CA1117512A - Zeolite synthesis - Google Patents
Zeolite synthesisInfo
- Publication number
- CA1117512A CA1117512A CA000301357A CA301357A CA1117512A CA 1117512 A CA1117512 A CA 1117512A CA 000301357 A CA000301357 A CA 000301357A CA 301357 A CA301357 A CA 301357A CA 1117512 A CA1117512 A CA 1117512A
- Authority
- CA
- Canada
- Prior art keywords
- sio2
- reaction mixture
- zsm
- zeolite
- alkali metal
- 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
An improved process for synthesizing an improved crystalline aluminosilicate zeolite is provided. The improved process comprises forming a reaction mixture containing one or more sources of alkali metal oxide, organic nitrogen-containing cations, acid ions, an oxide of silicon, an oxide of aluminum and water wherein the mole ratio of hydroxide ions/silica in said reaction mixture is at most about 10-2 and the acid ions are present in said reaction mixture in amount less than the equivalents of organic nitrogen present therein, and wherein the pH of said reaction mixture is at least about 7, and maintaining the reaction mixture at a temperature and pressure for a time necessary to crystallize therefrom said crystalline aluminosilicate zeolite. Improvement in the present synthesis process resides, for example, in reduced crystallization time and reduced organic nitrogen-containing cation source requirement. Improvement in zeolite produce from the present improved process resides, for example, in enhanced purity.
An improved process for synthesizing an improved crystalline aluminosilicate zeolite is provided. The improved process comprises forming a reaction mixture containing one or more sources of alkali metal oxide, organic nitrogen-containing cations, acid ions, an oxide of silicon, an oxide of aluminum and water wherein the mole ratio of hydroxide ions/silica in said reaction mixture is at most about 10-2 and the acid ions are present in said reaction mixture in amount less than the equivalents of organic nitrogen present therein, and wherein the pH of said reaction mixture is at least about 7, and maintaining the reaction mixture at a temperature and pressure for a time necessary to crystallize therefrom said crystalline aluminosilicate zeolite. Improvement in the present synthesis process resides, for example, in reduced crystallization time and reduced organic nitrogen-containing cation source requirement. Improvement in zeolite produce from the present improved process resides, for example, in enhanced purity.
Description
7~
Thls invention relates to an lmproved method ~or syntheslzlng crystalllne aluminoslllcate zeclites requiring a reactlon mixture for crystallization thereof which contains an organic nitrogen-containing catlon source. Zeolites which may be advantageously synthesized by the present improved method lnclude, for ex~mple, ZSM-5, 2SM-ll, ZSM-12, ZSM-23, ZSM-34, ZSM-35 and ZSM-38. Th~ present improved process requlres a zeolite reaction mixture composltlon comprising an e~tremely low mole ratio of hydroxide ions/sillca o~ only at most about 10-2, the presence of acid ions in amount less than the equivalents of organic nitrogen present therein and a reaction mlxture of pH o~ at least about 7.
This inventlon ~urther relates to an improved crystalllne aluminosilicate zeolite produc' of the improved method of synthesls and to organic compound conversion in the presence of the improved zeolite as catalyst.
Zeolitic materials, both natural and synthetic~
have been demonstrated in the past to have catalytlc propertles for various types of hydrocarbon conversions. Certain zeolitic materials are ordered, porous crystalline aluminosillcates having a de~inite crystalline structure within which there are a large number of smaller cavities which may be inter-cor.nected by a number of still smaller channels. Since the
Thls invention relates to an lmproved method ~or syntheslzlng crystalllne aluminoslllcate zeclites requiring a reactlon mixture for crystallization thereof which contains an organic nitrogen-containing catlon source. Zeolites which may be advantageously synthesized by the present improved method lnclude, for ex~mple, ZSM-5, 2SM-ll, ZSM-12, ZSM-23, ZSM-34, ZSM-35 and ZSM-38. Th~ present improved process requlres a zeolite reaction mixture composltlon comprising an e~tremely low mole ratio of hydroxide ions/sillca o~ only at most about 10-2, the presence of acid ions in amount less than the equivalents of organic nitrogen present therein and a reaction mlxture of pH o~ at least about 7.
This inventlon ~urther relates to an improved crystalllne aluminosilicate zeolite produc' of the improved method of synthesls and to organic compound conversion in the presence of the improved zeolite as catalyst.
Zeolitic materials, both natural and synthetic~
have been demonstrated in the past to have catalytlc propertles for various types of hydrocarbon conversions. Certain zeolitic materials are ordered, porous crystalline aluminosillcates having a de~inite crystalline structure within which there are a large number of smaller cavities which may be inter-cor.nected by a number of still smaller channels. Since the
-2-dimensions of these pores are such as to accept for adsorptlon molecules o~ certain dimensions while re~ecting those o~
larger dimenslons, these materials have come ~co be known as "molecular sieves" an~ are utllized ln a variety of ways to take advantage of these properkies.
Such molecular sieves, both natural and synthetic, include a wide variety of posltive ion-contalnlng crystalline aluminosilicates. These aluminosilicates can be described as a rigid three-dimensional framework of SiO4 and A104 in which the tetrahedra are cross lin~ed by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electro~alence of the tetrahedra containing aluminum ls balanced by the inclusion in the crystal of a cation, for example, an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratlo of aluminum to the number of various cations, such as Ca, Sr, Na, K or Li is equal to unity. One type of cation may be exchanged either entirely or partially by another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation. The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
Prior art techniques have resulted in the formation of a great variety of synthetic aluminosilicates. A number of these aluminosilicates require the presence of a source of organic nitrogen-containing cations in the reaction mixture used to prepare them. Those aluminosilicate zeolites include, for example, zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ~7S~
ZSM-ll (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent
larger dimenslons, these materials have come ~co be known as "molecular sieves" an~ are utllized ln a variety of ways to take advantage of these properkies.
Such molecular sieves, both natural and synthetic, include a wide variety of posltive ion-contalnlng crystalline aluminosilicates. These aluminosilicates can be described as a rigid three-dimensional framework of SiO4 and A104 in which the tetrahedra are cross lin~ed by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electro~alence of the tetrahedra containing aluminum ls balanced by the inclusion in the crystal of a cation, for example, an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratlo of aluminum to the number of various cations, such as Ca, Sr, Na, K or Li is equal to unity. One type of cation may be exchanged either entirely or partially by another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation. The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
Prior art techniques have resulted in the formation of a great variety of synthetic aluminosilicates. A number of these aluminosilicates require the presence of a source of organic nitrogen-containing cations in the reaction mixture used to prepare them. Those aluminosilicate zeolites include, for example, zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ~7S~
ZSM-ll (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent
3,832,449), zeolite ZSM-35 (U.S. Patent 4,016,245), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZK-22 (U.S. Patent 3,791,964), zeolite " alpha" (U.S. Patent 3,375,205), zeolite "beta" (U.S. Patent 3,308,069), a synthetic erionite ~U.S.
Patent 3,699,139) and a synthetic offretlte (U.S. Patent 3,578,398).
Applicant knows of no prior art methods of crystalline aluminosilicate zeolite synthesis, said synthesis requiring a source of organlc nitrogen-containing cations in the reaction mixture used therein, utilizing the present improvement.
SUMMARY OF_THE INVENTION
An improved method for preparing an improved crystalline aluminosilicate zeolite exhibiting enhanced .purity as synthesized is provided which comprises forming a reaction mixture containing one or more sources of an alkali metal oxide, any organic nitrogen-containing oxides required for preparation of the particular zeolite to be synthesized, acid ions, an oxide of silicon, an oxide of aluminum and water wherein the mole ratio of hydroxide ions/silica in said reaction mixture is at most about 10-2, preferably from about lO-l to about 10-2, and the acid ions are present in said reaction mixture in amount less than the equivalents of organic nitrogenpresent therein, and wherein the pH of said reaction mixture is at least about 7, preferably from about 7 to ~bout 12, and maintaining the reactlon mixture at a temperature and pressure for a time necessary to crystallize therefrom said crystalline aluminosilicate zeolite.
Reaction condlt~ons ~nclude heating the reaction mixture to a temperature of from about 70~ to a~out 500F for a per~od of time of ~rom about l hour to about 180 days. At a given reaction temperature, crystalllzation time can be signiflcantly reduced from that required by the prior art by the present improved method. Further, the amount of organic nitrogen-containing cation source required in the reaction mixture can be reduced from that required by the prior art by the present improved method. Still further, the crystalline aluminosilicate zeolite synthesized by the present improved method can be of hi~her purity than normally obtainable by prior art methods of synthesis.
.
DESCRIPTION OF SPECIFIC EMBODIMENTS
The present invention offers a means of synthesizing improved crystalline aluminosilicate zeolites requiring a reaction mixture for crystallization thereof which contains a source of organic nitrogen-containing cations. Improved zeolites which may be prepared in accordance herewith include, for-example, ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-34, ZSM-35 and ZSM-38.
1~7~Z
Zeolite zsM--5 and the conventional prepar~tion thereof are described in U.S. Patent 3,702,886. Zeolite ZSM-ll and the conventional preparation thereof are described in U.S. Patent 3,709,979. Zeolite ZSM-12 and the conventional preparation thereof are described in U.S. Patent 3,832,449.
Zeolite ZSM-35 and the conventional preparation thereof are described in U.S. Patent 4,016,245.
Zeolite ZSM-23 and the conventional preparation there-of are more particularly described in Canadian Patent la 1,064,980. This zeolite can be identified, in terms of mole ratios of oxides and in the anhydrous state, as follows:
(o.58-3.4)M20 : A12O3 : (40-250)Sio2 where M is at least one cation and n is the valence thereof. It will be noticed that the ratio of M2O may n exceed unity in this material. This is probably due to the occlusion of excess organic species, used in the preparation of ZSM-23, within the zeolite pores.
In a preferred synthesized form, zeolite ZSM-23 has a 2Q formula, in terms of mole ratios of oxides and in the anhydrous state, as follows:
(0.5-3.0)R20 : (0.08-0.4)M20 : A12O3 : (40-250)SiO2 wherein R is an organic nitrogen-containing cation derived from pyrrolidine and M is an alkali metal cation. It will be noticed that in this preferred form the ratio of R2O
to A12O3 may exceed ~$ ' unity, probably due to the occlusion of eY.cess nitrogen-containing organlc species (R20) within the zeolite pores.
The synthetic ZSM-23 zeollte possesses a definite distinguishing crystalline structure whose X-ray di~fraction pattern shows substantially the slgnl~icant lines set forth ln Table I.
5~Z
TABLE I
_ _ d(A) I/Io 11.2 + 0.23 Medium lO.l + 0.20 Weak 7.87 ~ 0.15 Weak 5.59 + 0.10 Weak 5.44 ~ 0.10 Weak
Patent 3,699,139) and a synthetic offretlte (U.S. Patent 3,578,398).
Applicant knows of no prior art methods of crystalline aluminosilicate zeolite synthesis, said synthesis requiring a source of organlc nitrogen-containing cations in the reaction mixture used therein, utilizing the present improvement.
SUMMARY OF_THE INVENTION
An improved method for preparing an improved crystalline aluminosilicate zeolite exhibiting enhanced .purity as synthesized is provided which comprises forming a reaction mixture containing one or more sources of an alkali metal oxide, any organic nitrogen-containing oxides required for preparation of the particular zeolite to be synthesized, acid ions, an oxide of silicon, an oxide of aluminum and water wherein the mole ratio of hydroxide ions/silica in said reaction mixture is at most about 10-2, preferably from about lO-l to about 10-2, and the acid ions are present in said reaction mixture in amount less than the equivalents of organic nitrogenpresent therein, and wherein the pH of said reaction mixture is at least about 7, preferably from about 7 to ~bout 12, and maintaining the reactlon mixture at a temperature and pressure for a time necessary to crystallize therefrom said crystalline aluminosilicate zeolite.
Reaction condlt~ons ~nclude heating the reaction mixture to a temperature of from about 70~ to a~out 500F for a per~od of time of ~rom about l hour to about 180 days. At a given reaction temperature, crystalllzation time can be signiflcantly reduced from that required by the prior art by the present improved method. Further, the amount of organic nitrogen-containing cation source required in the reaction mixture can be reduced from that required by the prior art by the present improved method. Still further, the crystalline aluminosilicate zeolite synthesized by the present improved method can be of hi~her purity than normally obtainable by prior art methods of synthesis.
.
DESCRIPTION OF SPECIFIC EMBODIMENTS
The present invention offers a means of synthesizing improved crystalline aluminosilicate zeolites requiring a reaction mixture for crystallization thereof which contains a source of organic nitrogen-containing cations. Improved zeolites which may be prepared in accordance herewith include, for-example, ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-34, ZSM-35 and ZSM-38.
1~7~Z
Zeolite zsM--5 and the conventional prepar~tion thereof are described in U.S. Patent 3,702,886. Zeolite ZSM-ll and the conventional preparation thereof are described in U.S. Patent 3,709,979. Zeolite ZSM-12 and the conventional preparation thereof are described in U.S. Patent 3,832,449.
Zeolite ZSM-35 and the conventional preparation thereof are described in U.S. Patent 4,016,245.
Zeolite ZSM-23 and the conventional preparation there-of are more particularly described in Canadian Patent la 1,064,980. This zeolite can be identified, in terms of mole ratios of oxides and in the anhydrous state, as follows:
(o.58-3.4)M20 : A12O3 : (40-250)Sio2 where M is at least one cation and n is the valence thereof. It will be noticed that the ratio of M2O may n exceed unity in this material. This is probably due to the occlusion of excess organic species, used in the preparation of ZSM-23, within the zeolite pores.
In a preferred synthesized form, zeolite ZSM-23 has a 2Q formula, in terms of mole ratios of oxides and in the anhydrous state, as follows:
(0.5-3.0)R20 : (0.08-0.4)M20 : A12O3 : (40-250)SiO2 wherein R is an organic nitrogen-containing cation derived from pyrrolidine and M is an alkali metal cation. It will be noticed that in this preferred form the ratio of R2O
to A12O3 may exceed ~$ ' unity, probably due to the occlusion of eY.cess nitrogen-containing organlc species (R20) within the zeolite pores.
The synthetic ZSM-23 zeollte possesses a definite distinguishing crystalline structure whose X-ray di~fraction pattern shows substantially the slgnl~icant lines set forth ln Table I.
5~Z
TABLE I
_ _ d(A) I/Io 11.2 + 0.23 Medium lO.l + 0.20 Weak 7.87 ~ 0.15 Weak 5.59 + 0.10 Weak 5.44 ~ 0.10 Weak
4.90 ~ 0.10 Weak 4.53 + 0.10 Strong o 3 . go + o . o8 Very Strong 3. 72 + o.o8 Very Strong 3.62 + 0,07 Very Strong 3. 54 ~ o,07 Medium 3.44 ~ 0.07 Strong 3-36 + 0.07 Weak 3.16 + 0.07 Weak . 3.05 + 0.06 Weak 2.99 + 0.06 Weak 2.85 + 0.06 Weak .2.54 + 0.05 Medium 2.47 + 0.05 Weak 2.40 + 0.05 Weak 2.34 + 0.05 Weak 75i~
Zeolite ZSM~23 can be conventionally synthesized by preparing a solutlon containing sources o~ an alkali metal oxide, pre~erably sodium oxide, sources of nltrogen-contalning cation, preferably pyrrolidine, an oxide of aluminum, an oxide of silicon and water and having a composition, in terms of mole ratios of oxides, ~alling within the following ranges:
R+
R~ ~ M~ 0.85 - 0.95 OH /SiO2 0.01 - 0.049 X2O/OH- 200 ~ 600 SiO2/A12O3 55 - 70 wherein R ls an organic nitrogen-contalning cation and M
is an alkali metal ion, and maintaining the mixture until crystals of the zeolite are formed. The quantity of OH-is calculated only ~rom the lnorganic sources of alkali without any organic base contributlon. Thereafter, the crystals are separated from the liquid and recovered.
Typical reaction conditions consist of heating the foregoing reaction mixture to a temperature above 280F to about 400F for a period of time of from about 6 hours to about 14 days. A more preferred temperature range is from about 300F to about 375F with the amount of time at a temperature in such range being from about 24 hours to about 11 days.
The digestion of the gel particles is carried out until crystals form. The solid product is separated from the reaction medium, as by cooling the whole to room temperature, filtering and water washlng.
The crystalline product is dried, e.g. at 230F, for from about 8 to 24 hours. Of course, milder conditions may be employed if desired, e.g. room temperature under vacuum.
~7S~
Zeolite ZSM-34 and the conventional preparation thereof are more partlc~llarly described in West German Published Applica~ion No. 2,749,024. This zeolite can be identified, in terms of mole ratios of oxides and in the anhydro~s state, as follows:
(0.5-1.3)R20 : (0-0.15)Na20: (0.10-0.50)K20: A12O3: XSiO2 where R is the organic nitrogen-containing cation derived from choline [(CH3)3N-CE~2CH2OH] and X is 8 to 50.
The synthetic ZS~-34 zeolite possesses a definite 1~ distinguishing crystalline structure whose X-ray diffrac-tion pattern shows substasntially the significant lines set forth in Table II.
Zeolite ZSM~23 can be conventionally synthesized by preparing a solutlon containing sources o~ an alkali metal oxide, pre~erably sodium oxide, sources of nltrogen-contalning cation, preferably pyrrolidine, an oxide of aluminum, an oxide of silicon and water and having a composition, in terms of mole ratios of oxides, ~alling within the following ranges:
R+
R~ ~ M~ 0.85 - 0.95 OH /SiO2 0.01 - 0.049 X2O/OH- 200 ~ 600 SiO2/A12O3 55 - 70 wherein R ls an organic nitrogen-contalning cation and M
is an alkali metal ion, and maintaining the mixture until crystals of the zeolite are formed. The quantity of OH-is calculated only ~rom the lnorganic sources of alkali without any organic base contributlon. Thereafter, the crystals are separated from the liquid and recovered.
Typical reaction conditions consist of heating the foregoing reaction mixture to a temperature above 280F to about 400F for a period of time of from about 6 hours to about 14 days. A more preferred temperature range is from about 300F to about 375F with the amount of time at a temperature in such range being from about 24 hours to about 11 days.
The digestion of the gel particles is carried out until crystals form. The solid product is separated from the reaction medium, as by cooling the whole to room temperature, filtering and water washlng.
The crystalline product is dried, e.g. at 230F, for from about 8 to 24 hours. Of course, milder conditions may be employed if desired, e.g. room temperature under vacuum.
~7S~
Zeolite ZSM-34 and the conventional preparation thereof are more partlc~llarly described in West German Published Applica~ion No. 2,749,024. This zeolite can be identified, in terms of mole ratios of oxides and in the anhydro~s state, as follows:
(0.5-1.3)R20 : (0-0.15)Na20: (0.10-0.50)K20: A12O3: XSiO2 where R is the organic nitrogen-containing cation derived from choline [(CH3)3N-CE~2CH2OH] and X is 8 to 50.
The synthetic ZS~-34 zeolite possesses a definite 1~ distinguishing crystalline structure whose X-ray diffrac-tion pattern shows substasntially the significant lines set forth in Table II.
5~
I/Io 11.5 ~ .2 Very S~rong 9.2 + .2 Weak 7.58 + .15 Medium
I/Io 11.5 ~ .2 Very S~rong 9.2 + .2 Weak 7.58 + .15 Medium
6.61 + .13 Strong 6.32 ~ .12 Weak 5.73 + .11 Medium 5.35 + .10 Weak 4.98 + .10 Weak 4.57 + .09 Strong-Very Strong 4.32 + .08 . Very Strong 4.16 ~ .08 Weak 3.81 ~ .07 Strong-Very Strong 3.74 + .07 Very Strong 3.59 + .07 Strong-Very Strong 3. 30 + . o6 Medium-Stron~
3.15 + .o6 Medium 2.92 + .05 Weak 2.85 + .05 Very Strong 2.80 + .05 Weak 2.67 ~ .05 Weak 2.52 ~ .05 Weak 2.48 + .05 Weak-Medium 2.35 + .04 Weak 2.28 + .04 Weak L7~5~
zs~-34 can be convent~onally synthesized by preparing a gel reaction mixture having a composition, in terms of mole ratios of oxides, falling within the following ranges:
Broad Prefer~ed ___ SiO2/Al2O3 10-70 10-55 OH /SiO2 0O3-1.0 0.3-0.8 H2O/O~1 20-100 20-80 K20/M2o 0.1-1.0 0.1-1.0 R /R ~ ~l 0.1~0~8 0.1-0.50 where R+ is choline [(CH3)3N-CH2CH2OH] and M is ~la + K and maintaining the mixture until crystals of the zeolite are formed. The quantity of OH is calculated from inorganic base (hyAroxide ion not neutralized by added mineral acid or acid salt. Resulting zeolite crystals are separated and recovered. Typical reaction conditons consist of heating the foregoing reaction mixture to a temperature of from about 80C to about 175C for a period of time of from about 12 hours to 200 days. A more preferred temperature range is from ahout 90 to 160C with the amount of time at a temperature in such range being from about 12 hours to 50 days.
The resulting crystalline product is separated from the mother liquor by filtration, water washing and drying, e.g., at 230F for from 4 to 48 hours. Milder conditions may be employed, if desired, e.g., room temperature under vacuum.
Zeolite ZSM-38 and the conventional preparation thereof are more particularly described in U.S. Patent 4,046,859. This zeolite can be identified, in terms of mole ratios of oxides and in thè anhydrous state, as follows:
.. .
,, 7S~
(0-3 2-5)R20 : (0~0-B)M20 : Al203 : xS102 wherein x ls greater than 8, R ls an organic nitrogen-containlng cation derived from a 2-(hydroxyalkyl) trialkylammonium compound and ~ i5 an alkall metal catlo~, and is characterized by a speclfled X-ray powder diffraction pattern.
In a preferred synthesized form, zeolite ZSM-38 has a formula, in terms of mole ratios Or oxides and in the anhydrous state, as follow~:
(o.4-2.5)R20 : (o-o.6)M2o : Al203 : ySiO2 wherein R is an organic nitrogen-containing cation derived from a 2-(hydroxyalkyl) trialkylammonium compound, wherein alkyl is methyl, ethyl or a combination thereof, M is an alkali metal, especially sodiumg and y is from greater than 8 to about 50.
The synthetic ZSM-38 zeolite possesses a definite distinguishing crystalline structure whose X-ray dlffraction pattern shows substantially the significant lines set forth in Table III.
~7 T,4EILE III
I/Io 9 . 8 * O . 20 StronG
9.1+ 0.19 ~ledium 5 8.o_ 0.16 Weak
3.15 + .o6 Medium 2.92 + .05 Weak 2.85 + .05 Very Strong 2.80 + .05 Weak 2.67 ~ .05 Weak 2.52 ~ .05 Weak 2.48 + .05 Weak-Medium 2.35 + .04 Weak 2.28 + .04 Weak L7~5~
zs~-34 can be convent~onally synthesized by preparing a gel reaction mixture having a composition, in terms of mole ratios of oxides, falling within the following ranges:
Broad Prefer~ed ___ SiO2/Al2O3 10-70 10-55 OH /SiO2 0O3-1.0 0.3-0.8 H2O/O~1 20-100 20-80 K20/M2o 0.1-1.0 0.1-1.0 R /R ~ ~l 0.1~0~8 0.1-0.50 where R+ is choline [(CH3)3N-CH2CH2OH] and M is ~la + K and maintaining the mixture until crystals of the zeolite are formed. The quantity of OH is calculated from inorganic base (hyAroxide ion not neutralized by added mineral acid or acid salt. Resulting zeolite crystals are separated and recovered. Typical reaction conditons consist of heating the foregoing reaction mixture to a temperature of from about 80C to about 175C for a period of time of from about 12 hours to 200 days. A more preferred temperature range is from ahout 90 to 160C with the amount of time at a temperature in such range being from about 12 hours to 50 days.
The resulting crystalline product is separated from the mother liquor by filtration, water washing and drying, e.g., at 230F for from 4 to 48 hours. Milder conditions may be employed, if desired, e.g., room temperature under vacuum.
Zeolite ZSM-38 and the conventional preparation thereof are more particularly described in U.S. Patent 4,046,859. This zeolite can be identified, in terms of mole ratios of oxides and in thè anhydrous state, as follows:
.. .
,, 7S~
(0-3 2-5)R20 : (0~0-B)M20 : Al203 : xS102 wherein x ls greater than 8, R ls an organic nitrogen-containlng cation derived from a 2-(hydroxyalkyl) trialkylammonium compound and ~ i5 an alkall metal catlo~, and is characterized by a speclfled X-ray powder diffraction pattern.
In a preferred synthesized form, zeolite ZSM-38 has a formula, in terms of mole ratios Or oxides and in the anhydrous state, as follow~:
(o.4-2.5)R20 : (o-o.6)M2o : Al203 : ySiO2 wherein R is an organic nitrogen-containing cation derived from a 2-(hydroxyalkyl) trialkylammonium compound, wherein alkyl is methyl, ethyl or a combination thereof, M is an alkali metal, especially sodiumg and y is from greater than 8 to about 50.
The synthetic ZSM-38 zeolite possesses a definite distinguishing crystalline structure whose X-ray dlffraction pattern shows substantially the significant lines set forth in Table III.
~7 T,4EILE III
I/Io 9 . 8 * O . 20 StronG
9.1+ 0.19 ~ledium 5 8.o_ 0.16 Weak
7~ OD 14 kI9diUm . 6.t7~ 0.14 ~edium 6 . 0~ 0.12 Weak ,, 4. 37+ 0. 09 Weak 4, 23* 0 . 09 ~Jeak .ol + o.o8 Very Strong 3.81. ~ o.o8 ;: Very Strong 3. 69 ~ 0, 07 ~edium 3-57 ~ 0.07 . . Very Strong --~3-51 ~ 0.07 . Very Strong 3~34 ~ 0~07 Medium 3.17 ~ o~o6 . Strong 3 . o8 ~ o ~ o6 : Medium 3.oo ~ o~o6 WeaX
2. 92 ~ 0,. o6 MedilLm 2 . 73 ~ o, o6 Weak 2 . 66 ~ 0. 05 Weak 2, 60 ~ 0. 05 ~Jeak 2.~'9 + 0.. 0~. Weak ,' . - ''' . ".
~14-Zeolite ZS~-38 can be conventionally synthesized by preparing a solutlon containlng sources of an alkali metal oxide, preferably sodlum oxide, an organlc nitrogen-conkaining oxide, an oxide of alumlnum, an oxide of sllicon and water and havlng a composltion, in terms of mole ratios of oxides falling within the following ranges:
Broad _ Preferred R+/(R+ + M+)0.2 -1.0 0.3 -0.9 OH-/SiO2 0.05-0.5 0.07-0.49 SiO2/A1203 8.8 -200 12-60 wherein R ls an organlc nitrogen-contalning cation derlved from a 2-(hydroxyalkyl) trialkylammonium compound and M is an alkali metal ion, and maintaining the m~ture until crystals of the zeolite are formed. Thereafter, the crystals are separated ~rom the liquid and recovered. Typical reaction conditions consist of heating the foregoing reaction mixture to a temperature of from about 90F to about 400F for a period o~ time of from about 6 hours to about 100 days. A more preferred temperature range is from about 150~ to about 400F with the amount of time at a temperature in such range being from about 6 hours to about 80 days.
The digestion of the gel particles is carried out until crystals form. The solid product is separated from the reaction medium, as by cooling the whole to room temperature, filtering and water washing. The crystalline product is there-after dried, e.g. at 230F for ~rom about 8 to 24 hours.
The values of Tables I, II and III were determined by standard techniques. The radiation was th~ K-alpha doublet of copper, and a Gelger counter spectrometer wlth a strip chart pen recorder ~as used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intenslties, 100 I/Io, where Io is the intensity of the strongest line or peak, and d(~), the interplanar spacing in Angstrom units, corresponding to the recorded lines, were calculated.
In the present improved method of zeolite synthesis, a reaction mixture is formed containing one or more sources Or alkali metal oxide, organic nitrogen-containing catlons, acid ions, an oxide of silicon, an oxide of aluminum and water.
The composition of the reaction mlxture must contain hydroxide ions and silica in the extremely low mole ratio of at most about 10-2, preferably from about 10-1 to about 10-2. The composition must also contain acid ions in amount less than the equlvalents of organic nitrogen present therein. The reaction mixture, further, must have a pH of at least 7, preferably from about 7 to about 12.
The sources of alkali metal oxide may be, for example J sodium, lithium or potassium hydroxides, oxides, carbonates, halides (e.g. chlorides and bromides), sulfates, nitrates, acetates, silicates, aluminates, phosphates and salts of carboxylic acids.
The sources of organic nitrogen-containin~ cations, depending, of course, on the particular zeolite product to result from crystallization from the reaction mixture, may be primary, secondary or tertiary amines or quarternary ammonium compounds, examples of which include salts of tetramethylammonium, ~7.~
tetraethylammonium, tetraprop~lammonium, tetrabutylammonium, dlethylammonlum, triethylammonium~ dibenzylammcnlum, dibenzyl-dlmethylammonlum, dibenzyldiethylammonium, benzyltrimethyl-ammonium and choline; or the compounds of trimethylamine~
trlethylamine, tripropylamine, ethylenediamine, propanediamine, butanedlamine, pentanediamine, hexanediamlne, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine, aniline, pyridine,piperidine and pyrrolidine.
The sources o~ acid ions may be, for example, HC1, H2SO4, H3PO4, HNO3, carboxylic acids, aluminum sulfates, nitrates, chlorides, phosphates or acid salts of primary, secondary or tertiary amines.
Sources of silicon oxides may be, for example, silica sols, alkali metal silicates, silica gels, siliclc acid or aluminosilicates.
Sources of aluminum oxides may be, for example, alkali metal aluminates, aluminum metal, hydrated aluminum oxides or aluminum salts of acids such as H2SO4, HCl, HNO3 and ~he like.
In general, the reaction mixture for the present improved synthesis process will have a composition, in terms of mole ratios of oxides, as follows:
Broadly Most Acce~table Pre~erred Preferred _ _ _ _ SiO2/A12O3 5-1000 10-200 15-100 oH-/SiO2 10-1_lo-2 1o-7-lo-2 10-6_1o-2 H2O/siO2 5-200 10-100 10-100 M/SiO2 0.01-5.0 0.1-2.0 0.2-1.0 R/SiO2 0.01-3.0 0.04-2.0 0.1-1.0 3o wherein R is an organic nitrogen-containing cation or organic nitrogen-containing cation source and M is an alkali metal ion.
~17S~lZ
Specifically~ when ZSM-5 is the desired zeolite product Or the present lmproved synthesis process, the reactlon mixture will have a composltion, in terms of mole ratios of oxides, as follows:
S102/Alz03 ~ 5-1000 3H-/SiO2 = lo~10 ~0 2 H20/SiO2 = 5-200 M/SiO2 = 0.01-3.0 F~/S102 = O.01-1.O
wherein R is a tetrapropylammonium cation and M is an alkali metal ion. The reaction mlxture must be malntained at a temperature of from about 100F to about 400F for a period of time of from about 3 hours to about 150 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-11 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have 2 composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 10-180 OH-/SiO~ = lO-lO-lb-2 H20/SiOz ~ 5-100 M/SiO2 = 0.1-2.0 R/S102 = 0.04-1.0 ~75~
whereln R is a tetrabutyla~nonium cation and M ls an alkali metal ion. The reaction mixture must be maint2ined at a temperature of from about 100F to about 400F for a period of time o~ from about 4 hours ~o about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-12 is the desired ~eolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 40-200 OH /SiO2 = lo~10_lo~2 H20/SiO2 = 5-100 M/S102 = 0.1-3.0 R/SiO2 ~ = 0.1-2.0 wherein R is a tetraethylammonium cation or a cation derived from triethylamine and M is an alkali metal ion. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reactton mixture must be maintained at a temperature of from about 100F
to about 400F for a period of time of from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered.
Separation may be accomplished by, for example~ cooling the whole to room temperature, filtering and water washing.
7~
When ZSM-23 ls the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 10-200 OH /SiO2 = 10-1_lo-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from pyrrolidlne and M is an alkali metal lon. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reaction mixture must be maintained at a temperature Or from about 100~F to about 400F for a period of time o~ from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-34 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 5-100 OH-/SiO2 = 1o~10_1o~2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from choline and M is an alkali metal ion. The reaction mixture must be maintained at a temperature of from about 100F to abou~ 400F for a period Or time of ~rom about 3 hours ~o about ].50 days until crystals form. Thereafter, the crystals are separated ~rom the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-35 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as lQ follows:
SiO2/Al203 = 8.8-200 OH-/SiO2 = 10-1_lo-2 H20/SiO2 = 5~100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.05-2.0 wherein R is a cation derived from ethylenediamine or pyrrolidine and M is an alkali metal ion. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reaction mixture must be maintained at a temperature of from about 100F to about 400F for a period of time of from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, ~iltering and water washing.
When ZSM-38 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
7S~
SiO2/A12O3 - 8 . 8-200 OH-/3iO2 ~ 10-10 10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3. 0 R/SiO2 - 0.1-2. 0 s~
wherein R is derived from a 2-(hydroxyalkyl) trlalkylammCniUm compound wherein alkyl is methyl, ethyl or a combination thereof, and M is an alkali metal ion. The reaction mixture must be maintained at a temperature o~ ~rom about 100F to about 400F
for a period o~ tlme o~ ~rom about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated ~rom the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
It is recalled that in calculating the mole ratio of hydroxide ions/silica, it is conventional to calculate hydroxide by summing moles o~ OH-, whether added as NaOH, as quaternary ammonium hydroxide, as sodium silicate (NaOH + SiG2), as sodium aluminate (NaOH + Al2O3), or the 1 ke, and to subtract from that sum any moles o~ acid added. Acid m?y be added simply as HCl, HNO3, H2SO4, acetic acid, and the like or it may be added as an aluminum sulfate (A12O3 + H2SO4), chloride (Al2O3 + HCl), nitrate (Al2O3 + HNO3), etc. I~ particular, no contribution is assigned to organic bases such as amines ln this calculation.
Although the usefulness of this invention is to be ~ound with quaternary ammonium cations at OH-/Si02 ratios below those recognized earlier, it is with theaminesthat this invention is ideally suited. Amines present in reaction mixtures having an 0H~/SiO2 ratio o~ 0.01 are protonated when further acid is added. Until said additlonal acid exceeds the amine present, the pH remains above 7.
~1~7S~
In a conventional calculation which does not consider amlnes, the total moles of acid could thereby exceed the moles of hydroxlde added in said reaction mixture and subtraction would thereby lead to apparent "ne~atlve" OH /S102 ratios. A negative ratio is, of course, not possible since the true moles of hydroxide (per liter) in an aqueous mixture are always positlve and equal to 10-14 divided by the moles per liter of acid.
Calculated from the krue moles of hydroxlde, the present invention would include an OH /SiO2 range of about 10 10 to about 10-2. Maintaining the convention which has been established in describing reaction mixture compositions, we define the quantity of acid added in excess of the hydroxide added by the ratio H~(additional)/SiO2.
The improved zeolites prepared by the present improved method may be used for organic compound conversion ~75~:
in the hydrogen form or they may be base exchanged or impregnated to co~tain a~monium or 2 metal catlon complement.
It is desirable to calcine the cataiyst after base e~change.
The metal cations that may be present include any G~ the cations o~ the metals o~ Groups I through VI~I of the PerioGic Table, especiaIly rare earth metals. However~ in the case Or Group IA metals, the cation content should ln no case be so large as to effectively inactivate the catalyst.
- As in the case Or many catalysts, it is desirable to incorporate the improved catalyst prepared by the present improved method with another material resistant to the temperature and other conditions employed in some organic compound conversion processes. Such matrix materials i~clude active and inactlve materials and synthetic or naturally occurring zeolites as well as inorganic material such as clays, silica and/or metal oxides.
The latter may be either natur lly occurring or in the form of gelatinous precipitates, sols or gels including mixtures o~
silica and me~al oxides. Inactive materials suitably~ serve as diluents to control the amount of conversion in a given process so that products can be obtained econom~cally and orderly without employing other means ~or controlling the rate of reaction. Frequently, zeolite materials have been incorporated into naturally occurring clays, e~.g. bentonite and kaolin.
These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength so it may be used in a process where the catalyst is subjected to rough handling,such as in a ~luidized system, which may tend to break the catalyst down into powder-like materials which cause problems in processing.
1~75~
~aturally occurring clays which can be composited with the i~lproved zeolites pr~pared hereby include the montmorillonite and kaolin families, which include the su~-bentonites and the kaolins com~only kno~:n as Dixie, McNammee, Georgia and Florida clays or others in which the main mineral cons~ituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially sub~ected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the zeolites made hereby can be composited ~Jith one or more porous matrix materials such as alumina, silica-alumina, sllica-mag~esla, silica-zirconia, silica-thoria, silica-beryllia, sillca-titania, titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina zirconia, silica-alumina-magnesia and sllica-magnesla-zirconia. The matrix can be in the form o~ a cogel. A mixture of these components, one w1th the other and/or wlth a clay, could also be used. The relati~e proportions of zeolite and inorganic oxide gel matrix and/or clay vary widely with the crystalline aluminosilic~te content ranging from about 1 to about 90 percent by weight a~d more usually in the range of about 2 to about 50 percent by weight of the composite.
Zeolites prepared by the present improved method are valuable catalysts in ~arious organic compound, e.g.
hydrocarbon compounds and oxygenates such as methanol, conversion processes. Such processes include, for example, alkylation of aromatics with olefins, aromatization o~ normally gaseous olefins and paraffins, aromatization f normally liquid low molecular weight parrafins 2nd olefins, isomerization of aromatics~ paraffins and ole~ins, disproportion2tion o aromatics, transal~:ylation of 2romatics, oligo~eri~tion o~
~75~Z
ole~ins and crackin~ and hydrocracking. All o~ ~he 1 ore~oin~
catalytic processes are of value since they result in upgra~ing ol the organic charge being processed.
The process rOr upgrading re~ ormates ~rherein a zeolite prepared in accordance herewith is employed as catalyst ~enerally involves contact during processing with a refor~ate or refor~.er effluent, wlth or withou~ added hydrogen, at a temperature bet~een 500F and about 1100F and prerer~bly between about 550F and about 1000F. The reaction pressure in such operation is generally wi~hin th~ range of about 25 and about Z000 psig and pre~erably about 50 to aboùt 1000 psig. The liquid hourly space velocity, i.e. the liquld volume o~
hydrocarbon per hour per volume of catalyst, is between about 0.1 and about 250, and preferably between about 1 and 100. Although hydrogen is not essential to this process, when it is used the molar ratio of hydrogen to hydrocarbon charge employed is between about 0.1 and about 80 and preferably between about 1 and about 10.
Oligomerization of ole~ins, i.e. olefins having 2 to 10 carbon atoms, is effectively carried out with t~e zeolite prepared in accordance herewith 25 catalyst. Such - reaction is suitably effected at a temperature between about 550F and about 1150F, a pressure between about 0.01 and about 1000 psig utilizing a weight hourly space velocity within the approximate range o~ 0.1 to 1000.
Alkylation of aromatic hydrocarbons, e.g. benzene, with an alkylating agent such as an alkyl h21ide, an alcohol or an olefin,~is also readily e~fected in the presence of the presently made zeolite as catalyst with reduced agin~.
Alkylation conditions include a temperature between about 400F and about 1000F, a pressure between about 25 and about 1000 psig utilizing an aromatic hydrocarbon/alkylating agent mole ratio of 2 to 200 and an alkylatin~ agent weigh~ hourly space velocity within the approximate range of 0.5 ~o 50.
a75~;~
Xylene isomer~zat~on is another reactiun suitably condllcted in the presence of the zeolite made in accord2nce here~lth as catalyst. Isomeriza~o~ ccnditions include a tempe~ature between about 300F and about 900F, a pressure between about 25 and abou~ 1000 psig utilizing a wei~ht hourly space veloc~ty within the approximate range of 0.2 to 100.
Aromatics, such as, for example, toluene, ~ay be disproportionated in the presence of the presently made zeolite under a temperature of from about 450F to about 1100F, a pressure of from about 50 psig to about 800 psig and a liquid hourly space velocity within the approximate range of about 0.1 to about 20. Aliphatic hydrocarbons may also be disp~o-portionated in the presence of zeolite prepared by the present improved method at a temperature of from about 350F to about 900F, a pressure between 0 and 3,000 psig and a liquid hourly space velocity of between about 0.01 and about 5.
When the conversion of organic compounds with the presently made zeolite 2S catalyst is cracking, catalytic conversion condltions should be maintained within certain ranges, including a tempera~ure of from about 700F to about 1200F, preferably from about 800F to about 1000F, a pressure of from about atmospheric to about 200 psig, and a liquid hourly space velocity of from about 0.5 hr 1 to about 50 hr 1, pre~erably from about 1 hr 1 to about 10 hr 1 When the conversion is hydrocracking, catalytic conversion conditions should be maintained within some~lhat different ranges, including a temperature of from about 400F to about 1000F, preferably from about 500F to about 850F, a pressure of from about 500 psig to about 3500 psig, a liquid hourly space velocity of from about 0.1 hr~l to about 10 hr-l, pre~erably ~rom about 0.2 hr~l to about 5 hr~l, and a hydrogen/hydrocarbon ratio of from about 1000 sc~/bbl to about 20,000 sc~/bbl, preferably from about 3,000 scf/bbl to about 10,000 scf/bbl.
It may be desirable ln some lnst~nces to add a hydrogenation/dehydrogena~ion component to the zeolite prepared in accordance herewith ~or use as catalyst. The amount of the hydrogenation/dehydrogenation component employed is not narrowly critical and can range rrom about 0.01 to about 30 welght percen~ based on the entire catalyst. A variety of hydrogenation components may be combined with either the zeolite and/or matrix in any feasible manner which affords intimate contact of the components, employing well known techniques such as base ex~hange, impregnation, coprecipitatlon, cogellation, mechanical admixture of one component with the . other and the like. The hydrogenation component can include ~30-7~
metals, oxldes and sul~ides o~ metals o~ the Periodic Table ~hich fall in Group VI-3 lncluding chromium~ molybdenum, tungsten and the like; Group II-B including zinc and cadmium;
Group VIII including cobalt, nickel, platinum, palladium, ruthenium, rhodium, osmium and irldium; Group IV-A such as germanium and t~n and combinations of metals, sulfides and oxides Or ~etals of Group VI-~ and VIII, such as nickel-tungsten~sulfide, cobal~ oxide-molybdenum oxide and the like.
Pre-treatment before use varies depending on the hydrogenation component present. For example, with components such as nickel-tungsten, cobalt-molybdenum, platinum and palladium, the catalyst may desirably be sulfided. With metals like platinum or palladlum, a hydrogenation step may also be employed. These techniques are well known in the art and are accomplished in a conventional manner.
In order to more fully illustrate the nature of the invention and the manner o~ practicing same, the ~ollowing examples are presented.
7~
Exam~_e 1 In accordance with the prior art m~thod o~
preparing zeolite ZSM-5, to a solution o~ 63.3 grams Q-brand sodium sillca (28.5 wt. % SiO2, 7.75 wt. %
Na20 and 63.75 wt. % H20) in 79.2 grams o~ water in a polypropylene bo~tle was added a solu~ion of 2.05 grams A12(S04)3-16H20, 3.8 grams H2S04 and 7.85 grams tetrapropyl-ammonium bromlde in 108.3 grams of water. A~ter vigorous mixing the pH o~ the mixture was measured to be ~ 10.
The bottle was placed in a steam chest at 90-95C.
The reaction mlxture ha~ a molar composition as ~ollows:
SiO2/A1203 = 92 OH-/SiO2 = 0.20 H20/SiO2 = 42 ~/S102 ~ 0.53 R/S102 = 0.10 After 30 days, a sample of the gel was taken, washed with water, and dried. An X-ray diffraction pattern showed the sample to contain about 40% ZSM-5 together wlth amorphous material.
ExamPle ?
In accordance wlth the present improved method of preparing zeolite ZSM-5, to a solution of 63.3 grams Q-brand sodium sllicate ln 79.2 grams o~ water in a poIypropylene bottle was added a solution o~ 2.05 grams A12(S04)3-16H20, 7.2 grams H2S04 and 7.85 grams tetrapropylammonium bromide in 108 . 3 grams o~ water. The acid ions in this reaction mixture were present in amount suf~icient to reduce the OH-/SiO2 ~7~
r~tio below lo-2. A~ter vigorous mlxin~ the pH was determined to be 7. The bottle was then placed in a steam chest at 90-95C. I~e reaction mlxture had a molar composition as follows.
SiO2/A12O3 = 92 OH /SlO2 = ~10-2 H2O/SiO2 = 42 M/SiO2 = 0.53 R/SlO2 = 0.10 Although successful crystallization was noted earlier, the product ZSM-5 was removed, washed, and dried after 30 days in the steam chest. The X-ray di~raction pattern showed 100~ ZSM-5. Scanning electron micrograms showed the material to be relatively uniform crystals of 6-12 micron diameter.
Examples 3-6 In these exampies, prior art and present improved , methods of syntheses of zeolite ZSM-35 were conducted.
¦ Crystallization at 100C was conducted in polypropylene bottles under static conditions in a steam chest. The slIicate source was Q-brand (27.8% SiO2, 8.42% Na2O) and the alumina source was A12(SO4)2 16H20. The organic nitrogen-containing cation source was pyrrolidine. Reaction mixture compositions (mole ratios), total days in a steam chest ~or crystalli~ation to occur and zeolite product compositions are tabulated in Table IV, hereinafter presented. It is observed from these examples that prior art methods (Ex2mples 5 and 6) ~ail to compare favorably with the present improved method of synthesis ~Examples 3 and 4) for zeol~te ZSM-35. After only 35 and 39 days ln the steam chest, 100% ZSM-35 was obtained from the improved methcd of Examples 3 and 4. After as many as 85 days in the steam chest for the reactlon mixture of Example 5, the product contained 50% ZSM-35 and 50~ mordenite. ~fter 70 days in the steam chest for the reaction mixture of Example 6, only 10% ZSM-35 resulted.
z tU ~ 3 3 :r ~ ,~ ~1 ~ Co t-- o Cl~
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OO O O
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O ~1 U~ ~
~q O ~1 0 O rl ~ ~ O O O O
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:~ ~9 H rl N
:~: o c~
~ ~ L~
m o z o o o o .- ~d ~: o ~ ~ ~ o~
V~ I I ~U
o o o o . o ~O
o~l v~ c~ o 3 ~r N
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t~ tr ) 3 Lt'~
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~ :. O O V
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_~ ~ ~ I I ~d h _ r~l ~ Cr~
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Example 7 A sample of crystalllne alumlnosillcate zeollte ZSM-5 prepared as ln Example 2 was evaluated for catalytlc activity with a flve-component feedstock of n-hexane, 3-methylpentane, 2,3-dimethylbutane, benzene and toluene at 2Q0 psig, a weight hourly space velocity (WHSV) o~ 2.9 hr-l, a temperature of 427C and a hydrogen/hydrocarbon mole ratio of 3.6. This zeolite, after exchange, provided 94%
conversion of n-hexane and 46% conversion o~ 3-methylpentane.
Of the converted paraffln charge, 11% reacted with benzene and toluene to produce alkyl aromatics.
ExamE~e_8 A sample of ZSM-35 was prepared as in Example 3, but at a temperatur.~ of 160C and with R/SiO2 = 0.14 and H+(additional)/SiO2 = 0.03. The ZSM-35 product was evaluated for catalytic activity with a ~eedstock as in Example 7.
Test conditions were 200 psig, 3.2 hr 1 WHSV, 427C and a hydrogen/hydrocarbon mole ratio of 4.8. Thls ZSM-35 converted 96% n-hexane and 20% 3-methylpentane.
.
-37~
2. 92 ~ 0,. o6 MedilLm 2 . 73 ~ o, o6 Weak 2 . 66 ~ 0. 05 Weak 2, 60 ~ 0. 05 ~Jeak 2.~'9 + 0.. 0~. Weak ,' . - ''' . ".
~14-Zeolite ZS~-38 can be conventionally synthesized by preparing a solutlon containlng sources of an alkali metal oxide, preferably sodlum oxide, an organlc nitrogen-conkaining oxide, an oxide of alumlnum, an oxide of sllicon and water and havlng a composltion, in terms of mole ratios of oxides falling within the following ranges:
Broad _ Preferred R+/(R+ + M+)0.2 -1.0 0.3 -0.9 OH-/SiO2 0.05-0.5 0.07-0.49 SiO2/A1203 8.8 -200 12-60 wherein R ls an organlc nitrogen-contalning cation derlved from a 2-(hydroxyalkyl) trialkylammonium compound and M is an alkali metal ion, and maintaining the m~ture until crystals of the zeolite are formed. Thereafter, the crystals are separated ~rom the liquid and recovered. Typical reaction conditions consist of heating the foregoing reaction mixture to a temperature of from about 90F to about 400F for a period o~ time of from about 6 hours to about 100 days. A more preferred temperature range is from about 150~ to about 400F with the amount of time at a temperature in such range being from about 6 hours to about 80 days.
The digestion of the gel particles is carried out until crystals form. The solid product is separated from the reaction medium, as by cooling the whole to room temperature, filtering and water washing. The crystalline product is there-after dried, e.g. at 230F for ~rom about 8 to 24 hours.
The values of Tables I, II and III were determined by standard techniques. The radiation was th~ K-alpha doublet of copper, and a Gelger counter spectrometer wlth a strip chart pen recorder ~as used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intenslties, 100 I/Io, where Io is the intensity of the strongest line or peak, and d(~), the interplanar spacing in Angstrom units, corresponding to the recorded lines, were calculated.
In the present improved method of zeolite synthesis, a reaction mixture is formed containing one or more sources Or alkali metal oxide, organic nitrogen-containing catlons, acid ions, an oxide of silicon, an oxide of aluminum and water.
The composition of the reaction mlxture must contain hydroxide ions and silica in the extremely low mole ratio of at most about 10-2, preferably from about 10-1 to about 10-2. The composition must also contain acid ions in amount less than the equlvalents of organic nitrogen present therein. The reaction mixture, further, must have a pH of at least 7, preferably from about 7 to about 12.
The sources of alkali metal oxide may be, for example J sodium, lithium or potassium hydroxides, oxides, carbonates, halides (e.g. chlorides and bromides), sulfates, nitrates, acetates, silicates, aluminates, phosphates and salts of carboxylic acids.
The sources of organic nitrogen-containin~ cations, depending, of course, on the particular zeolite product to result from crystallization from the reaction mixture, may be primary, secondary or tertiary amines or quarternary ammonium compounds, examples of which include salts of tetramethylammonium, ~7.~
tetraethylammonium, tetraprop~lammonium, tetrabutylammonium, dlethylammonlum, triethylammonium~ dibenzylammcnlum, dibenzyl-dlmethylammonlum, dibenzyldiethylammonium, benzyltrimethyl-ammonium and choline; or the compounds of trimethylamine~
trlethylamine, tripropylamine, ethylenediamine, propanediamine, butanedlamine, pentanediamine, hexanediamlne, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine, aniline, pyridine,piperidine and pyrrolidine.
The sources o~ acid ions may be, for example, HC1, H2SO4, H3PO4, HNO3, carboxylic acids, aluminum sulfates, nitrates, chlorides, phosphates or acid salts of primary, secondary or tertiary amines.
Sources of silicon oxides may be, for example, silica sols, alkali metal silicates, silica gels, siliclc acid or aluminosilicates.
Sources of aluminum oxides may be, for example, alkali metal aluminates, aluminum metal, hydrated aluminum oxides or aluminum salts of acids such as H2SO4, HCl, HNO3 and ~he like.
In general, the reaction mixture for the present improved synthesis process will have a composition, in terms of mole ratios of oxides, as follows:
Broadly Most Acce~table Pre~erred Preferred _ _ _ _ SiO2/A12O3 5-1000 10-200 15-100 oH-/SiO2 10-1_lo-2 1o-7-lo-2 10-6_1o-2 H2O/siO2 5-200 10-100 10-100 M/SiO2 0.01-5.0 0.1-2.0 0.2-1.0 R/SiO2 0.01-3.0 0.04-2.0 0.1-1.0 3o wherein R is an organic nitrogen-containing cation or organic nitrogen-containing cation source and M is an alkali metal ion.
~17S~lZ
Specifically~ when ZSM-5 is the desired zeolite product Or the present lmproved synthesis process, the reactlon mixture will have a composltion, in terms of mole ratios of oxides, as follows:
S102/Alz03 ~ 5-1000 3H-/SiO2 = lo~10 ~0 2 H20/SiO2 = 5-200 M/SiO2 = 0.01-3.0 F~/S102 = O.01-1.O
wherein R is a tetrapropylammonium cation and M is an alkali metal ion. The reaction mlxture must be malntained at a temperature of from about 100F to about 400F for a period of time of from about 3 hours to about 150 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-11 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have 2 composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 10-180 OH-/SiO~ = lO-lO-lb-2 H20/SiOz ~ 5-100 M/SiO2 = 0.1-2.0 R/S102 = 0.04-1.0 ~75~
whereln R is a tetrabutyla~nonium cation and M ls an alkali metal ion. The reaction mixture must be maint2ined at a temperature of from about 100F to about 400F for a period of time o~ from about 4 hours ~o about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-12 is the desired ~eolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 40-200 OH /SiO2 = lo~10_lo~2 H20/SiO2 = 5-100 M/S102 = 0.1-3.0 R/SiO2 ~ = 0.1-2.0 wherein R is a tetraethylammonium cation or a cation derived from triethylamine and M is an alkali metal ion. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reactton mixture must be maintained at a temperature of from about 100F
to about 400F for a period of time of from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered.
Separation may be accomplished by, for example~ cooling the whole to room temperature, filtering and water washing.
7~
When ZSM-23 ls the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 10-200 OH /SiO2 = 10-1_lo-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from pyrrolidlne and M is an alkali metal lon. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reaction mixture must be maintained at a temperature Or from about 100~F to about 400F for a period of time o~ from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-34 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
SiO2/A1203 = 5-100 OH-/SiO2 = 1o~10_1o~2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from choline and M is an alkali metal ion. The reaction mixture must be maintained at a temperature of from about 100F to abou~ 400F for a period Or time of ~rom about 3 hours ~o about ].50 days until crystals form. Thereafter, the crystals are separated ~rom the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
When ZSM-35 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as lQ follows:
SiO2/Al203 = 8.8-200 OH-/SiO2 = 10-1_lo-2 H20/SiO2 = 5~100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.05-2.0 wherein R is a cation derived from ethylenediamine or pyrrolidine and M is an alkali metal ion. The quantity of hydroxide ions is calculated only from the inorganic sources of alkali without any organic base contribution. The reaction mixture must be maintained at a temperature of from about 100F to about 400F for a period of time of from about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated from the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, ~iltering and water washing.
When ZSM-38 is the desired zeolite product of the present improved synthesis process, the reaction mixture will have a composition, in terms of mole ratios of oxides, as follows:
7S~
SiO2/A12O3 - 8 . 8-200 OH-/3iO2 ~ 10-10 10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3. 0 R/SiO2 - 0.1-2. 0 s~
wherein R is derived from a 2-(hydroxyalkyl) trlalkylammCniUm compound wherein alkyl is methyl, ethyl or a combination thereof, and M is an alkali metal ion. The reaction mixture must be maintained at a temperature o~ ~rom about 100F to about 400F
for a period o~ tlme o~ ~rom about 6 hours to about 180 days until crystals form. Thereafter, the crystals are separated ~rom the reaction medium and recovered. Separation may be accomplished by, for example, cooling the whole to room temperature, filtering and water washing.
It is recalled that in calculating the mole ratio of hydroxide ions/silica, it is conventional to calculate hydroxide by summing moles o~ OH-, whether added as NaOH, as quaternary ammonium hydroxide, as sodium silicate (NaOH + SiG2), as sodium aluminate (NaOH + Al2O3), or the 1 ke, and to subtract from that sum any moles o~ acid added. Acid m?y be added simply as HCl, HNO3, H2SO4, acetic acid, and the like or it may be added as an aluminum sulfate (A12O3 + H2SO4), chloride (Al2O3 + HCl), nitrate (Al2O3 + HNO3), etc. I~ particular, no contribution is assigned to organic bases such as amines ln this calculation.
Although the usefulness of this invention is to be ~ound with quaternary ammonium cations at OH-/Si02 ratios below those recognized earlier, it is with theaminesthat this invention is ideally suited. Amines present in reaction mixtures having an 0H~/SiO2 ratio o~ 0.01 are protonated when further acid is added. Until said additlonal acid exceeds the amine present, the pH remains above 7.
~1~7S~
In a conventional calculation which does not consider amlnes, the total moles of acid could thereby exceed the moles of hydroxlde added in said reaction mixture and subtraction would thereby lead to apparent "ne~atlve" OH /S102 ratios. A negative ratio is, of course, not possible since the true moles of hydroxide (per liter) in an aqueous mixture are always positlve and equal to 10-14 divided by the moles per liter of acid.
Calculated from the krue moles of hydroxlde, the present invention would include an OH /SiO2 range of about 10 10 to about 10-2. Maintaining the convention which has been established in describing reaction mixture compositions, we define the quantity of acid added in excess of the hydroxide added by the ratio H~(additional)/SiO2.
The improved zeolites prepared by the present improved method may be used for organic compound conversion ~75~:
in the hydrogen form or they may be base exchanged or impregnated to co~tain a~monium or 2 metal catlon complement.
It is desirable to calcine the cataiyst after base e~change.
The metal cations that may be present include any G~ the cations o~ the metals o~ Groups I through VI~I of the PerioGic Table, especiaIly rare earth metals. However~ in the case Or Group IA metals, the cation content should ln no case be so large as to effectively inactivate the catalyst.
- As in the case Or many catalysts, it is desirable to incorporate the improved catalyst prepared by the present improved method with another material resistant to the temperature and other conditions employed in some organic compound conversion processes. Such matrix materials i~clude active and inactlve materials and synthetic or naturally occurring zeolites as well as inorganic material such as clays, silica and/or metal oxides.
The latter may be either natur lly occurring or in the form of gelatinous precipitates, sols or gels including mixtures o~
silica and me~al oxides. Inactive materials suitably~ serve as diluents to control the amount of conversion in a given process so that products can be obtained econom~cally and orderly without employing other means ~or controlling the rate of reaction. Frequently, zeolite materials have been incorporated into naturally occurring clays, e~.g. bentonite and kaolin.
These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength so it may be used in a process where the catalyst is subjected to rough handling,such as in a ~luidized system, which may tend to break the catalyst down into powder-like materials which cause problems in processing.
1~75~
~aturally occurring clays which can be composited with the i~lproved zeolites pr~pared hereby include the montmorillonite and kaolin families, which include the su~-bentonites and the kaolins com~only kno~:n as Dixie, McNammee, Georgia and Florida clays or others in which the main mineral cons~ituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially sub~ected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the zeolites made hereby can be composited ~Jith one or more porous matrix materials such as alumina, silica-alumina, sllica-mag~esla, silica-zirconia, silica-thoria, silica-beryllia, sillca-titania, titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina zirconia, silica-alumina-magnesia and sllica-magnesla-zirconia. The matrix can be in the form o~ a cogel. A mixture of these components, one w1th the other and/or wlth a clay, could also be used. The relati~e proportions of zeolite and inorganic oxide gel matrix and/or clay vary widely with the crystalline aluminosilic~te content ranging from about 1 to about 90 percent by weight a~d more usually in the range of about 2 to about 50 percent by weight of the composite.
Zeolites prepared by the present improved method are valuable catalysts in ~arious organic compound, e.g.
hydrocarbon compounds and oxygenates such as methanol, conversion processes. Such processes include, for example, alkylation of aromatics with olefins, aromatization o~ normally gaseous olefins and paraffins, aromatization f normally liquid low molecular weight parrafins 2nd olefins, isomerization of aromatics~ paraffins and ole~ins, disproportion2tion o aromatics, transal~:ylation of 2romatics, oligo~eri~tion o~
~75~Z
ole~ins and crackin~ and hydrocracking. All o~ ~he 1 ore~oin~
catalytic processes are of value since they result in upgra~ing ol the organic charge being processed.
The process rOr upgrading re~ ormates ~rherein a zeolite prepared in accordance herewith is employed as catalyst ~enerally involves contact during processing with a refor~ate or refor~.er effluent, wlth or withou~ added hydrogen, at a temperature bet~een 500F and about 1100F and prerer~bly between about 550F and about 1000F. The reaction pressure in such operation is generally wi~hin th~ range of about 25 and about Z000 psig and pre~erably about 50 to aboùt 1000 psig. The liquid hourly space velocity, i.e. the liquld volume o~
hydrocarbon per hour per volume of catalyst, is between about 0.1 and about 250, and preferably between about 1 and 100. Although hydrogen is not essential to this process, when it is used the molar ratio of hydrogen to hydrocarbon charge employed is between about 0.1 and about 80 and preferably between about 1 and about 10.
Oligomerization of ole~ins, i.e. olefins having 2 to 10 carbon atoms, is effectively carried out with t~e zeolite prepared in accordance herewith 25 catalyst. Such - reaction is suitably effected at a temperature between about 550F and about 1150F, a pressure between about 0.01 and about 1000 psig utilizing a weight hourly space velocity within the approximate range o~ 0.1 to 1000.
Alkylation of aromatic hydrocarbons, e.g. benzene, with an alkylating agent such as an alkyl h21ide, an alcohol or an olefin,~is also readily e~fected in the presence of the presently made zeolite as catalyst with reduced agin~.
Alkylation conditions include a temperature between about 400F and about 1000F, a pressure between about 25 and about 1000 psig utilizing an aromatic hydrocarbon/alkylating agent mole ratio of 2 to 200 and an alkylatin~ agent weigh~ hourly space velocity within the approximate range of 0.5 ~o 50.
a75~;~
Xylene isomer~zat~on is another reactiun suitably condllcted in the presence of the zeolite made in accord2nce here~lth as catalyst. Isomeriza~o~ ccnditions include a tempe~ature between about 300F and about 900F, a pressure between about 25 and abou~ 1000 psig utilizing a wei~ht hourly space veloc~ty within the approximate range of 0.2 to 100.
Aromatics, such as, for example, toluene, ~ay be disproportionated in the presence of the presently made zeolite under a temperature of from about 450F to about 1100F, a pressure of from about 50 psig to about 800 psig and a liquid hourly space velocity within the approximate range of about 0.1 to about 20. Aliphatic hydrocarbons may also be disp~o-portionated in the presence of zeolite prepared by the present improved method at a temperature of from about 350F to about 900F, a pressure between 0 and 3,000 psig and a liquid hourly space velocity of between about 0.01 and about 5.
When the conversion of organic compounds with the presently made zeolite 2S catalyst is cracking, catalytic conversion condltions should be maintained within certain ranges, including a tempera~ure of from about 700F to about 1200F, preferably from about 800F to about 1000F, a pressure of from about atmospheric to about 200 psig, and a liquid hourly space velocity of from about 0.5 hr 1 to about 50 hr 1, pre~erably from about 1 hr 1 to about 10 hr 1 When the conversion is hydrocracking, catalytic conversion conditions should be maintained within some~lhat different ranges, including a temperature of from about 400F to about 1000F, preferably from about 500F to about 850F, a pressure of from about 500 psig to about 3500 psig, a liquid hourly space velocity of from about 0.1 hr~l to about 10 hr-l, pre~erably ~rom about 0.2 hr~l to about 5 hr~l, and a hydrogen/hydrocarbon ratio of from about 1000 sc~/bbl to about 20,000 sc~/bbl, preferably from about 3,000 scf/bbl to about 10,000 scf/bbl.
It may be desirable ln some lnst~nces to add a hydrogenation/dehydrogena~ion component to the zeolite prepared in accordance herewith ~or use as catalyst. The amount of the hydrogenation/dehydrogenation component employed is not narrowly critical and can range rrom about 0.01 to about 30 welght percen~ based on the entire catalyst. A variety of hydrogenation components may be combined with either the zeolite and/or matrix in any feasible manner which affords intimate contact of the components, employing well known techniques such as base ex~hange, impregnation, coprecipitatlon, cogellation, mechanical admixture of one component with the . other and the like. The hydrogenation component can include ~30-7~
metals, oxldes and sul~ides o~ metals o~ the Periodic Table ~hich fall in Group VI-3 lncluding chromium~ molybdenum, tungsten and the like; Group II-B including zinc and cadmium;
Group VIII including cobalt, nickel, platinum, palladium, ruthenium, rhodium, osmium and irldium; Group IV-A such as germanium and t~n and combinations of metals, sulfides and oxides Or ~etals of Group VI-~ and VIII, such as nickel-tungsten~sulfide, cobal~ oxide-molybdenum oxide and the like.
Pre-treatment before use varies depending on the hydrogenation component present. For example, with components such as nickel-tungsten, cobalt-molybdenum, platinum and palladium, the catalyst may desirably be sulfided. With metals like platinum or palladlum, a hydrogenation step may also be employed. These techniques are well known in the art and are accomplished in a conventional manner.
In order to more fully illustrate the nature of the invention and the manner o~ practicing same, the ~ollowing examples are presented.
7~
Exam~_e 1 In accordance with the prior art m~thod o~
preparing zeolite ZSM-5, to a solution o~ 63.3 grams Q-brand sodium sillca (28.5 wt. % SiO2, 7.75 wt. %
Na20 and 63.75 wt. % H20) in 79.2 grams o~ water in a polypropylene bo~tle was added a solu~ion of 2.05 grams A12(S04)3-16H20, 3.8 grams H2S04 and 7.85 grams tetrapropyl-ammonium bromlde in 108.3 grams of water. A~ter vigorous mixing the pH o~ the mixture was measured to be ~ 10.
The bottle was placed in a steam chest at 90-95C.
The reaction mlxture ha~ a molar composition as ~ollows:
SiO2/A1203 = 92 OH-/SiO2 = 0.20 H20/SiO2 = 42 ~/S102 ~ 0.53 R/S102 = 0.10 After 30 days, a sample of the gel was taken, washed with water, and dried. An X-ray diffraction pattern showed the sample to contain about 40% ZSM-5 together wlth amorphous material.
ExamPle ?
In accordance wlth the present improved method of preparing zeolite ZSM-5, to a solution of 63.3 grams Q-brand sodium sllicate ln 79.2 grams o~ water in a poIypropylene bottle was added a solution o~ 2.05 grams A12(S04)3-16H20, 7.2 grams H2S04 and 7.85 grams tetrapropylammonium bromide in 108 . 3 grams o~ water. The acid ions in this reaction mixture were present in amount suf~icient to reduce the OH-/SiO2 ~7~
r~tio below lo-2. A~ter vigorous mlxin~ the pH was determined to be 7. The bottle was then placed in a steam chest at 90-95C. I~e reaction mlxture had a molar composition as follows.
SiO2/A12O3 = 92 OH /SlO2 = ~10-2 H2O/SiO2 = 42 M/SiO2 = 0.53 R/SlO2 = 0.10 Although successful crystallization was noted earlier, the product ZSM-5 was removed, washed, and dried after 30 days in the steam chest. The X-ray di~raction pattern showed 100~ ZSM-5. Scanning electron micrograms showed the material to be relatively uniform crystals of 6-12 micron diameter.
Examples 3-6 In these exampies, prior art and present improved , methods of syntheses of zeolite ZSM-35 were conducted.
¦ Crystallization at 100C was conducted in polypropylene bottles under static conditions in a steam chest. The slIicate source was Q-brand (27.8% SiO2, 8.42% Na2O) and the alumina source was A12(SO4)2 16H20. The organic nitrogen-containing cation source was pyrrolidine. Reaction mixture compositions (mole ratios), total days in a steam chest ~or crystalli~ation to occur and zeolite product compositions are tabulated in Table IV, hereinafter presented. It is observed from these examples that prior art methods (Ex2mples 5 and 6) ~ail to compare favorably with the present improved method of synthesis ~Examples 3 and 4) for zeol~te ZSM-35. After only 35 and 39 days ln the steam chest, 100% ZSM-35 was obtained from the improved methcd of Examples 3 and 4. After as many as 85 days in the steam chest for the reactlon mixture of Example 5, the product contained 50% ZSM-35 and 50~ mordenite. ~fter 70 days in the steam chest for the reaction mixture of Example 6, only 10% ZSM-35 resulted.
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Example 7 A sample of crystalllne alumlnosillcate zeollte ZSM-5 prepared as ln Example 2 was evaluated for catalytlc activity with a flve-component feedstock of n-hexane, 3-methylpentane, 2,3-dimethylbutane, benzene and toluene at 2Q0 psig, a weight hourly space velocity (WHSV) o~ 2.9 hr-l, a temperature of 427C and a hydrogen/hydrocarbon mole ratio of 3.6. This zeolite, after exchange, provided 94%
conversion of n-hexane and 46% conversion o~ 3-methylpentane.
Of the converted paraffln charge, 11% reacted with benzene and toluene to produce alkyl aromatics.
ExamE~e_8 A sample of ZSM-35 was prepared as in Example 3, but at a temperatur.~ of 160C and with R/SiO2 = 0.14 and H+(additional)/SiO2 = 0.03. The ZSM-35 product was evaluated for catalytic activity with a ~eedstock as in Example 7.
Test conditions were 200 psig, 3.2 hr 1 WHSV, 427C and a hydrogen/hydrocarbon mole ratio of 4.8. Thls ZSM-35 converted 96% n-hexane and 20% 3-methylpentane.
.
-37~
Claims (9)
1. A process for synthesizing a crystalline aluminosilicate zeolite which comprises forming a reaction mixture containing one or more sources of alkali metal oxide, organic nitrogen-containing cations, acid ions, an oxide of silicon, an oxide of aluminum and water wherein the mole ratio of hydroxide ions/silica in said reaction mixture is at most about 10-2 and the acid ions are present in said reaction mixture in amount less than the equivalents of organic nitrogen present therein, and wherein the pH of said reaction mixture is at least about 7, and maintaining the reaction mixture at a temperature and pressure for a time necessary to crystallize therefrom said crystalline aluminosilicate zeolite.
2. The method of Claim 1 wherein said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 5-1000 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-200 M/SiO2 = 0.01-5.0 R/SiO2 = 0.01-3.0 wherein R is an organic nitrogen-containing cation or an organic nitrogen-containing cation source and M is an alkali metal ion.
SiO2/Al2O3 = 5-1000 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-200 M/SiO2 = 0.01-5.0 R/SiO2 = 0.01-3.0 wherein R is an organic nitrogen-containing cation or an organic nitrogen-containing cation source and M is an alkali metal ion.
3. The method of Claim 2 wherein the zeolite prepared is ZSM-5 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 5-1000 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-200 M/SiO2 = 0.01-3.0 R/SiO2 = 0.01-1.0 wherein R is a tetrapropylammonium cation and M is an alkali metal ion.
SiO2/Al2O3 = 5-1000 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-200 M/SiO2 = 0.01-3.0 R/SiO2 = 0.01-1.0 wherein R is a tetrapropylammonium cation and M is an alkali metal ion.
4. The method of Claim 2 wherein the zeolite prepared is ZSM-11 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 10-180 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 - 0.04-1.0 wherein R is a tetrabutylammonium cation and M is an alkali metal ion.
SiO2/Al2O3 = 10-180 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 - 0.04-1.0 wherein R is a tetrabutylammonium cation and M is an alkali metal ion.
5. The method of Claim 2 wherein the zeolite prepared is ZSM-12 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 40-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.1-2.0 wherein R is a tetraethylammonium cation or a cation derived from triethylamine and M is an alkali metal ion.
SiO2/Al2O3 = 40-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.1-2.0 wherein R is a tetraethylammonium cation or a cation derived from triethylamine and M is an alkali metal ion.
6. The method of Claim 2 wherein the zeolite prepared is ZSM-23 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 10-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from pyrrolidine and M is an alkali metal ion.
SiO2/Al2O3 = 10-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from pyrrolidine and M is an alkali metal ion.
7. The method of Claim 2 wherein the zeolite prepared is ZSM-34 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/A12O3 = 5-100 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from choline and M is an alkali metal ion.
SiO2/A12O3 = 5-100 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-2.0 R/SiO2 = 0.1-1.0 wherein R is a cation derived from choline and M is an alkali metal ion.
8. The method of Claim 2 wherein the zeolite prepared is ZSM-35 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 8.8-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.05-2.0 wherein R is a cation derived from ethylenediamine or pyrrolidine and M is an alkali metal ion.
SiO2/Al2O3 = 8.8-200 OH-/SiO2 = 10-10-10-2 H2O/SiO2 = 5-100 M/SiO2 = 0.1-3.0 R/SiO2 = 0.05-2.0 wherein R is a cation derived from ethylenediamine or pyrrolidine and M is an alkali metal ion.
9. The method of Claim 2 wherein the zeolite prepared is ZSM-38 and said reaction mixture has a composition in terms of mole ratios of oxides as follows:
SiO2/Al2O3 = 8.8-200 OH- /SiO2 = 10-10-10-2 H2O/SiO2 = 5-l00 M/Sio2 = 0.1-3.0 R/SiO2 = 0.1-2.0 wherein R is a cation derived from a 2-(hydroxyalkyl) trialkylammonium compound, wherein alkyl is methyl, ethyl or a combination thereof, and M is an alkali metal ion.
SiO2/Al2O3 = 8.8-200 OH- /SiO2 = 10-10-10-2 H2O/SiO2 = 5-l00 M/Sio2 = 0.1-3.0 R/SiO2 = 0.1-2.0 wherein R is a cation derived from a 2-(hydroxyalkyl) trialkylammonium compound, wherein alkyl is methyl, ethyl or a combination thereof, and M is an alkali metal ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78990177A | 1977-04-22 | 1977-04-22 | |
| US789,901 | 1991-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117512A true CA1117512A (en) | 1982-02-02 |
Family
ID=25149040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000301357A Expired CA1117512A (en) | 1977-04-22 | 1978-04-18 | Zeolite synthesis |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS53134798A (en) |
| AU (1) | AU515185B2 (en) |
| BE (1) | BE866272A (en) |
| CA (1) | CA1117512A (en) |
| DE (1) | DE2817577A1 (en) |
| FR (1) | FR2442795A1 (en) |
| GB (1) | GB1588613A (en) |
| IT (1) | IT1095609B (en) |
| NL (1) | NL188568C (en) |
| NZ (1) | NZ186957A (en) |
| ZA (1) | ZA782292B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2862096D1 (en) * | 1977-12-23 | 1982-12-30 | British Petroleum Co Plc | Method for producing aluminosilicates and their use as catalysts and supports |
| EP0002899B1 (en) | 1977-12-23 | 1983-03-16 | The British Petroleum Company p.l.c. | Method for preparing aluminosilicates and their use as catalyst supports and catalysts |
| NL7812162A (en) * | 1978-12-14 | 1980-06-17 | Shell Int Research | PROCESS FOR THE PREPARATION OF FERRIERITE. |
| US4205053A (en) * | 1979-02-01 | 1980-05-27 | Mobil Oil Corporation | Manufacture of nitrogenous zeolites |
| ZA80767B (en) * | 1979-02-21 | 1981-09-30 | Mobil Oil Corp | Crystalline zeolitic synthesis and use thereof |
| NZ193928A (en) * | 1979-06-11 | 1982-09-07 | Mobil Oil Corp | Preparation of large crystal zeolite zsm-5 |
| DE3068017D1 (en) * | 1979-07-12 | 1984-07-05 | Mobil Oil Corp | Method of preparing zeolite zsm-48, the zeolite so prepared and its use as catalyst for organic compound conversion |
| ZA803365B (en) * | 1979-10-09 | 1981-05-27 | Mobil Oil Corp | Synthesis of large crystal zeolite zsm-5 |
| NZ193929A (en) * | 1979-10-09 | 1982-09-07 | Mobil Oil Corp | Preparation of large crystal zeolite zsm-5 |
| CA1144137A (en) * | 1979-12-26 | 1983-04-05 | Donald A. Hickson | Method for preparing crystalline zeolites |
| AU540104B2 (en) * | 1980-01-10 | 1984-11-01 | Mobil Oil Corp. | Calytic reforming |
| DE3006471A1 (en) * | 1980-02-21 | 1981-08-27 | Basf Ag, 6700 Ludwigshafen | CRYSTALLINE ISOTACTIC ZEOLITES, METHOD FOR PRODUCING THE SAME AND THEIR USE AS CATALYSTS |
| CA1167071A (en) * | 1980-03-15 | 1984-05-08 | William J. Ball | Process for the production of aromatic hydrocarbons |
| CA1157450A (en) * | 1980-03-18 | 1983-11-22 | Martin F.M. Post | Process for the preparation of crystalline aluminium silicates, crystalline aluminium silicates so prepared and process for the production of an aromatic hydrocarbon mixture |
| CA1153867A (en) * | 1980-05-16 | 1983-09-20 | Michael A. M. Boersma | Process for the preparation of crystalline silicates, crystalline silicates so prepared and process for carrying out catalytic reactions |
| US4309313A (en) * | 1980-05-23 | 1982-01-05 | W. R. Grace & Co. | Synthesis of cesium-containing zeolite, CSZ-1 |
| JPS577820A (en) * | 1980-06-18 | 1982-01-16 | Mitsubishi Heavy Ind Ltd | Novel crystalline silicate and its manufacture |
| DE3139355A1 (en) * | 1980-10-02 | 1982-06-09 | Inui, Tomoyuki, Joyo | Crystalline aluminosilicate zeolite catalyst and process for the preparation thereof |
| JPS57191222A (en) * | 1981-05-13 | 1982-11-25 | Mobil Oil Corp | Crystalline zeolite substance, manufacture and conversion of organic raw material using same |
| JPS5891032A (en) * | 1981-11-26 | 1983-05-30 | Toray Ind Inc | Manufacture of crystalline aluminosilicate zeolite |
| NL8202992A (en) * | 1982-07-26 | 1984-02-16 | Shell Int Research | PROCESS FOR DECAPINIFYING HYDROCARBON OILS |
| JPS5973427A (en) * | 1982-10-16 | 1984-04-25 | Res Assoc Petroleum Alternat Dev<Rapad> | Novel zeolite and preparation thereof |
| CA1281746C (en) * | 1986-06-27 | 1991-03-19 | Rene Bernard Lapierre | Direct catalytic alkylation of mononuclear aromatics with lower alkanes |
| IL79906A (en) * | 1986-09-01 | 1990-08-31 | Yeda Res & Dev | Crystalline aluminosilicate zeolite catalyst for the selective isomerization of xylene |
| JPH0360929U (en) * | 1989-10-18 | 1991-06-14 | ||
| CZ299372B6 (en) * | 2005-09-23 | 2008-07-09 | Výzkumný ústav anorganické chemie, a. s. | Process for producing ZSM-5 zeolite with controlled crystal size |
| JP6070336B2 (en) * | 2012-03-26 | 2017-02-01 | 東ソー株式会社 | MFI type zeolite having uniform mesopores and method for producing the same |
| CZ2016150A3 (en) * | 2016-03-15 | 2017-08-09 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of production of the ZSM-5 zeolite with a high proportion of pairs of aluminium atoms |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US3709979A (en) * | 1970-04-23 | 1973-01-09 | Mobil Oil Corp | Crystalline zeolite zsm-11 |
| US3832449A (en) * | 1971-03-18 | 1974-08-27 | Mobil Oil Corp | Crystalline zeolite zsm{14 12 |
| CA933911A (en) * | 1971-03-18 | 1973-09-18 | Mobil Oil Corporation | Method of preparation for crystalline aluminosilicate zeolites |
| US4016245A (en) * | 1973-09-04 | 1977-04-05 | Mobil Oil Corporation | Crystalline zeolite and method of preparing same |
| CA1064890A (en) * | 1975-06-10 | 1979-10-23 | Mae K. Rubin | Crystalline zeolite, synthesis and use thereof |
-
1978
- 1978-04-12 NZ NZ186957A patent/NZ186957A/en unknown
- 1978-04-18 CA CA000301357A patent/CA1117512A/en not_active Expired
- 1978-04-18 GB GB15189/78A patent/GB1588613A/en not_active Expired
- 1978-04-19 AU AU35237/78A patent/AU515185B2/en not_active Expired
- 1978-04-19 FR FR7811482A patent/FR2442795A1/en active Granted
- 1978-04-21 NL NLAANVRAGE7804289,A patent/NL188568C/en not_active IP Right Cessation
- 1978-04-21 DE DE19782817577 patent/DE2817577A1/en active Granted
- 1978-04-21 JP JP4672578A patent/JPS53134798A/en active Granted
- 1978-04-21 IT IT22609/78A patent/IT1095609B/en active
- 1978-04-21 ZA ZA00782292A patent/ZA782292B/en unknown
- 1978-04-21 BE BE187030A patent/BE866272A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NL188568B (en) | 1992-03-02 |
| GB1588613A (en) | 1981-04-29 |
| JPS53134798A (en) | 1978-11-24 |
| NL7804289A (en) | 1978-10-24 |
| AU515185B2 (en) | 1981-03-19 |
| ZA782292B (en) | 1979-12-27 |
| FR2442795B1 (en) | 1985-03-01 |
| FR2442795A1 (en) | 1980-06-27 |
| IT7822609A0 (en) | 1978-04-21 |
| IT1095609B (en) | 1985-08-10 |
| DE2817577A1 (en) | 1978-10-26 |
| NL188568C (en) | 1992-08-03 |
| NZ186957A (en) | 1979-10-25 |
| AU3523778A (en) | 1979-10-25 |
| BE866272A (en) | 1978-10-23 |
| DE2817577C2 (en) | 1988-08-04 |
| JPS624326B2 (en) | 1987-01-29 |
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