GB2077709A - Zeolite EU-2 - Google Patents
Zeolite EU-2 Download PDFInfo
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- GB2077709A GB2077709A GB8116192A GB8116192A GB2077709A GB 2077709 A GB2077709 A GB 2077709A GB 8116192 A GB8116192 A GB 8116192A GB 8116192 A GB8116192 A GB 8116192A GB 2077709 A GB2077709 A GB 2077709A
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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Abstract
Zeolite EU-2 having a molar composition expressed by the formula: 0.5 to 1.5 R2O:Y2O3:at least 70 XO2:0 to 100 H2O wherein R is a monovalent cation or <1>/n of a cation of valency n, X is silicon and/or germanium, Y is one or more of aluminium, iron, gallium or boron, and H2O is water of hydration additional to water notionally present when R is H, and having an X-ray pattern substantially as set out in Table 1 is prepared from a reaction mixture containing XO2 (preferably silica), Y2O3 (preferably alumina) and an alkylated derivative of a polymethylene diamine an amine degradation product thereof or a precursor thereof. The zeolite is useful in catalytic processes, especially for the conversion of methanol to hydrocarbons.
Description
SPECIFICATION
Zeolite EU-2
The present invention relates to a novel zeolite material, hereinafter referred to as zeolite EU-2, to a method of making it and to processes using it as a catalyst.
According to the present invention we provide zeolite EU-2 having a molar composition expressed by the formula: 0.5 to 1.5 R20:Y703:at least 70 To2:0 to 100 H20 wherein R is a monovalent cation or 1/n of a cation of valency n, X is silicon and/or germanium, Y is one or more of aluminium, iron, gallium or boron, and H20 is water of hydration additional to water notionally present when R is H, and having an X-ray pattern substantially as set out in Table 1 (as determined by standard technique using copper Ka radiation). Members of the EU-2 family of zeolites possess a unique crystalline structure whose X-ray diffraction pattern shows the significant lines listed in Table 1.
TABLE 1
Zeolite EU-2
Interplanar Relative Intensity
Spacings d(A) 100 '/iso 11.74 17 10.13 14
6.33 7
5.85 7
4.33 5
4.18 86
3.89 100
3.69 7
3.37 7
3.08 5
2.85 18
2.09 5
Within the above definition of chemical composition, the number of moles of XO2 is typically in the range 100 to 5000 and zeolite EU-2 appears to be most readily formed in a state of high purity when the number of moles of X 2 is in the range 1 50 to 3000.
This definition includes both freshly prepared zeolite EU-2 ("freshly prepared" means the product of synthesis and washing, with optional drying, as hereinafter described) and also forms of it resulting from dehydration, and/or calcination, and/or ion exchange. In freshly prepared zeolite EU-2, R may include an alkali metal cation; especially sodium, and/or ammonium, and usually or when prepared from alkylated nitrogen compounds, includes nitrogen-containing organic cations as described below or cationic degradation products thereof, or precursors thereof. These nitrogen containing cations are hereinafter referred to as Q.
The freshly prepared zeolite EU-2 may also contain nitrogen-containing compounds well in excess of the 1.5 moles set out in the aforesaid definition of the composition of zeolite EU-2, typically in the range 1 to 50 moles per mole of Y203. Since EU-2 is a zeolite, the excess base must be physically trapped within the crystal lattice, because it is too large to escape. It can be removed by thermal or oxidative degradation. This physically trapped basic material does not constitute part of the composition for the purposes of the definition.Thus a zeolite EU-2 as made typically has the following molar composition:
O to 0.8 M20: 1.0 to 50 Q: Y203: 100 to 5000 XO2: : to 100 H20 wherein M is an alkali metal or ammonium, and M20 + Or1.0 The H20 content of freshly prepared zeolite EU-2 depends on the conditions in which it has been dried after synthesis.
In calcined forms of zeolite EU-2, R may be alkali metal but includes less or no nitrogencontaining organic compounds, since these are burnt out in the presence of air, leaving hydrogen as the other balancing cation.
Among the ion-exchanged forms of zeolite EU-2 the ammonium (NH4+) is of importance since it can be readily converted to the hydrogen form by calcination. The hydrogen form can also be prepared directly be exchange with an acid. The hydrogen-form and forms containing metals introduced by ion exchange are described further below.
Zeolite EU-2 is a novel zeolite with very characteristic molecular sieve properties as demonstrated by typical sorption results given in Table 2. These results pertain to sodium hydrogen EU-2 having a SiO2/AI203 molar ratio of 450 (as described in Example 6).
TABLE 2
Sorption at 25"C p/po = 0.5
Kinetic Diameter Wt sorbed Voidage available
Sorbate o,A Time (mins) g/100g cc/100 g 10 0.1
Water 2.7 120 0.2 Negligible
1440 0.5
10 5.9 8.9 n-hexane 60 6.4 9.7
120 6.7 10.2
10 5.7 7.6 p-xylene 5.85 60 7.6 10.1
120 7.6 10.1
10 3.8 5.0 m-xylene 6.8 60 5.7 7.6
120 5.7 7.6
10 3.2 4 cyclohexane 6.0 60 3.5 4.4
120 3.9 4.9
Symm trimethyl 10 0.1 benzene 7.6 1440 0.3 Negligible * Lennard Jones Kinetic Diameter
see D W Breck "Zeolite Molecular Sieves" Wiley Interscience, 1974, p 636
The results demonstrate that zeolite EU-2 is extremely hydrophobic. Only a negligible fraction of the voidage available to hydrocarbons is available to water.The results with xylenes and cyclohexane suggest a port size near to 6A but with some pillar box type openings (10 ring window) which deny access of cyclohexane to about half of the voidage available to p-xylene.
The invention provides also a method of making zeolite EU-2 which comprises reacting an aqueous mixture comprising at least one oxide XO2, at least one oxide Y203 and at least one alkylated derivative of a polymethylene a-co diamine having the formula
which by our definition is Q2+ an amine degradation product thereof, or a precursor thereof, wherein n is in the range from 3 to 12, R, to R6 which may be the same or different, can be alkyl or hydroxyalkyl groups containing from 1 to 8 carbon atoms and up to five of the groups R1-R6 can be hydrogen, the mixture having the molar composition:: X 2/Y2 3 at least 70, preferably at least 150 OH/XO 0.1 to 6.0 preferably 0.1 to 1.0 (M + + Q)/Yz03 0.5 to 100 0.1 to 1.0 K2O/XO2 1 to 100 where X is silicon and/or germanium, Y is one or more of aluminium, iron, gallium, boron. M is an alkali metal or ammonium and Q is the aforesaid alkylated derivative of a polymethylene diamine, an amine degradation product thereof, or a precursor thereof, or a related compound.
M and/or Q can be present as hydroxides or salts of inorganic or organic acids provided that OH - /XO2 requirement is fulfilled.
Preferred alkylated polymethylene diamine starting materials include alkylated hexamethylene diamines, especially methylated hexamethyler,e diamines, for example 1:6-N, N,N, N', N', N'- hexamethyl hexane-1,6-diammonium salts (e.g. hlide, hydroxide, sulphate, silicate, aluminate).
Suitable precursors of the alkylated polymethylene diamine starting materials include the parent diamine along with alcohols or alkyl halides which can be used as such or can be preheated together in the reaction vessel preferably in solution (e.g. in methyl ethyl ketone) prior to addition of the other reactants required for zeolite EU-2 synthesis.
The preferred alkali metal (M) is sodium. The preferred oxide X02 is silica (six2) and the preferred oxide Y203 is alumina (Al203).
The silica source can be any of those commonly considered for use in synthesising zeolites, for example powdered solid silica, silicic acid, colloidal silica or dissolved silica. Among the powdered silicas usable are precipitated silicas, especially those made by precipitation from an alkali metal silicate solution, such as the type known as "KS 300" made by AKZO, and similar products, aerosil silicas, fume silicas and silica gels suitably in grades for use in reinforcing pigments for rubber or silicone rubber. Colloidal silicas of various particle sizes may be used, for example 10-15 or 40-50 microns, as sold under the Registered Trade Marks "LUDOX" NALCOAG" and "SYTON".The usable dissolved silicas include commercially available waterglass silicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of SiO2 per mol . alkali metal oxide, "active" alkali metal silicates as defined in UK Patent 1,193,254, and silicates made by dissolving silica in an alkali metal hydroxide or quaternary ammonium hydroxide or a mixture thereof.
The alumina source is most conveniently sodium aluminate, but can be aluminium, an aluminium salt, for example the chloride, nitrate or sulphate, an aluminium alkoxide or alumina itself, which should preferably be in a hydrated or hydratable form such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina or the alpha or beta trihydrate.
The reaction mixture is usually reacted under autogenous pressure, optionally with added gas, e.g. nitrogen, at a temperature between 85 and 250"C until crystals of zeolite EU-2 form, which can be from 1 hour to more months depending on the reactant composition and the operating temperature. Agitation is optional, but is preferable since it reduces the reaction time.
At the end of the reaction, the solid phase is collected on a filter and washed and is then ready for further steps such as drying, dehydration and ion-exchange.
If the product of the reaction contains alkali metal ions, these have to be at least partly removed in order to prepare the hydrogen form of EU-2 and this can be done by ion exchange with an acid, especially a strong mineral acid such as hydrochloric acid or by way of the ammonium compound, made by ion exchange with a solution of an ammonium salt such as ammonium chloride. Ion exchange can be carried out by slurrying once or several times with the ion-exchange solution. The zeolite is usually calcined after ion exchange but this may be effected before ion-exchange or during ion-exchange if the latter is carried out in a number of stages.
In general, the cation(s) of zeolite EU-2 can be replaced by any cation(s) of metals, and particularly those in Groups IA, IB, IIA, IIB, III (including rare earths) VIII (including noble metals) and by lead, tin and bismuth. (The Periodic Table is as in "Abridgements of
Specifications" published by the UK Patent Office) Exchange is carried out using any water soluble salts containing the appropriate cation.
When used as a catalyst, zeolite EU-2 can be associated with an inorganic matrix, which can be either inert or catalytically active The matrix may be present simply as a binding agent to hold the small zeolite particles (0.005 to 10 microns) together, or it may be added as a diluent to control the amount of conversion in a process which may otherwise proceed at too high a rate, leading to catalyst fouliny as a result of excessive coke formation. Typical inorganic diluents include catalyst support materials such as alumina, silica, kaolinic clays, bentonites, montmorillonites, sepiolite. attapulgite, Fullers earth, synthetic porous materials such as SiO?-AI203, SiO2-ZrO SiO -ThO, SiO2-BeO, SiO2-TiO2 or any combination of these diluents.
An effective way of mixing zeolite EU-2 with such diluents is to mix appropriate aqueous slurries in a mixing nozzle and then to spray-dry the slurry. Other ways of mixing can be used.
If zeolite EU-2 in any cationic form or as a catalytic composite is exchanged or impregnated with hydrogenation/dehydrogenation components, such as Ni, Co, Pt, Pd, Re, Rh, shape selective hydrocracking and reforming catalysts can be made, especially if the Na2O content is less than 0.1% w/w.
A wide range of shape selective hydrocarbon conversion catalysts can be prepared from zeolite EU-2 by ion exchange or impregnation with cations, or oxides, selected from the following, Cu, Ag, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, noble metals.
Usually the Eu-2 catalyst will be in acid form, thus stoichiometry is maintained by H + or H30+ as an additional balancing cation, or as sole cation. Such catalysts may find application in the following processes; hydrodesulphurization, hydrodenitrification, catalytic dewaxing, selective alkylation or alkanes, dehydration reactions and oxidation.
Methanol on dehydration by EU-2 or H-EU2 yields a wide range of aliphatic and aromatic hydrocarbons, demonstrating, high acidity and selectivity for propene, cis butene-2 and 2methyl propane which is very surprising. H-EU2 may also be an effective aromatization catalyst.
Zeolite EU-2 may also find applications in the separation of aromatics and cycloparaffins, and in pollution control by its ability to remove organic contaminants from aqueous effluents as a result of its extreme hydrophobicity.
The invention is illustrated by the following Examples.
Examples 1-5
In these examples, the solid silica (CAB-O-SIL M5 SiO2/Al20., ratio 3,400) was suspended in a mixture of hexamethonium bromide and water. Next a solution containing sodium hydroxide, and where appropriate sodium aluminate, was stirred in. The mixture was reacted in a stirred stainless steel autoclave under the reaction conditions indicated in Table 3.
TABLE 3
Reaction Mixture Composition
Example Temp C Time (hrs) Product
Na2O Q Al2O3 SiO2 H2O 1 567 567 1 3400 170,000 180 120 EU-2 2 25 25 1 150 7,500 180 120 EU-2 + trace EU-1* 3 14.9 14.9 89.6 4.778 200 48 EU-2 + trace EU-1* 4 50 50 1 300 15,000 200 16 EU-2 5 100 100 1 600 30,000 180 16 EU-2 *Zeolite EU-1 is described in our copending UK Application No 8,019,210 Example 6
Hydrogen EU-2 was prepared from the product of Example 5 as follows. First the product was dried overnight at 120 C and then calcined for 48 hours in air at 450 C. The resulting sodium hydrogen EU-2 was used in the sorption work detailed in Table 2. A portion of this material was exchanged by slurrying for 1 hour at 25"C with 5 ml NHCI per g of zeolite.The resulting hydrogen zeolite contained less than 500 ppm Na2O Example 7
The catalytic activity of hydrogen EU-2 in the conversion of methanol to hydrocarbons was demonstrated in two pulse microreactors. Both were essentially the same except for the analysis systems, one of which determined C,-C4 hydrocarbons and the other of which determined C5 (and above) hydrocarbons, particularly aromatics. A catalyst bed of about 0.3 ml of 3 mm pellets of hydrogen EU-2 was activated by calcination at 450 C for 3 hours in a stream of nitrogen. With the catalyst temperature still at 450 C a sample of methanol (0.6 l) was injected above the catalyst bed. The C1-C4 hydrocarbon analysis in given in Table 4.
TABLE 4
C,-C4 hydrocarbon analysis % v/v
Methane 1.7
Ethane 0.5
Ethene 8.8
Propane 7.5
Propene 17.8 2-methyl propane 30.4
Butane 0.7
Butene-1 1.9 2-methyl propene 0 trans-butene-2 2.9 cis-butene-2 27.8
The high selectivities for propene, cis-butene-2 and 2-methylpropane are especially surprising.
Another sample of hydrogen EU-2 was activated in the same way and a 2 Iel pulse of methanol was passed over the catalyst. The analysis of the aromatics formed is given in column
A in Table 5. A second 2 ssll pulse of methanol gave the results in column B. Two 10 Itl pulses of methanol were separately passed over the catalyst bed, followed by a further single pulse of 2 1. The results are given in column C. Six 10 IL1 pulses of methanol were separately passed over the catalyst, followed again by a further single pulse of 2 pl. The results are given in column D.
TABLE 5
Aromatics analysis (% v/v)
A B C D
Benzene 7.9 7.0 6.8 4.6
Toluene 26.8 26.3 27.9 28.9
Ethylbenzene)
+ m,p-xylene) 35.1 34.7 32.7 35.3 o-xylene 6.7 6.9 8.1 6.5 Cg aromatics 9.6 9.8 10.5 10.8 C,O+ aromatics 14.0 15.3 13.9 13.8
Some C5 and C, aliphatic hydrocarbons were also formed. The total yield of hydrocarbons did not change perceptibly with ageing.
Claims (12)
1. Zeolite EU-2 having a molar composition expressed by the formula: 0.5 to 1.5 R20 : Y203 : at least 70 X02 : 0 to 100 H20 wherein R is a monovalent cation or 1/ of a cation of valency n, X is silicon and/or germanium,
Y is one or more of aluminium, iron, gallium or boron, and H20 is water of hydration additional to water notionally present when R is H, and having an X-ray diffraction pattern substantially as set out in Table 1.
2. Zeolite EU-2 according to claim 1 wherein the molar composition is expressed by the formula: 0.5 to 1.5 R20 : Y203 150 to 3000 X02: 0 to 100 H20
3. Zeolite EU-2 according to claim 1 or claim 2 wherein R is or includes hydrogen.
4. Zeolite EU-2 according to claim 1 as freshly made having a molar composition expressed by the formula: 0 to 0.8 M2O : 1.0 to 50 Q : Y2O3 : 10 to 5000 XO2 : O to 100 H2O wherein M is an alkali metal or ammonium, Q is a nitrogen-containing organic cation and
M20 + Ct > 1.0.
5. A method of making zeolite EU-2 as defined in claim 1 which comprises reacting an aqueous mixture comprising at least one oxide X02, at least one oxide Y203 and at least one alkylated derivative of a polymethylene ot diamine having the formula:
an amine degradation product thereof, or a precursor thereof, wherein n is in the range from 3 to 12, R1 to R5 which may be the same or different, can be an alkyl or hydroxyalkyl group containing from 1 to 8 carbon atoms and up to five of the groups R1 to R6 can be hydrogen, the mixture having the molar composition:: XO2/Y203 at least 70
OH-/XO2 0.1 to 6.0 (M+ +Q)/Y203 0.5 to 100
Q/M+ + Q) 0.1 to 1.0 H20/X02 1 to 100 where X is silicon and/or germanium, Y is one or more of aluminium, iron, gallium, boron, M is an alkali metal or ammonium and 0 is the aforesaid alkylated derivative of a polymethylene diamine, an amine degradation product thereof, or a precursor thereof.
6. A method according to claim 5 wherein the X 2/Y2 3 molar ratio is at least 150.
7. A method according to claim 5 or claim 6 wherein the 011-/X02 ratio is in the range 0.1 to 1.0.
8. A method according to any one of claims 5 to 7 wherein the alkylated derivative of a polymethylene diamine is an alkylated hexamethylene diamine.
9. A method according to claim 8 wherein the alkylated hexamethylene diamine is an N, N,
N, N', N', N1-hexamethyl-1,6-hexamethylene diammonium salt.
10. A catalyst comprising zeolite EU-2 as claimed in any one of claims 1 to 4.
11. A catalytic process employing the catalyst claimed in claim 10.
12. A process according to claim 11 wherein hydrocarbons are produced by contacting methanol with the catalyst under conversion conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8116192A GB2077709B (en) | 1980-06-12 | 1981-05-27 | Zeolite eu-2 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8019211 | 1980-06-12 | ||
| GB8116192A GB2077709B (en) | 1980-06-12 | 1981-05-27 | Zeolite eu-2 |
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| Publication Number | Publication Date |
|---|---|
| GB2077709A true GB2077709A (en) | 1981-12-23 |
| GB2077709B GB2077709B (en) | 1983-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8116192A Expired GB2077709B (en) | 1980-06-12 | 1981-05-27 | Zeolite eu-2 |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482531A (en) * | 1983-04-29 | 1984-11-13 | Mobil Oil Corporation | Synthesis of ZSM-12 zeolite |
| US4490342A (en) * | 1983-04-29 | 1984-12-25 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite |
| US4539193A (en) * | 1984-05-23 | 1985-09-03 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-12 |
| US4557919A (en) * | 1983-04-12 | 1985-12-10 | Teijin Petrochemical Industries Ltd. | Production of crystalline zeolites |
| US4559213A (en) * | 1983-04-29 | 1985-12-17 | Mobil Oil Corporation | Synthesis of ZSM-12 zeolite |
| EP0168167A1 (en) * | 1984-06-09 | 1986-01-15 | BP Chemicals Limited | Catalysis using supported strong base catalysts and supported catalysts |
| US4568654A (en) * | 1982-11-03 | 1986-02-04 | Mobil Oil Corporation | Zeolite ZSM-51 composition |
| US4585639A (en) * | 1984-04-16 | 1986-04-29 | Mobil Oil Corporation | Preparation of crystalline silicate ZSM-12 |
| US4585638A (en) * | 1984-07-16 | 1986-04-29 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-5 |
| US4619820A (en) * | 1984-10-17 | 1986-10-28 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite and the product produced |
| US4637923A (en) * | 1985-06-27 | 1987-01-20 | Mobil Oil Corporation | Synthetic crystalline silicate |
| EP0142317A3 (en) * | 1983-11-16 | 1987-07-22 | Mobil Oil Corporation | Crystalline silicate zsm-48 and method for its preparation |
| US4708857A (en) * | 1983-07-26 | 1987-11-24 | Centre De Recherche Industrielle Du Quebec | Process for preparing a crystalline iron-borosilicate |
| EP0148038A3 (en) * | 1983-07-26 | 1988-09-14 | Centre De Recherche Industrielle Du Quebec | Crystalline ironborosilicates and process of preparing same |
| EP0178846A3 (en) * | 1984-10-17 | 1989-04-19 | Mobil Oil Corporation | Synthesis of zsm-23 zeolite |
| US4840780A (en) * | 1983-03-28 | 1989-06-20 | Mobil Oil Corporation | ZSM-51, method of preparing same and catalytic conversion therewith |
| US4851605A (en) * | 1984-07-13 | 1989-07-25 | Exxon Research & Engineering Co. | Process for synthesizing a zeolite catalyst on a pH controlled sodium free basis |
| US4902406A (en) * | 1982-04-30 | 1990-02-20 | Mobil Oil Corporation | Synthesis of zeolite ZSM-22 |
| CN1073888C (en) * | 1990-06-21 | 2001-10-31 | 帝国化学工业公司 | Zeolite catalysts and various processes carried out in pressure of said zeolite catalysts |
| FR2893019A1 (en) * | 2005-11-04 | 2007-05-11 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF ZBM-30 ZEOLITES USING ETHERDIAMMONIUM COMPOUND AS ORGANIC STRUCTURING |
| US10076747B2 (en) | 2011-12-16 | 2018-09-18 | Shell Oil Company | Anatase polymorph titania-bound ZSM-12 zeolite composition and method of making and using such composition |
| US10449525B2 (en) | 2010-10-25 | 2019-10-22 | Shell Oil Company | Hydrocarbon conversion catalyst composition |
| US11198114B2 (en) | 2016-12-16 | 2021-12-14 | Shell Oil Company | Catalyst system for dewaxing |
| US11351528B2 (en) | 2018-04-17 | 2022-06-07 | Shell Usa, Inc. | Catalyst system for dewaxing |
-
1981
- 1981-05-27 GB GB8116192A patent/GB2077709B/en not_active Expired
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902406A (en) * | 1982-04-30 | 1990-02-20 | Mobil Oil Corporation | Synthesis of zeolite ZSM-22 |
| US4568654A (en) * | 1982-11-03 | 1986-02-04 | Mobil Oil Corporation | Zeolite ZSM-51 composition |
| US4840780A (en) * | 1983-03-28 | 1989-06-20 | Mobil Oil Corporation | ZSM-51, method of preparing same and catalytic conversion therewith |
| US4557919A (en) * | 1983-04-12 | 1985-12-10 | Teijin Petrochemical Industries Ltd. | Production of crystalline zeolites |
| US4482531A (en) * | 1983-04-29 | 1984-11-13 | Mobil Oil Corporation | Synthesis of ZSM-12 zeolite |
| US4490342A (en) * | 1983-04-29 | 1984-12-25 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite |
| US4559213A (en) * | 1983-04-29 | 1985-12-17 | Mobil Oil Corporation | Synthesis of ZSM-12 zeolite |
| US4708857A (en) * | 1983-07-26 | 1987-11-24 | Centre De Recherche Industrielle Du Quebec | Process for preparing a crystalline iron-borosilicate |
| EP0148038A3 (en) * | 1983-07-26 | 1988-09-14 | Centre De Recherche Industrielle Du Quebec | Crystalline ironborosilicates and process of preparing same |
| EP0142317A3 (en) * | 1983-11-16 | 1987-07-22 | Mobil Oil Corporation | Crystalline silicate zsm-48 and method for its preparation |
| US4585639A (en) * | 1984-04-16 | 1986-04-29 | Mobil Oil Corporation | Preparation of crystalline silicate ZSM-12 |
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| US4851605A (en) * | 1984-07-13 | 1989-07-25 | Exxon Research & Engineering Co. | Process for synthesizing a zeolite catalyst on a pH controlled sodium free basis |
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| AU583297B2 (en) * | 1984-10-17 | 1989-04-27 | Mobil Oil Corporation | Improved synthesis of ZSM-23 zeolite |
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| US4619820A (en) * | 1984-10-17 | 1986-10-28 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite and the product produced |
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| US7622099B2 (en) | 2005-11-04 | 2009-11-24 | Institut Francais Du Petrole | Process for preparation of ZBM-30-type zeolites using a diammonium ether-type compound as an organic structuring agent |
| US10449525B2 (en) | 2010-10-25 | 2019-10-22 | Shell Oil Company | Hydrocarbon conversion catalyst composition |
| US10076747B2 (en) | 2011-12-16 | 2018-09-18 | Shell Oil Company | Anatase polymorph titania-bound ZSM-12 zeolite composition and method of making and using such composition |
| US11198114B2 (en) | 2016-12-16 | 2021-12-14 | Shell Oil Company | Catalyst system for dewaxing |
| US11351528B2 (en) | 2018-04-17 | 2022-06-07 | Shell Usa, Inc. | Catalyst system for dewaxing |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2077709B (en) | 1983-12-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940527 |