en) | 1978-11-02 | 1978-11-02 | Crystalline zeolite composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127134A true CA1127134A (en) | 1982-07-06 |
Family
ID=4112872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA315,748A Expired CA1127134A (en) | 1978-11-02 | 1978-11-02 | Crystalline zeolite composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1127134A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5186918A (en) * | 1987-12-15 | 1993-02-16 | Uop | Substitution of Cr in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| US5401488A (en) * | 1987-12-15 | 1995-03-28 | Uop | Substitution of Sn in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| US5677254A (en) * | 1993-02-16 | 1997-10-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for purifying an exhaust gas |
| US5869021A (en) * | 1994-12-30 | 1999-02-09 | China Petro-Chemical Corporation | Rare earth--ZSM-5/ZSM-11 cocrystalline zeolite |
-
1978
- 1978-11-02 CA CA315,748A patent/CA1127134A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5186918A (en) * | 1987-12-15 | 1993-02-16 | Uop | Substitution of Cr in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| US5401488A (en) * | 1987-12-15 | 1995-03-28 | Uop | Substitution of Sn in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| US5677254A (en) * | 1993-02-16 | 1997-10-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for purifying an exhaust gas |
| US5869021A (en) * | 1994-12-30 | 1999-02-09 | China Petro-Chemical Corporation | Rare earth--ZSM-5/ZSM-11 cocrystalline zeolite |
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