GB1601915A - Method of preparation of large crystal alumino-silicate zeolite catalyst - Google Patents
Method of preparation of large crystal alumino-silicate zeolite catalyst Download PDFInfo
- Publication number
- GB1601915A GB1601915A GB18959/78A GB1895978A GB1601915A GB 1601915 A GB1601915 A GB 1601915A GB 18959/78 A GB18959/78 A GB 18959/78A GB 1895978 A GB1895978 A GB 1895978A GB 1601915 A GB1601915 A GB 1601915A
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- GB
- United Kingdom
- Prior art keywords
- crystallization
- ammonium compound
- alkyl ammonium
- bromide
- agitation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 40
- 239000013078 crystal Substances 0.000 title claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 32
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims description 19
- 239000010457 zeolite Substances 0.000 title claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003054 catalyst Substances 0.000 title description 7
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 238000013019 agitation Methods 0.000 claims description 26
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 150000003868 ammonium compounds Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000010899 nucleation Methods 0.000 claims description 5
- 230000006911 nucleation Effects 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- RULRTQRLYQBEHV-UHFFFAOYSA-N CC(=O)CC.C(CC)Br.C(CC)N(CCC)CCC Chemical compound CC(=O)CC.C(CC)Br.C(CC)N(CCC)CCC RULRTQRLYQBEHV-UHFFFAOYSA-N 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2876—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures from a reacting mixture containing an amine or an organic cation, e.g. a quaternary onium cation-ammonium, phosphonium, stibonium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) METHOD OF PREPARATION OF LARGE CRYSTAL ALUMINOSILICATE
ZEOLITE CATALYST
(71) We, MOBIL OIL CORPORATION, a Corporation organised under the laws of the State of New York, United States of America, of 150 East 42nd Street, New York, New
York 10017, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention is directed to a method of preparing certain crystalline aluminosilicate zeolites werein crystalline aluminosilicate zeolites of high purity are crystallized in the form of large particles having an ultimate crystal size greater than about one micron, that is from about 1 micron to 2 microns or larger.ZSM-5 catalysts having the above-described crystal size are highly useful in selective toluene disproportionation and methanol conversion processes and other selective aromatics conversion processes.
ZSM-5 crystalline aluminosilicate zeolites are well known in the art, being particularly described in U.S. Patent 3,702,886 and although large particle ZSM-5 type zeolites have previously been prepared, such processes have generally not been commercially viable procedures. It was previously thought that ultimate zeolite crystal size was predominantly dependent on the nature of the reaction mixture employed. It has now been discovered that crystal size is also significantly affected by' the rate of addition of the organic compound, that is. its effective concentration in the crystallization media, and the temperature and pH conditions and the degree of agitation of the crystallization medium.
Accordingly, this invention is directed to a process for preparing a large crystal aluminosilicate zeolite catalyst which is characterised by having at least one crystalline dimension of at least 1 micron, and preferably from 1 to 2 microns or more, which comprises preparing an aluminosilicate gel, generally heating it to a temperature of 260 + 60OF. preferably heating it to at least 220OF, adding an alkyl ammonium compound (e.g., tetrapropyl ammonium bromide) or precursors therefor, to the gel in such manner that only nucleating-inhibiting concentrations thereof exist during crystallization, and thereafter raising the temperature of the mixture to 320 + 100OF, preferably at least 3000F, to promote crystallization.
The term large crystal is a relative term defined herein to include crystals having a diameter in excess of 1 micron, e.g., of from 1 to 2 microns or more. Such crystal size has proven advantageous for ZSM-5 type catalysts useful in hydroconversion processes. For example, as mentioned hereinabove ZSM-5 catalysts comprising crystals of such size are highly useful in selective toluene disproportionation and methanol conversion processes.
Zeolites prepared by the process of the present invention are exemplified by ZSM-5,
ZSM-11, ZSM-12, ZSM-35. ZSM-38. and other similar materials. As noted hereinabove,
U.S. Patent 3.702,886 describes and claims ZSM-5.
ZSM-11 is more particularly described in U.S. Patent 3,709,979.
ZSM-12 is more particularly described in U.K. Patent Specification 1,365,317.
ZSM-35 is more particularly described in U.S. Patent 4,016,245.
ZSM-38 is more particularly described in U.S. Patent 4,046,859.
The organic component employed in preparing the large size zeolite crystals in accordance with this invention is selected from alkyl ammonium compounds and more particularly from quaternary compounds, (preferably from C1-C1() alkyl ammonium compounds and ions thereof, especially from tetra-alkyl halogenated ammonium compounds. such as tetra-methylammonium or tetrapropylammonium bromide). Furthermore, instead of the alkyl ammonium compound itself, precursors thereof may also be advantageously used. In the case of tetra-n-propylammonium bromide, tri-n-propylamine and n-propyl bromide may be used.
The method of preparation of the instant large crystal catalysts incorporates techniques to inhibit nucleation of the aluminosilicate zeolite while promoting crystal growth from the crystallization reaction mixture. Specifically, the technique utilizes the fact that crystal growth is promoted by higher temperatures and nucleation is promoted by high concentrations of the quaternary or other organic compound essential to the crystallization of the zeolite.One method that successfully produces large aluminosilicate zeolite crystals is to prepare the aluminosilicate gel without the necessary organic component, heat to an elevated temperature, or within the range of 260 + 60"F usually > 220 F, then introduce the organic compound in controlled, nucleating-inhibiting, concentrations or in such a manner that only nucleating-inhibiting concentrations of the organic compound effectively exist at any time during the crystallization, and then raise to a crystallization temperature to within the range of 320 + 100OF, usually > 300 F. Another method of controlling the organic concentration which is a preferred embodiment is to introduce a mixture of the precursor materials for the organic compound synthesis, e.g., for tetrapropylammonium bromide, tri-n-propylamine and n-propyl bromide, to the alumino-silicate gel at the elevated temperature and under conditions of agitation and controlled crystallization temperature.
The high agitation (generally from 90-140 rpm) disperses the organic precursors uniformly throughout the mix in such a way that reaction to form the quaternary compound is inhibited; therefore, a uniform nucleating-inhibiting concentration of the quaternary is maintained throughout the crystallization. The quarternary compound (i.e., alkyl ammonium compound, or the precursor materials) can be introduced during or before crystallization. Also, the alkyl ammonium compound can be introduced at the crystallization temperature and/or at small controlled rates.
The high temperature preparations in the following three tables demonstrate the effect of concentration of the essential organic species. The concentration has been varied by replacement of tetra-n-propylammonium bromide with its precursors, tri-n-propylamine and n-propyl bromide, and limiting the extent of reaction by agitation. In said Tables 1 and 2 as well as Table 4 the crystal size is given in terms of the large dimension of the respective crystal while in Table 3 crystal size is given in terms of the crystals large and small dimensions.
TABLE 1
High concentrarion of organic species and variable agitation
Examples 1. 2 and 3 are normal preparations of ZSM-5 using the quarternary salt, tetra-n-propylammonium bromide. There is no difference in crystal size as agitation is varied since concentration of the nucleating species remains the same. Example 4 demonstrates the capability of reacting the quaternary precursors in the presence of methylethyl ketone to produce a significant concentration of the nucleating species. A quiescent period of time was required for reaction of the precursors.
TABLE 1
High concentration of organic species
variable agitation
Example No. 1 2 3 4
Mole Ratio of Charge
(Basis: 1.0 mole Al203) Awl203 1 1 1 1
SiO2 94 94.0 94.0 94
Na 181 181 181 181
Tri-n-propylamine - - - 9.19
n-propyl bromide - - - 9.19
Methylethyl ketone - - - 30.2
TPA Br 9.17 9.17 9.16 H2O 3880 3880 3880 3890
Crystallization Data
Prereaction
Temp. "F - - - 260
Time Hr - - - 14
Agitation RPM - - - 0
Crystallization
Temp. "F 316 317 321 320
Time Hr < 21 < 8 < 16 < 9
Agitation RPM 76 121 121 167
Mole Ratio of Product
(Basis: 1.0 mole AlO) .
Al2O3 1 1 1 1 SiO2 70.4 72.5 75.0 72.5
Na2O 0.62 0.71 0.55 0.59
N2O 1.17 1.30 1.23 1.16
C 34.3 30.9 34.7 34.3
CIN Ratio 14.7 11.9 14.1 14.8 (Na20f N2O)/Al2O:) 1.78 2.01 1.78 1.75
Nitrogen Content,
Liquor Wt. % .10 0.11 .09 .02 Crystal Size .1 .1 .1 .1 est est est est
TABLE 2
Low concentraton of organic species and low agitation
Examples 5. 6 and 7 produced larger crystals than were attained by preparations shown in
Table 1. The largercrystals resulted from a low concentration of the organic species necessary for nucleation. The low concentration, caused by limiting reaction of the precursors by agitating the mixture, is demonstrated by the low nitrogen content of the mother liquor.Although this agitation was not severe enough to disperse the organic precursors throughout the mix, the effect on precursor reaction is apparent when Example 7 is compared with Example 4. Example 7 resulted in crystals of greater than about 1 micron while Example 4 produced crystals with dimensions of only about 0.1 micron. This was due to the lower effective concentration of the organic species in Example 7 as verified by the low nitrogen content of the mother liquor after crystallization.
TABLE 3
Low concentration of organic species and high agitation
A higher degree of agitation than that employed by Example 5-7 was employed during preparation of Examples 8, 9, 10, 11 and 12. This degree of agitation resulted in increased dispersion of the precursors and generally larger crystals than those attained with a lower degree of agitation. Clearly the data of Table 3 shows that large crystals can be readily obtained by low concentration of the organic species with high agitation.
TABLE 2
Low concentration of organic species
low agitation
Example No. 5 6 7
Mole Ratio of Charge
(Basis: 1.0 mole Al203) Al2O3 1.0 1.0 1.0
SiO, 94.0 94.0 94.0
Na 181 181 181
Tri-n-proplyamine 9.17 9.17 9.19
n-Propyl bromide 9.17 9.17 9.19
Methylethyl ketone - - 30.2
TPA Br.
H2O 3880 3880 3890
Crystallization Data
Prereaction
Temp. "F Time Hr
Agitation RPM -
Crystallization
Temp. "F 318 319 316
Time Hr. < 20 < 13 < 18
Agitation RPM 76 76 76
Mole Ratio of Product
(Basis: 1.0 mole Al2O) Al2O3 1.0 1.0 1.0 SiO2 74.5 70.7 67.8 Na2O 0.29 0.20 0.40 N2O 1.38 1.31 0.95
C 26.1 25.2 22.5
C/N Ratio 9.48 9.64 11.8 (Na2O+N2O)/Al2O3 1.66 1.52 1.35
Nitrogen Content,
Liquor Wt. % .003 .001 .001
Crystal Size F > 1 > 1 > 1
The effect of temperature on rate of crystal growth is shown in Table 4. Both preparations employed tetra-n-propyl ammonium bromide.Example 15, crystallized at 210OF required 192 hours and produced crystals less than 0.05 micron in diameter.
Crystallization of Example 14, a substantially identical reaction mixture at 317OF resulted in crystals of at least twice that size ( .1 micron).
TABLE 3
Low concentration of organic species - high agitation
Example No. 8 9 10 11 12
Mole Ratio of Charge (Basis: 1.0 mole Al2O) Al2O3 1 1 1 1 1
SiO2 94.0 94.0 94.0 94.0 94.0
Na 181 181 181 181 181
Tri-n-propylamine 9.17 9.17 9.17 9.17 9.17 n-Propyl bromide 9.17 9.17 9.17 9.17 9.17
Methylethyl ketone - - - 30.2 30.2
TPA Br.
H2O 3880 3880 3880 3880 3880
Crystallization Data
Prereaction
Temp. F
Time Hr.
Agitation RPM
Crystallization
Temp. F 320 320 320 320 320
Time Hr. < 14 < 17 < 18 < 17 < 17
Agitation RPM 121 121 121 121 121
Mole Ratio of Product (Basis: 1.0 mole Al2O) Al,O l 1. 1 1 1 1
SiO2 70.3 74.4 71.5 76.8 71.9 Na2O 0.35 0.31 0.25 0.30 0.29
N2O 0.79 1.13 1.33 1.17 1.08 C 15.5 21.9 26.2 27.3 25.2
C/N Ratio 9.78 9.69 9.88 11.7 11.7 (Na2O+N2O)/Al203 1.14 1.44 1.58 1.47 1.37
Nitrogen Content, Liquor Wt.% .001 < .001 < .001 < .001 < .001
Crystal Size u A~3 5 ~3-5 3-4 34 3-5 B~1-2 ~ 1-2 1 1-2 ~ 1-2
A Large dimension of crystal
B Small dimension of crystal
TABLE 4
Effect of crystallization temperature
Example No. 14 15
Mole Ratio of Charge
(Basis: 1.0 mole Awl203) Al203 1 1
SiO2 94.0 99
Na 181 162
Tri-n-propylamine -
n-propyl bromide -
Methylethyl ketone -
TPA Br 9.17 9.68
H2O 3880 4096
Crystallization Data
Crystallization
Temp. "F 317 210
Time Hr < 8 192
Mole Ratio of Product
(Basis: 1.0 mole Al2O) Al2O3 1 1 SiO2 72.5 73.9 Na.O 0.71 0.87 N2O 1.30 1.32 C 30.9
C/N Ratio 11.9 (Na2O+N2O)/Al2O3 2.01 2.18
Nitrogen Content,
Liquor Wt. % 0.11
Crystal Size 11 .1 est < .05
WHAT WE CLAIM IS:
1.A process for preparing a crystalline aluminosilicate zeolite characterized by having at least one crystalline dimension of 1 micron or more which comprises preparing an aluminosilicate gel, and then adding an alkyl ammonium compound or precursors thereof to the gel under conditions such that only nucleation-inhibiting concentrations of said compound exist during crystallization and thereafter raising the temperature of the mixture to 320 + 100OF to promote crystallization.
2. The process of claim 1 wherein the alkyl ammonium compound consists of C,-Cl(, alkyl ammonium compounds or ions thereof.
3. The process of claim 2 wherein said alkyl ammonium compound is a tetraalkyl halogenated ammonium compound.
4. The process of claim 3 wherein said ammonium compound is tetra-n-propyl ammonium bromide.
5. The process of claim 4 utilizing the following precursor materials of tetra-npropylammonium bromide: tri-n-propylamine and n-propyl bromide.
6. The process of any of claims 1 to 5 wherein the aluminosilicate gel is heated to an elevated temperature of from 260 + 60"F prior to adding the alkyl ammonium compound.
7. The process of claim 6 wherein said elevated temperature is at least 220OF.
8. The process of any of claims 1 to 7 wherein said crystallization temperature is at least 300OF.
9. The process of any of claims 1 to 8 wherein said zeolite has at least one crystalline dimension greater than 2 microns.
10. The process of claim 9 wherein said crystalline dimension is from about 3-5 microns.
11. The process of any of claims 1 to 10 wherein the conentration of the alkyl
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (15)
1.0 mole Al2O) Al2O3 1 1 SiO2 72.5 73.9 Na.O 0.71 0.87 N2O 1.30 1.32 C 30.9
C/N Ratio 11.9 (Na2O+N2O)/Al2O3 2.01 2.18
Nitrogen Content,
Liquor Wt. % 0.11
Crystal Size 11 .1 est < .05
WHAT WE CLAIM IS:
1.A process for preparing a crystalline aluminosilicate zeolite characterized by having at least one crystalline dimension of 1 micron or more which comprises preparing an aluminosilicate gel, and then adding an alkyl ammonium compound or precursors thereof to the gel under conditions such that only nucleation-inhibiting concentrations of said compound exist during crystallization and thereafter raising the temperature of the mixture to 320 + 100OF to promote crystallization.
2. The process of claim 1 wherein the alkyl ammonium compound consists of C,-Cl(, alkyl ammonium compounds or ions thereof.
3. The process of claim 2 wherein said alkyl ammonium compound is a tetraalkyl halogenated ammonium compound.
4. The process of claim 3 wherein said ammonium compound is tetra-n-propyl ammonium bromide.
5. The process of claim 4 utilizing the following precursor materials of tetra-npropylammonium bromide: tri-n-propylamine and n-propyl bromide.
6. The process of any of claims 1 to 5 wherein the aluminosilicate gel is heated to an elevated temperature of from 260 + 60"F prior to adding the alkyl ammonium compound.
7. The process of claim 6 wherein said elevated temperature is at least 220OF.
8. The process of any of claims 1 to 7 wherein said crystallization temperature is at least 300OF.
9. The process of any of claims 1 to 8 wherein said zeolite has at least one crystalline dimension greater than 2 microns.
10. The process of claim 9 wherein said crystalline dimension is from about 3-5 microns.
11. The process of any of claims 1 to 10 wherein the conentration of the alkyl
ammonium compound is controlled by introducing a mixture of the precursor materials to the aluminosilicate gel at an elevated temperature under agitation of from 90 to 150 RPM.
12. The process of any of claims 1 to 11 wherein the alkyl ammonium compound or the precursor materials are introduced to the crystallization medium under agitation prior to crystallization.
13. The process of any of claims 1 to 11 wherein-the alkyl ammonium compound or precursor materials are introduced under agitation during crystallization.
14. The process of claim 12 or 13 wherein the agitation is at least 90 RPM.
15. A process of preparing a crystalline aluminosilicate zeolite according to Claim 1 substantially as described in any one of the foregoing Examples 5 to 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80025977A | 1977-05-25 | 1977-05-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1601915A true GB1601915A (en) | 1981-11-04 |
Family
ID=25177919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB18959/78A Expired GB1601915A (en) | 1977-05-25 | 1978-05-11 | Method of preparation of large crystal alumino-silicate zeolite catalyst |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS53147699A (en) |
| DE (1) | DE2822725A1 (en) |
| FR (1) | FR2391958A1 (en) |
| GB (1) | GB1601915A (en) |
| IT (1) | IT1096322B (en) |
| NL (1) | NL7805627A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908342A (en) * | 1985-09-04 | 1990-03-13 | Mobil Oil Corporation | ZSM-5 zeolites having uniformly large crystals |
| US7229941B2 (en) | 2002-12-01 | 2007-06-12 | Sud-Chemie Ag | Catalysts based on crystalline aluminosilicate |
| US9511361B2 (en) | 2009-11-19 | 2016-12-06 | Clariant Produkte (Deutschland) Gmbh | Spherical zeolitic catalyst for converting methanol into olefins |
| US10252250B2 (en) | 2010-07-12 | 2019-04-09 | Gotz Burgfels | Process of producing zeolite-based catalysts for converting oxygenates to lower olefins |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650656A (en) * | 1977-05-25 | 1987-03-17 | Mobil Oil Corporation | Large crystal ZSM-5 from template addition to the gel |
| AU527116B2 (en) * | 1978-11-13 | 1983-02-17 | Mobil Oil Corp. | Method for synthesis of zeolite zsm-5 |
| US4205053A (en) * | 1979-02-01 | 1980-05-27 | Mobil Oil Corporation | Manufacture of nitrogenous zeolites |
| NZ193928A (en) * | 1979-06-11 | 1982-09-07 | Mobil Oil Corp | Preparation of large crystal zeolite zsm-5 |
| NZ193929A (en) * | 1979-10-09 | 1982-09-07 | Mobil Oil Corp | Preparation of large crystal zeolite zsm-5 |
| US4957320A (en) * | 1988-08-31 | 1990-09-18 | Trustees Of The University Of Pennsylvania | Methods and apparatus for mechanically intelligent grasping |
| DE102010052258A1 (en) | 2010-11-23 | 2012-05-24 | Süd-Chemie AG | Process for the preparation of supported ZSM-5 zeolites |
| CN104192859B (en) * | 2014-08-21 | 2018-02-06 | 陕西延长石油(集团)有限责任公司研究院 | A kind of Fast back-projection algorithm method of the molecular sieve of fine grain ZSM-5 5 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1567714C3 (en) * | 1965-11-24 | 1979-01-18 | Mobil Oil Corp., New York, N.Y. (V.St.A.) | Crystalline aluminosilicate zeolite |
| GB1161974A (en) * | 1967-04-14 | 1969-08-20 | Mobil Oil Corp | Synthetic Crystalline Aluminosilicate and method of preparing the same |
| US3642434A (en) * | 1969-01-10 | 1972-02-15 | Mobil Oil Corp | Production of synthetic faujasite |
| FR2228721A1 (en) * | 1973-05-07 | 1974-12-06 | Mobil Oil | ZSM-21 synthetic crystalline aluminosilicate zeolites - for use as hydrocarbon conversion catalysts |
-
1978
- 1978-05-11 GB GB18959/78A patent/GB1601915A/en not_active Expired
- 1978-05-17 JP JP5772878A patent/JPS53147699A/en active Granted
- 1978-05-24 IT IT23765/78A patent/IT1096322B/en active
- 1978-05-24 FR FR7815399A patent/FR2391958A1/en active Granted
- 1978-05-24 NL NL7805627A patent/NL7805627A/en not_active Application Discontinuation
- 1978-05-24 DE DE19782822725 patent/DE2822725A1/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908342A (en) * | 1985-09-04 | 1990-03-13 | Mobil Oil Corporation | ZSM-5 zeolites having uniformly large crystals |
| US7229941B2 (en) | 2002-12-01 | 2007-06-12 | Sud-Chemie Ag | Catalysts based on crystalline aluminosilicate |
| US9511361B2 (en) | 2009-11-19 | 2016-12-06 | Clariant Produkte (Deutschland) Gmbh | Spherical zeolitic catalyst for converting methanol into olefins |
| US10252250B2 (en) | 2010-07-12 | 2019-04-09 | Gotz Burgfels | Process of producing zeolite-based catalysts for converting oxygenates to lower olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2391958B1 (en) | 1982-08-20 |
| DE2822725C2 (en) | 1988-04-21 |
| JPS6215487B2 (en) | 1987-04-08 |
| IT7823765A0 (en) | 1978-05-24 |
| FR2391958A1 (en) | 1978-12-22 |
| NL7805627A (en) | 1978-11-28 |
| DE2822725A1 (en) | 1978-12-07 |
| IT1096322B (en) | 1985-08-26 |
| JPS53147699A (en) | 1978-12-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |