NZ201113A - A method of preparing an ams-1b crystalline borosilicate molecular sieve - Google Patents
A method of preparing an ams-1b crystalline borosilicate molecular sieveInfo
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- NZ201113A NZ201113A NZ201113A NZ20111382A NZ201113A NZ 201113 A NZ201113 A NZ 201113A NZ 201113 A NZ201113 A NZ 201113A NZ 20111382 A NZ20111382 A NZ 20111382A NZ 201113 A NZ201113 A NZ 201113A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Silicates, Zeolites, And Molecular Sieves (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
New Zealand Paient Spedficaiion for Paient Number £01113
201113
Priority Date(s): 7.?!-.
Complete Specification Filed:
Class:
$ l/f tf -j B G{
WR AUG W*5*
Publication Date: ........V.T. "
P.O. Journal, No:
Patents Form No.5
29J[|y[^i5g2
;•*£; .V;7?c»
NEW ZEALAND PATENTS ACT 19 53
COMPLETE SPECIFICATION
"MANUFACTURE OF AMS-1B CRYSTALLINE BOROSILICATE MOLECULAR SIEVE"
-I,WE STANDARD OIL COMPANY, a corporation of the State of Indiana, U.S.A., of 200 East Randolph Drive, Chicago, Illinois, 60601, U.S.A.
hereby declare the invention, for which T/we pray that a patent may be granted to ifie/us,,and the method by which it is to be performed, to be particularly described in and by the following statement:-
i (followed by page 1 A >
201 1
Background of the Invention
This invention relates to a new method to manufacture molecular sieves and more particularly to a new method to manufacture crystalline borosilicate AMS-lB molecular sieve and to a product made from that method.
Zeolitic materials, both natural and synthetic, are known to have catalytic capabilities for many hydrocarbon processes. Zeolitic materials typically are ordered porous crystalline aluminosilicates having a definite structure with cavities interconnected by channels. The cavities and channels throughout the crystalline material generally are uniform in size allowing selective separation of hydrocarbons. Consequently, these materials in many instances are known in the art as "molecular sieves" and are used, in addition to selective adsorptive processes, for certain catalytic properties. The catalytic properties of these materials are affected to some extent by the size of the molecules which selectively penetrate the crystal structure, presumably to contact active catalytic sites within the ordered structure of these materials.
Generally, the term "molecular sieve" includes a wide va'riety of both natural and synthetic positive-ion-containing crystalline zeolite materials. They generally are characterized as crystalline aluminosilicates which comprise networks of SiC>4 and AIO4 tetrahedra in which silicon and aluminum atoms are cross-linked by sharing of oxygen atoms. The negative
201113
framework charge resulting from substitution of an aluminum atom for a silicon atom is balanced by positive ions, for example, alkali-metal or alkaline-earth-metal cations, ammonium ions, or hydrogen ions.
Boron is not considered a replacement for aluminum or silicon in a zeolitic composition. However, recently a new crystalline borosilicate molecular sieve AMS-lB was disclosed in U.S. Patent 4,268,420 and 4,269,813 incorporated by reference herein. According to these 10 patents AMS-lB can be synthesized by crystallizing a source of an oxide of silicon, an oxide of boron, an oxide of sodium and an organic template compound such as a tetra-n-propylammonium salt. In order to form a catalytically-active species of AMS-lB, sodium ion 15 typically is removed by one or more exchanges with ammonium ion followed by calcination. Other methods to produce borosilicate molecular sieves include using a combination of sodium hydroxide and aqueous ammonia together with an organic template as disclosed in 20 U.S. Patent 4,285,919, incorporated herein by reference, and using high concentrations of amine such as hexa-methylenediamine as described in European Patent Specification No:7081. British Patent Application 2,024,790 discloses formation of a borosilicate using 25 ethylene diamine with sodium hydroxide. Aluminosili-cates have been prepared with low sodium content using diamines containing four or more carbon atoms as described in European Published Patent Applications 669 and 11 362. U.S. Patents 4,139,600 and 4,151,189 30 describe methods to produce aluminosilicate sieves containing low sodium using diamines or C2-C5 alkyl amines.
A method to produce AMS-lB crystalline borosilicate molecular sieve which is low in sodium would be desir-35 able in that an exchange procedure to remove sodium would be unnecessary. Also a method to produce
A
crystalline borosilicate having a higher boron-content
1
i1-
y\
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than usually prepared by conventional techniques would be very advantageous. Further, a method to produce AMS-lB crystalline borosilicate without use of added alkali or ammonium hydroxides would be desirable. In addition a product formed from such method which shows increased activity over conventionally-prepared material would be most advantageous.
Summary of the Invention This invention is a method to prepare AMS-lB crystalline borosilicate molecular sieve comprising reacting under crystallization conditions, in substantial absence of a metal or ammonium hydroxide, an aqueous mixture containing an oxide of silicon, an oxide of boron, an alkylammonium cation or a precursor of an alkylammonium cation, and ethylenediamine, and the product formed from such method.
Brief Description of the Invention Conventionally, AMS-lB borosilicate molecular sieve is prepared by crystallizing an aqueous mixture of an oxide of boron, an oxide of silicon, and an organic template compound in the presence of an alkali metal hydroxide, usually sodium hydroxide. When such a mixture is crystallized, the resulting AMS-lB molecular sieve contains alkali metal, usually sodium,
ions to balance the negative framework charge caused by substitution of a boron atom for silicon in the crystalline sieve structure. However, when used for catalytic purposes, presence of sodium ion usually is detrimental. Typically, before a catalytic composition is made, the hydrogen form of AMS-lB is prepared by exchange with ammonium ion followed by drying and calcination. This invention is a method of directly crystallizing AMS-lB molecular sieve having a low sodium content which uses less of expensive alkylammonium template compound than used in conventional preparations.
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In another aspect of this invention, AMS-lB crystalline borosilicate can be formed having higher boron contents than usually formed using conventional techniques.
Still another aspect of this invention is the product formed by a method which does not use a metal or ammonium hydroxide and in which AMS-lB crystalline borosilicate is formed from an aqueous mixture containing a low water to silica ratio.
According to this invention, AMS-lB crystalline molecular sieve is formed by crystallizing an aqueous mixture containing sources for an oxide of boron, an oxide of silicon, a tetraalkylammonium compound and ethylenediamine in the substantial absence of a metal or ammonium hydroxide.
Typically, the mole ratios of the various reactants can be varied to produce the crystalline borosilicates of this invention. Specifically, the molar ratio of initial reactant concentration of silica to oxide of boron can range from about 2 to about 400, preferably about 4 to about 150 and most preferably about 5 to about 80. The molar ratio of water to silica can range from about 2 to about 500, preferably about 5 to about 60 and most preferably about 10 to about 35. It has been found that preparation using a water to silica molar ratio of about 10 to about 15 can be especially preferable. The molar ratio of ethylene-diamine to silicon oxide used in the preparation of AMS-lB crystalline borosilicate according to this invention should be above about 0.05, typically below about 5, preferably about 0.1 to about 1.0, and most preferably about 0.2 to about 0.5. The molar ratio of alkylammonium template compound or precursor to silicon oxide useful in the preparation of this invention can range from 0 to about 1 or above,
typically above about 0.005, preferably about 0.01 to
20111
about 0.1, and most preferably from about 0.02 to about 0.05.
It has been found that AMS-lB crystalline borosilicate molecular sieve formed using the method of this invention in which such sieve is formed in a mixture containing a low water to silica ratio exhibits surprisingly high catalytic activity in hydrocarbon conversion such as in converting ethylbenzene. AMS-lB crystalline borosilicate compositions showing exceptional conversion activity can be prepared by crystallizing a mixture of an oxide of silicon, an oxide of boron, a alkylammonium compound and ethylenediamine such that the initial reactant molar ratios of water to silica range from, about 5 to about 25, preferably about 10 to about 22 and most preferably about 10 to about 15. In addition, preferable molar ratios for initial reactant silica to oxide of boron range from about 4 to about 150, more preferably about 5 to about 80 and most preferably about 5 to about 20. The molar ratio of ethylenediamine to silicon oxide used in the preparation of AMS-lB crystalline borosilicate according to this invention should be above about 0.05, typically below about 5, preferably about 0.1 to about 1.0, and most preferably about 0.2 to about 0.5. The molar ratio of alkylammonium template compound or precursor to silicon oxide useful in the preparation of this invention can range from 0 to about 1 or above, typically above about 0.005, preferably about 0.01 to about 0.1, and most preferably about 0.01 to about 0.1, and most preferably from about 0.02 to about 0.05.
It is noted that the preferable amount of alkylammonium template compound used in the preparation of this invention is substantially less than that required to produce AMS-lB conventionally using an alkali metal cation base. The decrease in use of such alkylammonium compound substantially lowers the cost of preparation.
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The amount of alkylammonium template used in preparations of this invention generally is in inverse proportion to the amount of ethylenediamine used. If no alkylammonium compound is employed, preparations using ethylenediamine in a molar ratio to silica of above about 1 usually form highly crystalline borosilicate molecular sieves. At molar ratios below about 1 partially crystalline material is formed and at molar ratios below about 0.5 amorphous product is obtained. However, if an alkylammonium compound is included in a preparation using ethylenediamine in a molar ratio to silica less than about 1, crystalline AMS-lB borosilicate is formed. As the proportion of ethylenediamine is decreased, generally the proportion of alkylammonium compound may be increased. Nevertheless, in any preparation of this invention no added hydroxide, such as in the form of an alkali or alkaline earth metal hydroxide or ammonium hydroxide, is used, although in substantial amounts may be present as impurities in starting reagents.
By regulation of the quantity of boron oxide (represented as B2O3) in the reaction mixture, it is possible to vary the Si02/B2C>3 (silica/boria) molar ratio in the final product, although in many instances an excess of boron oxide is used in a preparation.
AMS-lB crystalline borosilicate molecular sieve generally can be characterized by the x-ray pattern listed in Table I and by the composition formula (in terms of oxides):
0.9 +0.2 M2/nO : B2O3 : ySi02 : ZH2O wherein M is at least one cation, n is the valence of the cation, y is between 4 and about 600 and z is between 0 and about 160.
201113
Table I
O
d-Spacinq A (1)
Assigned Strength (2)
11.2 + 0.2' 10.0 + 0.2
W-VS
W-MS
W-M
VS
MS
M-MS
W-M
W-M
.97 + 0.07 3.82 + 0.05 3.70 + 0.05 3.62 + 0.05 2.97 + 0.02 1.99 + 0.02
(1) Copper K alpha radiation
(2) VW = very weak; W = weak; M = medium; MS = medium strong; VS = very strong
It has been found that preparations of AMS-lB by conventional techniques using sodium hydroxide sometimes contain searlesite as an impurity especially if the concentration of reactants in the crystallizing mixture is high. However, AMS-lB crystalline borosilicate can be prepared according to this invention using higher than conventional concentrations of reactants without producing searlesite. In addition, preparations at higher concentrations of reactants produce a crystalline borosilicate with increased activity in some hydrocarbon conversion processes. Further, higher reactant concentration preparations are economically more efficient.
More specifically, the material of the present invention is prepared by mixing in water (preferably distilled or deionized) ethylenediamine, a boron oxide source, and, optionally, an organic template compound such as tetra-n-propylammonium bromide. The order of addition usually is not critical although a typical procedure is to dissolve ethylenediamine and boric acid in water and then add the template compound. Generally, the silicon oxide compound is added with intensive mixing such as that performed in a Waring
t t
Blendor. The resulting slurry is transferred to a closed crystallization vessel for a suitable time.
After crystallization, the resulting crystalline product can be filtered, washed with water, dried, and calcined.
During preparation, acidic conditions should be avoided. Advantageously, the pH of the reaction system falls within the range of about 8 to about 12 and most preferably between about 9 and about 10.5. The pH depends on the concentration of ethylenediamine.
Examples of oxides of silicon useful in this invention include silicic acid, sodium silicate, tetraalkyl silicates and Ludox, a stabilized polymer of silicic acid manufactured by E. I. du Pont de Nemours & Co. Typically, the oxide of boron source is boric acid although equivalent species can be used such as sodium borate and other boron-containing compounds.
Since AMS-lB crystalline borosilicate prepared according to this invention requires no alkali metal cation and thus requires no ion exchange procedure before formulation into a catalytic composition, it is advantageous that the starting materials, such as silicon oxide and boron oxide, contain as little alkali crystalline borosilicate include alkylammonium cations or precursors thereof such as tetraalkylammonium compounds. Useful organic templates include tetra-n-propylammonium bromide and tetra-n-propylammonium hydroxide.
In a more detailed description of a typical preparation of this invention, suitable quantities of ethylenediamine and boric acid (H3BO3) are dissolved in distilled or deionized water followed by addition of the organic template. The resulting slurry is transferred to a closed crystallization vessel and metal ion contaminant as practicable.
Organic templates useful in preparing AMS-lB
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reacted usually at a pressure at least the vapor pressure of water for a time sufficient to permit crystallization which usually is about 0.25 to about 20 days, typically is about one to about ten days and preferably is about two to about seven days, at a temperature is maintained below the decomposition temperature ranging from about 100° to about 250°C, preferably about 125° to about 200°C. The crystallizing material can be stirred or agitated as in a rocker bomb. Preferably, the crystallization temperature is maintained below the decomposition temperature of the organic template compound.
Especially preferred conditions are crystallizing at about 145°C for about two to about four days. Samples of material can be removed during crystallization to check the degree of crystallization and determine the optimum crystallization time.
The crystalline material formed can be separated and recovered by well-known means such as filtration with washing. This material can be mildly dried for anywhere from a few hours to a few days at varying temperatures, typically about 25-200°C, to form a dry cake which can then be crushed to a powder or to small particles and extruded, pelletized, or made into forms suitable for its intended use. Typically, materials prepared after mild drying contain the organic template compound and water of hydration within the solid mass and a subsequent activation or calcination procedure is necessary, if it is desired to remove this material from the final product. Typically, mildly dried product is calcined at temperatures ranging from about 260° to about 850°C and preferably about 525° to about 600°C. Extreme calcination temperatures or prolonged crystallization times may prove detrimental to the crystal structure or may totally destroy it. General there is no need to raise the calcination temperatur beyond about 600°C in order to remove organic mater from the originally formed crystalline material.
201113
Typically, the molecular sieve material is dried in a forced draft oven at about 145°-165°C for about 16 hours and is then calcined in air in a manner such that the temperature rise does not exceed 125°C per hour until a temperature of about 540°C is reached. Calcination at this temperature usually is continued for about 4 to 16 hours.
A catalytically active material can be placed onto the borosilicate structure by ion exchange, impregnation, a combination thereof, or other suitable contract means. Preferred replacing cations are those which render the crystalline borosilicate catalytically active, especially for hydrocarbon conversion. Typical catalytically active ions include hydrogen, metal ions of Groups IB, IIA, IIB, IIIA, and VIII, and of manganese, vanadium, chromium, uranium, and rare earth elements.
Also, water soluble salts of catalytically active materials can be impregnated onto the crystalline borosilicate of this invention. Such catalytically active materials include hydrogen, metals of Groups IB, IIA, IIB, IIIA, IVB, VIB, VIIB, and VIII, and rare earth elements.
In another aspect of this invention a catalytically active material can be placed onto the borosilicate structure by incorporating such catalytically active material in the initial crystallization. Generally the same elements can be placed onto the sieve structure in this manner as can be ion exchanged or impregnated. Specific metal ions which can be incorporated in such manner include ions of Ni, Co, Mn, V, Ti, Cu, Zn, Mo and Zr.
Ion exchange and impregnation techniques are well known in the art. Typically, an aqueous solution of a cationic species is exchanged one or more times at about 25° to about 100°C. Impregnation of a catalytically active compound on the borosilicate or
2 0 11 1
-li-
on a composition comprising the crystalline borosilicate suspended in and distributed throughout a matrix of a support material such as a porous refractory inorganic oxide such as alumina, often results 5 in a suitable catalytic composition. A combination of ion exchange and impregnation can be used. Presence of sodium ion in a composition usually is detrimental to catalytic activity. AMS-lB-based catalyst compositions useful in xylene isomerization can be based on 10 hydrogen form sieve or on that prepared by ion exchange with nickelous nitrate or by impregnation with ammonium molybdate.
The amount of catalytically active material placed on the AMS-lB borosilicate can vary from less than 15 one weight percent to about thirty weight percent,
typically from about 0.05 to about 25 weight percent, depending on the process use intended. The optimum amount can be determined easily by routine experimentation.
The AMS-lB crystalline borosilicate useful in this invention may be incorporated as a pure material in a catalyst or adsorbent, or may be admixed with or incorporated within various binders or matrix materials depending upon the intended process use. The crystal-25 line borosilicate can be combined with active or inactive materials, synthetic or naturally-occurring zeolites, as well as inorganic or organic materials which would be useful for binding the borosilicate. Well-known materials include silica, silica-alumina, 30 alumina, alumina sols, hydrated aluminas, clays such as bentonite or kaoline, or other binders well known in the art. Typically, the borosilicate is incorporated within a matrix material by blending with a sol of the matrix material and gelling the resulting mixture. 35 Also, solid particles of the borosilicate and matrix material can be physically admixed. Typically, such borosilicate compositions can be pelletized or extruded
-12- 201113
into useful shapes. The crystalline borosilicate content can vary anywhere up to 100 wt.% of the total composition. Catalytic compositions can contain about 0.1 wt.% to about 100 wt.% crystalline borosilicate 5 material and typically contain about 2 wt.% to about 65 wt.% of such material.
Catalytic compositions comprising the crystalline borosilicate material of this invention and a suitable matrix material can be formed by adding a finely-10 divided crystalline borosilicate and a catalytically active metal compound to an aqueous sol or gel of the matrix material. The resulting mixture is thoroughly blended and gelled typically by adding a material such as aqueous ammonia. The resulting gel can be 15 dried and calcined to form a composition in which the crystalline borosilicate and catalytically active metal compound are distributed throughout the matrix material.
Specific details of catalyst preparations are 20 described in U.S. Patent 4,268,420.
This invention is demonstrated but not limited by the following Examples and Comparative Runs.
Examples I-VI
A series of reaction mixtures prepared by dis-25 solving ethylenediamine, boric acid, and tetra-n-propylammonium bromide (TPABr) in distilled water.
While agitating this mixture in a Waring Blendor at maximum speed, a quantity of Ludox (40 wt.% SiC>2) was added quickly; agitation was continued for about ten 30 minutes. The resulting mixture was charged to a stirred autoclave and digested at 145°C. After the mixture was crystallized, the resulting product was filtered washed with distilled water, dried overnight at 130^jcy and calcined at 530°C for four hours preceded by a jp„ 1 35 programmed preheating at a temperature increase of more than 125°C/hour. The products were analyzed x-ray diffraction and elemental analysis. Products
* 11 A suitable matrix material" is a material that is capable of having the molecular sieve dispersed within the matrix material, with the matrix material acting as a binding material.
? 0 1 1!3
characterized as AMS-lB had an x-ray diffraction pattern similar to that contained in Table I and elemental analysis showing incorporation of boron. Details of these preparations and analyses are summarized in 5 Table II.
A catalyst composition was prepared by dispersing the above calcined sieve in PHF-alumina which is initially an acetic acid stabilized gamma alumina hydrosol containing about 9.8 wt.% AI2O3. Ten grams 10 of calcined sieve were added and thoroughly mixed with 405 grams of alumina hydrosol. The mixture was gelled (solidified) with addition of 60 milliliters of concentrated aqueous ammonia. The resulting solid was dried overnight in a forced air oven at 130°C. 15 The dried solid was program calcined at 530°C with the program as described above. The calcined solid was crushed and sized to 18 to 40 mesh (U.S. Sieve Series). Five grams of the 18-40 mesh catalyst were placed in a micro aromatics test unit having a 0.5 20 inch inside diameter tubular reactor and preconditioned for two hours at 399°C and 165 psig pressure with 0.3 SCF per hour flow of hydrogen. Xylene isomerization test results are shown in Table III.
^11
Reagents (grams)
Water
Ethylenediamine Boric Acid Tetra-n-propyl-
ammonium Bromide Ludox (HS-40, 40 wt.% Si02)
-14-Table II
2,000 79 102
27
666
Examples
II
6,000 120 306.6
80
2,000
III
2,000 40 102.7
81
666
Mole Ratios of
Reagents
Si02B203 H20/Si02 Ethylene-diamine/SiC>2 TPABr/Si02
Crystallization
Conditions Time (days) Temperature (°C) 25 Initial pH
.38 30
0.30 0.023
6
145 9.8
.38 30
0.15 0.023
3
16 5 8.8
.38 30
0.15 0.069
4
145 8.8
Elemental Analysis (wt.%) Si02 B
Na
93.5 0.82 0.01
94.7
0.031
92.2
0.030
2011
Table II (cont'd.) Examples
Reagents (grams)
Water
Ethylenediamine Boric Acid Tetra-n-propyl-
ammonium Bromide Ludox (HS-40, 40 wt.% SiC>2)
IV
2,000 132 102.7
81
666
9,000 600 460
120 3,000
VI
7,800 433 400
104
2,600 t1)
Mole Ratios of
Reagents
Si02/B2C>3
H20/Si02 Ethylene-diamine/Si02 20 TPABr/SiC>2
.38 30
0.45 0.069
.38 30
0.45 0.023
.38 30
0.375 0.023
Crystallization
Conditions Time (days) Temperature (°C) Initial pH
7
145 10.0
6
145 10.0
3
145 9.8
Elemental Analysis (wt.%) 30 Si02 B
Na
95.7 0.02
93.2 0.86 0.005
89.8 0.88 0.01
(1) Ludox AS-40 used which contains 40 wt.% SiC>2 and 35 0.08 wt.% Na20; Ludox HS-40 contains about 0.4
wt.% Na20.
2 01113
Table III Test Runs from Examples
Conditions
II (2)
Reactor
Temp. (°C)
399
399
Reactor
Pressure
(psig)
165
165
Space Velocity
7.
2
4
.9
(WHSV, hr"1)
Hydrogen/
hydrocarbon
4.
9
.7
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0.24
0.
27
0.00
0
.22
Naphthenes
Benzene
0.03
2.
37
0.03
1
.39
Toluene
0.07
0.
51
0.06
0
.35
Ethyl-
benzene
13.78
9.
85
14.30
12
.20
p-Xylene
.16
.
07
8.98
16
.84
m-Xylene
52.67
44.
11
53.25
46
.24
o-Xylene
22.98
19.
42
23.31
.79
C9+
0.07
3.
39
0.07
1
.97
Results(1)
PATE -
p-Xylene
104.
1
73
.5
Ethylbenzene
conversion (%)
28.
14
.7
(1) PATE = Percent Approach to Theoretical Equilibrium
(2) Test run on 20 grams of catalyst in a Berty reactor. Lower PATE appears to be a characteristic of this reactor.
11 |
Cond itions Reactor 5 Temp. (°C)
Reactor Pressure (psig)
Space Velocity 10 (WHSV, hr"1)
Hydrogen/ hydrocarbon (molar ratio) Components 15 (wt.%)
Paraffins and
Naphthenes Benzene Toluene 20 Ethyl-
benzene p-Xylene m-Xylene o-Xylene 25 C9+
Results(1)
PATE -
p-Xylene Ethylbenzene 30 conversion (%)
Table III (cont'd.)
Test Runs from Examples
III
399
Feed 0.01
0.07 0.07
14.59 8.86 52.50 23.84 0.08
165 6.9
.1
0.43
1.26 0.41
12.69 16.25 46.41 21.10 1.46
68.6
13.0
Feed 0.24
0.03 0.07
13.78 10.16 52.67 22.98 0.07
IV
399
165 6.9
.0
0.18
0.94 0.33
12.47 20.19 44.50 20.17 1.22
102.3
9.5
(1) PATE = Percent Approach to Theoretical Equilibrium
2011
Table III (cont'd.)
Conditions
V
VI
Reactor
Temp. (°C)
399
399
Reactor
Pressure
(psig)
165
165
Space Velocity
.0
6.9
(WHSV, hr"1)
Hydrogen/
hydrocarbon
.0
.0
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0.00
0
.26
0.24
0.29
Naphthenes
Benzene
0.03
1
.96
0.03
2.43
Toluene
0.06
0
.55
0.07
0.54
Ethyl-
benzene
14.30
.85
13.78
9.73
p-Xylene
8.98
16
.88
.16
.01
m-Xylene
53.25
46
.18
52.67
44.19
o-Xylene
23.31
.34
22.98
19.39
c9+
0.07
2
.97
0.07
3.42
Results(1)
PATE -
p-Xylene
74
.8
3.5
Ethylbenzene
conversion (%)
24
.1
29.4
(1) PATE = Percent Approach to
Theoretical
Equilibrium
V
201 1 1
Example VII
This example demonstrates crystallizing a crystalline borosilicate together with a nickel salt according to the method of this invention. A solution of 620 milliliters of ethylenediamine, 460 grams of boric acid, 120 grams of TPABr and 90 grams of Ni(CH3COO)2 *4H2O in 9,000 milliliters of water was placed in a five-gallon autoclave followed by 3,000 grams of Ludox HS-40. The autoclave was closed and maintained at 145°C for seven days. The resulting crystalline product after washing, drying and calcination had a 1.26 wt.% nickel content. A 20% sieve/80% AI2O3 catalyst composition was formed and tested for xylene isomerization and ethylbenzene conversion. The results showed a 37% ethylbenzene conversion and grater than 100% p-xylene approach to theoretical equilibrium.
Example VIII
An AMS-lB crystalline borosilicate was prepared using increased concentrations of reactants with respect to the water diluent. The molecular sieve was prepared in a manner similar to that described in Examples I-VI except that proportionately less water was used.
Details of the preparation and analyses are shown in Table IV. A catalyst composition was prepared by dispersing 10 grams of calcined sieve as described above in 405 grams of PHF-alumina hydrosol. The mixture was gelled with 20 milliliters of concentrated aqueous ammonia. The resulting solid was dried overnight in a forced air oven at 130°C and then program calcined at 530°C for twelve hours preceded by a temperature increase of 125°C/hour. The calcined solid was crushed and sized to 18-40 mesh (U.S. Sieve Series) and five grams of such 18-40 mesh catalyst were placed into a micro aromatics test unit having a 0.5-inch
Z01 t
inside diameter tubular reactor and preconditioned for two hours at 399°C an 165 psig pressure with 0.3 SCF per hour flow of hydrogen. Xylene isomerization test results are shown in Table V.
-21-Table IV
Reagents (grams)
Water
Ethylenediamine Boric Acid
Tetra-n-propylammonium
Bromide Ludox (HS-40f 40 wt.% SiC>2)
2011
Example VIII
,400 720 920
240
6,000
Mole Ratios of Reagents
SiC>2/B203 20 H20/SiC>2
Ethylenediamine/Si02 TPABr/Si02
.38 12.5 0.30 0.023
Crystallization Conditions
Time (days) Temperature (°C) Initial pH
7
145 9.8
Elemental Analysis (wt.%) B
1.09
2 0111
Conditions Reactor Temp. (°C) Reactor Pressure
(psig)
Space Velocity (WHSV, hr-1) Hydrogen/hydrocarbon
(molar ratio) Components (wt.%) Paraffins and
Naphthenes Benzene Toluene Ethylbenzene p-Xylene m-Xylene o-Xylene C9+
Results(1)
PATE - p-Xylene Ethylbenzene conversion (%)
Table V
Test Run for Example VIII
399 165
6.8
4.6
Feed 0.00
0.05 0.05 13.33 10.05 53.55 22.93 0.06
0.02
3.51 0.84 7.63 19.96 43.24 19.21 5.60
105.8 42.7
(1)
PATE = Percent Approach to Theoretical Equilibrium
Exaraples IX-XII A series of experiments was performed using ethylenediamine with no added alkylammonium salt. Preparations were attempted in a manner similar to 5 that described in Examples I-VI except that no tetra-n-propyl ammonium bromide was used. Details of the preparation and analyses are shown in Table VI.
2011
Reagents
(grams)
Water
Ethylenediamine Boric Acid Ludox (HS-40, 40 wt.% Si02)
Mole Ratios of
Reagents
Si02B203 H20/S i02 15 Ethylene-
diamine/Si02
Crystalli zation Conditions 20 Time (days)
Temperature (°C)
AMS-lB (% crystal linity
-24-Table VI
Examples (Run)
IX X XI
850 2,000 2,000
972 495 371
102 460
400 666 666
16.67 5.38 5.38
22.7 30 30
3.65 1.86 1.39
5 5
150 150 150
81 82 >80
Elemental Analysis (wt.%)
B
Na
0.92
2 011 | 3
Table VI (cont'd.)
Examples (Run)
Elemental Analysis (wt.%) B
Na
Reagents
(grams) XII
Water 2,000 2,000
Ethylenediamine 248 79
Boric Acid 400 102 Ludox (HS-40,
40 wt.% SiC>2) 666 666
Mole Ratios of Reagents
Si02B2C>3 0.186 0.186
H20/SiC>2 30 30 15 Ethylene-
diamine/Si02 0.93 0.30
Crystalli zation Conditions
Time (days) 5 5
Temperature (°C) 150 150
AMS-lB (% crystal-
linity 43 0
- y' L ti . L! C~JJ
Examples XIII-XIV A series of preparations of AMS-lB crystalline borosilicate was conducted according to this invention to show the substantial increase hydrocarbon conversion 5 catalytic activity of AMS-lB material made using increased concentrations of reactants with respect to water. The AMS-lB crystalline borosilicate of Example XIII was prepared using ethylenediamine with no added metal hydroxide and with a low water to silica 10 molar ratio. The material prepared in Example XIII is similar to that prepared in Example VIII. The AMS-lB of Example XIV was prepared in a manner similar to that described in Examples I-VII using a higher water to silica molar ratio. Comparative Run B was 15 prepared using sodium hydroxide as the base with no ethylenediamine.
Xylene isomerization/ethylbenzene conversion tests using catalysts prepared from the materials of Examples XIII and IV and Comparative Run B show the 20 catalyst prepared from the Example XIII material to have a substantially higher ethylbenzene conversion activity as compared to similarly-formulated catalysts made from the other materials.
The AMS-lB crystalline borosilicate molecular 25 sieve of Example XIII was prepared by mixing in an autoclave distilled water, ethylenediamine, boric acid, tetra-n-propylammonium bromide and Ludox HS-40 silica sol (40 wt.% solids). The resulting mixture was digested for four days at 145°C, after which time 30 the product was washed thoroughly with distilled water., dried at 130°C for 16 hours and calcined at 535°C for 12 hours after a programmed rate of heating of 125°C/hour for four hours. The resulting molecular sieve had particle sizes of 0.1-0.5 micrometers. Mole 35 ratios of reagents were Si02/B2C>3 = 5.38;
2 01113
H20/Si02 = 15; ethylenediamine/Si02 = 0.30;
TPABr/Si02 = 0.023. The AMS-lB crystalline borosilicate of Example XIII had a boron content of 0.85 wt.%.
Catalyst compositions were prepared by dispersing the above-prepared sieve in 1667 grams of PHF gamma alumina hydrosol (9.6 wt.% solids) and gelling with 80 milliliters of concentrated aqueous ammonia (28 wt.% NH3). Several catalysts were prepared using different sieve/alumina matrix weight ratios. The following amounts of sieve were used for the corresponding sieve/alumina matrix weight ratios: 20/80 = 40.0 grams; 30/70 = 68.6 grams; 35/65 = 86.2 grams; 40/60 = 106.7 grams; 45/55 = 130.9 grams; and 55/45 = 195.6 grams. The gelled solid was dried overnight in a forced air oven at 130°C, ground to 18-40
I
mesh (U.S. Sieve Series), and then calcined at 537°C for 12 hours preceded by a temperature increase of 125°C/hour. Five to ten grams of the resulting calcined catalyst was placed into an micro aromatics test unit having a 0.5-inch inside diameter tubular reactor and preconditioned for two hours at 371°C and 250 psig pressure with 0.3 SCF per hour hydrogen flow. Xylene isomerization/ethylbenzene conversion test results are shown in Table VII.
AMS-lB crystalline borosilicate molecular sieve of Example XIV was prepared in a manner similar to that described in Example I using Ludox HS-40 (40 wt.% SiC>2) , tetrapropylammonium bromide, boric acid, ethylenediamine and water such that the molar ratios of reactants were Si02/B203 =5.38;
H20/SiC>2 = 30; ethylenediamine/SiC>2 = 0.30 and TPABr/SiC>2 = 0.023. The reactant mixture was digested at 132-136°C for 4.5 days after which time the resulting solids were washed thoroughly with distilled water, dried at 130°C and calcined at 530°C.
11
The resulting AMS-lB crystalline borosilicate molecular sieve had particle sizes of 0.2-2 micrometers and a boron content of 0.85 wt.%. Catalyst compositions with various sieve/alumina matrix weight ratios were 5 prepared as described for Example XIII.
For a 20/80 sieve/alumina matrix catalyst,
417 grams of PHF gamma alumina sol (9.8 wt.% solids), 10.0 grams of sieve and 60 milliliters of concentrated aqueous ammonia (28 wt.% NH3) gelling agent were used; 10 for a 30/70 silica/matrix catalyst, 1215.9 grams of alumina sol, 51.39 grams of sieve and 120 milliliters of aqueous ammonia were used; for a 35/65 catalyst 1215.9 grams of alumina sol, 64.56 grams of sieve and 60 milliliters of aqueous ammonia were used; and for 15 a 40/60 catalyst 405.3 grams of alumina sol, 26.67
grams of sieve and 60 milliliters of aqueous ammonia were used. These catalyst compositions were tested for xylene isomerization/ethylbenzene conversion as described for Example XIII and the results shown in 20 Table VIII.
AMS-lB crystalline borosilicate molecular sieve of Comparative Run B was prepared by digesting a mixture of water, boric acid, sodium hydroxide, tetrapropylammonium bromide and Ludox HS-40 (40 wt.% 25 SiC>2) for 2.5 days at 145°C. The molar ratios of reactants were: Si02/B2C>3 = 5.06; H20/Si02 = 30.5; Na0H/Si02 = 0.42; and TPABr/SiC>2 = 0.14. Resulting solids were washed with water, dried and calcined. The calcined sieve then was exchanged twice with an 30 ammonium acetate solution at 90°C for two hours. Two grams of ammonium acetate in ten grams of water per gram of sieve were used in the exchanges. The resulting exchanged sieve was dried and calcined and then formulated into catalysts incorporated into a gamma alumina 35 matrix as described above for Example XIII. The AMS-lB
? © 11
crystalline borosilicate of Run B had particle sizes of 0.1-0.5 micrometers and a boron content of 0.5 wt.%. The quantities of PHF alumina sol (9.7 wt.% solids), sieve and aqueous ammonia for various sieve/alumina matrix weight ratios are: 20/80 - 2060 grams alumina sol, 50 grams of sieve and 400 milliliters aqueous ammonia; 30/70 - 1500 grams alumina sol, 62.3 grams of sieve and 218 milliliters aqueous ammonia; 35/65 - 1675.3 grams alumina sol, 87.5 grams of sieve and 325 milliliters of aqueous ammonia;
40/60 - 1546.4 grams alumina sol, 100 grams of sieve and 300 milliliters of aqueous ammonia. These catalyst compositions were tested for xylene isomerization/ethyl-benzene conversion as described for Example XIII and the results are shown in Table IX.
The data show that catalytic materials formulated from AMS-lB crystalline borosilicate molecular sieve of Example XIII are significantly more active for ethylbenzene conversion than similarly formulated materials prepared as in Example XIV and Run B.
*
£, U I
Table VII
Test Runs from
Example
XIII
Sieve/Alumina
Matrix (wt. ratio)
/80
/70
Conditions
Reactor
Temp. (°C)
372
371
Reactor
Pressure
(psig)
250
250
Space Velocity
6.0
6.1
(WHSV, hr-1)
Hydrogen/
hydrocarbon
2.1
1.9
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0.01
0.08
0
0.02
Naphthenes
Benzene
0.04
2.03
0.05
2.43
Toluene
0.05
0.56
0.05
0.80
Ethyl
benzene
13.90
.35
13.33
8.89
p-Xylene
.32
.22
.05
.11
m-Xylene
52.90
44.06
53.55
43.85
o-Xylene
22.71
19.03
22.93
19.05
c9+
0.07
3.67
0.05
4.85
Results(1)
PATE -
p-Xylene
105.6
105.0
Ethylbenzene
conversion (%)
.6
33.3
Xylene Loss (wt.%) 3.06 4.27
(1) PATE = Percent Approach to Theoretical Equilibrium
Table Test
VII (cont'd.)
Runs from Example
XIII
Sieve/Alumina
Matrix (wt. ratio)
/65
40/60
Conditions
Reactor
Temp. (°C)
371
371
Reactor
Pressure
(psig)
250
250
Space Velocity
6.0
6.0
(WHSV, hr-1)
Hydrogen/
hydrocarbon
2.0
2.0
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0.01
0.14
0.01
0.19
Naphthenes
Benzene
0.04
3.39
0.04
3.94
Toluene
0.05
0.96
0.05
1.21
Ethyl
benzene
13.90
8.24
13.90
7.28
p-Xylene
.32
19.67
.32
19.36
m-Xylene
52.90
42.94
52.90
42.58
o-Xylene
22.71
18.61
22.71
18.25
c9+
0.07
6.05
0.07
7.19
Results(1)
PATE -
p-Xylene
105.1
104.5
Ethylbenzene
conversion (%)
40.7
47.6
Xylene Loss (wt.%)
.43
6.72
(1) PATE = Percent Approach to Theoretical Equilibrium
2 0 H
1
Table
VII (cont
'd.)
Test
Runs from Example
XIII
Sieve/Alumina
Matrix (wt. ratio)
45/55
55/45
Conditions
Reactor
Temp. (°C)
371
372
Reactor
Pressure
(psig)
250
250
Space Velocity
6.0
6.
0
(WHSV, hr-1)
Hydrogen/
hydrocarbon
2.0
2.
0
(molar ratio)
Components
(wt.%) Feed
Feed
Paraffins and 0
0.03
0.01
0.
16
Naphthenes
Benzene 0.05
3.14
0.04
3.
08
Toluene 0.05
1.07
0.05
0.
81
Ethyl
benzene 13.33
7.68
13.90
8.
67
p-Xylene 10.05
19.79
.32
19.
92
m-Xylene 53.55
43.32
52.90
43.
36
o-Xylene 22.93
18.74
22.71
18.
83
Cg+ 0.05
6.23
0.07
.
17
Results(1)
PATE -
p-Xylene
104.5
105.
Ethylbenzene
conversion (%)
42.5
37.
7
Xylene Loss (wt.%)
.76
4.
48
<?■
I J
(1) PATE = Percent Approach to Theoretical Equilibrium
7 ^ ? ? y
Table VIII Test Runs from Example
XIV
Sieve/Alumina Matrix (wt. ratio) 5 Conditions Reactor
Temp. (°C)
Reactor Pressure 10 (psig)
Space Velocity
(WHSV, hr-1) Hydrogen/ hydrocarbon 15 (molar ratio)
Components (wt.%) Feed
/65
372
250 6.0
2.0
Feed
40/60
371
250 5.9
2.1
Paraffins and 0.01
0
.09
0
0.02
Naphthenes
Benzene
0.04
2
.77
0.04
1.88
Toluene
0.05
0
.80
0.06
0.77
Ethyl
benzene
13.90
9
.12
14.01
.51
p-Xylene
.32
.00
.36
.09
m-Xylene
52.90
43
.49
52.73
44.00
o-Xylene
22.71
18
.88
22.74
18.89
c9+
0.07
4
.86
0.06
3.85
Results(1)
PATE -
p-Xylene Ethylbenzene
105
.6
105.1
conversion
(%)
34
.4
.0
Xylene Loss
(wt.%)
4
.16
3.41
(1) PATE =
Percent Approach to
Theoretical
Equilibrium
2 01175
Table VIII (cont' Test Runs from a.)
Example
XIV
Sieve/Alumina
Matrix (wt. ratio)
/80
/70
Conditions
Reactor
Temp. (°C)
372
372
Reactor
Pressure
(psig)
250
250
Space Velocity
6.1
6.3
(WHSV, hr-1)
Hydrogen/
hydrocarbon
2.2
1.9
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0
0.02
0
0.03
Naphthenes
Benzene
0.05
1.67
0.05
2.23
Toluene
0.05
0.59
0.05
0.95
Ethyl
benzene
13.33
.19
13.33
9.34
p-Xylene
.05
.42
.05
.09
m-Xylene
53.55
44.53
53.55
43.68
o-Xylene
22.93
19.31
22.93
19.02
c9+
0.05
3.28
0.06
4.66
Results(1)
PATE -
p-Xylene
105.1
105.3
Ethylbenzene
conversion (%)
23.6
29.9
Xylene Loss (wt
.%)
2.81
4.31
(1) PATE = Percent Approach to Theoretical Equilibrium
| n
-35-Table IX
Test Runs from Run B
Sieve/Alumina
Matrix (wt. ratio)
/65
40/60
Conditions
Reactor
Temp. (°C)
373
373
Reactor
Pressure
(psig)
250
250
Space Velocity
6.0
6.0
(WHSV, hr"1)
Hydrogen/
hydrocarbon
2.0
2.0
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0
0.01
0
0.07
Naphthenes
Benzene
0.03
2.37
0.03
2.55
Toluene
0.05
0.58
0.05
0.62
Ethyl
benzene
14.32
.22
14.32
.00
p-Xylene
.14
19.94
.14
19.86
m-Xylene
52.24
43.55
52.24
43.29
o-Xylene
23.18
18.94
23.18
18.88
c9+
0.04
4.41
0.04
4.74
Results(1)
PATE -
p-Xylene
104.8
105.0
Ethylbenzene
conversion (%)
28.6
.2
Xylene Loss (wt
.%)
3.49
3.84
(!) PATE = Percent Approach to Theoretical Equilibrium
20111
Table IX (cont'd.)
Test Runs from Run B
Sieve/Alumina
Matrix (wt. ratio)
/80
/70
Conditions
Reactor
Temp. (°C)
373
371
Reactor
Pressure
(psig)
250
250
Space Velocity
6.0
6.0
(WHSV, hr"1)
Hydrogen/
hydrocarbon
2.0
1.8
(molar ratio)
Components
(wt.%)
Feed
Feed
Paraffins and
0
0
1.16
1.15
Naphthenes
Benzene
0.03
1.33
0
2.27
Toluene
0.05
0.32
0.85
1.68
Ethyl
benzene
14.32
12.17
14.65
.97
p-Xylene
.14
.41
7.79
18.30
m-Xylene
52.24
44.08
49.74
40.00
o-Xylene
23.18
19.24
21.13
16.90
c9+
0.04
2.45
4.67
8.73
Results(1)
PATE -
p-Xylene
106.3
105.2
Ethylbenzene
conversion (%)
.0
.1
Xylene Loss (wt
.%)
1.84
4.51
(1) PATE = Percent Approach to Theoretical Equilibrium
37
Claims (26)
- A method of preparing an AMS-lB crystalline borosilicate molecular sieve as hereinbefore defined comprising reacting under crystallization conditions, in the substantial absence of a metal or ammonium hydroxide and in non-acidic conditions, an aqueous mixture containing an oxide of silicon, an oxide of boron, ethylenediamine in a molar ratio to silica of above 0.05, and, optionally, an alkylammonium cation or precursor of an alkylammonium cation.
- 2. The method of claim 1 wherein the alkylammonium cation is tetra-n-propylammonium cation.
- 3. The method of claim 1 wherein the molar ratio of alkylammonium cation or precursor of an alkylammonium cation to silica is between 0.005 and 1.0, the molar ratio of silica to oxide of boron is 2 to 400, and the molar ratio of water to silica is 2 to
- 4. The method of claim 3 wherein the alkylammonium cation is tetra-n-propylammonium cation.
- 5. The method of claim 1, 2, 3 or 4 wherein the source for oxide of boron is boric acid.
- 6. The method of claim 2 wherein the molar ratio of tetra-n-propylammonium cation or precursor to silica is 0.01 to 0.1, the molar ratio of ethylenediamine to silica is 0.1 to 1.0, the molar ratio of silica to oxide of boron is 5 to 80, and the molar ratio of water to silica is 5 to 60.
- 7. The method of claim 6 wherein the molar ratio of ■t'h ethylenediamine to silica is 0.2 to 0.5, the il c molar ratio of tetra-n-propylammonium cation or precursor to ^ silica is 0.02 to 0.05, and the molar ratio of water to silica 500. is 10 to 35. 201113 -38-
- 8. The method of claim 6 wherein the molar ratio of water to silica is 10 to 15.
- 9. The method of claim 1 wherein a catalytically active material is placed on the borosilicate. 5
- 10. The method of claim 1 wherein the crystal lizing mixture is maintained at 125°C to 200°C for one to ten days.
- 11. The method of claim 1 wherein tl^e molecular sieve is incorporated within a suitable matrix material as hereinbefore defined. 10
- 12. The method of claim 11 wherein the matrix material is silica, silica-alumina or alumina.
- 13. The method of claim 1 wherein ions of nickel, cobalt, manganese, vanadium, titanium, copper, zinc, molybdenum or zirconium are incorporated within the 15 crystallizing, mixture,
- 14. A method of preparing/AMS-lB crystalline borosilicate molecular sieve comprising reacting under crystallization conditions, insubstantial absence of a metal or amonium hydroxide, an aqueous mixture 20 containing an oxide of silica, an oxide of boron, ethylenediamine in a molar ratio to silica of above 0.05, and, optionally, an alkylammonium cation or precursor o£ an alkylammonium cation; wherein the molar ratio/silica to oxide of boron is ^ 4 to 25 150 and the molar ratio of water to silica is 5 to below 25.
- 15. The method of claim 14 wherein the molar ratio of water to silica is 10 to 22.
- 16. The method of claim 14 or 15 wherein the 30 molar ratio of alkylammonium cation or precursor to silica is 0.01 to 0.1 and the molar ratio of ethylenediamine to silica is 0.1 to 1.0
- 17. The method of claim 14 wherein the alkyl- 35 ammonium cation is tetra-n-propylammonium cal % 201113 10 15 20 25 -39-
- 18. The method of claim 15 wherein the alkylammonium cation is tetra-n-propylammoniura cation.
- 19. The method of claim 18 wherein the molar ratio of tetra-n-propylammonium cation to silica is 0.01 to 0.1, the molar ratio of silica to oxide of boron is 5 to 80, and the molar ratio of ethylenediamine to silica is 0.1 to 1.0.
- 20. The method of claim 19 wherein the molar ratio of water to silica is 10 to 15.
- 21. The method of claim 18 wherein the molar ratio of tetra-n-propylammonium cation to silica is 0.02 to 0.05, the molar ratio of silica to oxide of boron is 5 to 20 and the molar ratio of ethylenediamine to silica is 0.2 to 0.5.
- 22. The method of claim 21 wherein the molar ratio of water to silica is 10 to 15.
- 23. The method of claim 17, 18, 19 or 21 wherein the source for oxide of boron is boric acid and the source for tetra-n-propylammonium cation is tetra-n-propylammonium bromide.
- 24. The AMS-lB crystalline borosilicate formed by the method of claim 14, 15, 17, 18, 19, 20, 21 or 22.
- 25. A method of manufacturing molecular sieves as claimed in Claim 1 / substantially as specifically described herein in any one of the Examples.
- 26. Molecular sieves manufactured by a method as claimed in.Claim 1 / substantially as specifically described herein in any one of the Examples. iPANY ys AREY
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US27920781A | 1981-06-30 | 1981-06-30 |
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JP (1) | JPS5826024A (en) |
EG (1) | EG15822A (en) |
ES (1) | ES8304519A1 (en) |
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US9168513B2 (en) | 2012-02-07 | 2015-10-27 | Basf Se | Process for preparation of zeolitic material |
CN104302577A (en) * | 2012-02-07 | 2015-01-21 | 巴斯夫欧洲公司 | Process for the preparation of a zeolitic material |
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US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
US4269813A (en) * | 1977-09-26 | 1981-05-26 | Standard Oil Company (Indiana) | Crystalline borosilicate and process of preparation |
IT1096596B (en) * | 1978-06-22 | 1985-08-26 | Snam Progetti | SYNTHETIC SILICA-BASED MATERIAL |
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-
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