Ferrierites; their process of manufacture

• US 4,853,203 A
• Filed: 11/23/1987
• Issued: 08/01/1989
• Est. Priority Date: 11/21/1986
• Status: Expired due to Term

• Current Assignee: Institut Francais Du Petrole (IFP Energies Nouvelles)
• Original Assignee: Institut Francais Du Petrole (IFP Energies Nouvelles)
• Inventors: Lamblin, Jean-Marc, Faust, Anne-Catherine, Guth, Jean-Louis, Raatz, Francis
• Primary Examiner(s): Doll, John
• Assistant Examiner(s): BRENEMAN, ROBERT B
• Application Number:
  US07/124,122
• Time in Patent Office: 617 Days
• Field of Search: 423/326, 423/328, 423/329, 423/277, 423/464, 423/624, 423/594, 502/60, 502/77, 502/61, 502/62, 502/65, 502/66
• US Class Current: 423/708
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/04 having base-exchange properties, e.g. crystalline zeolites B01J29/005 takes precedence
• CPC Class Codes: B01J 29/65 of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
• CPC Class Codes: B01J 29/655 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• CPC Class Codes: B01J 29/68 Iron group metals or copper
• CPC Class Codes: B01J 29/87 Gallosilicates; Aluminogallosilicates; Galloborosilicates B01J29/005 takes precedence
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/065 Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
• CPC Class Codes: C01B 39/082 Gallosilicates
• CPC Class Codes: C01B 39/12 the replacing atoms being at least boron atoms
• CPC Class Codes: C01B 39/445 using at least one organic template directing agent
• CPC Class Codes: C07C 2/12 with crystalline alumino-silicates or with catalysts comprising molecular sieves
• CPC Class Codes: C07C 2529/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
• CPC Class Codes: Y10S 423/23 Ferrierite, e.g. SR-D ZSM-33

Abstract

New ferrierites are disclosed as well as their process of manufacture.

According to the invention, these new ferrierites are characterized by:

(a) The following approximate formula:

M.sub.x/n (T.sup.III O.sub.2).sub.x (Si.sup.IV O.sub.2).sub.36-x

wherein T^III is at least one element selected from the group formed of boron (B^III),aluminum (Al^III),gallium (Ga^III) and iron (Fe^III)

x ranges from 0.05 and 6.6

M is a compensation cation

n is the valence of M.

(b) A particular X-ray diagram,

(c) A fluorine content after synthesis ranging from about 0.01 to 1.6% by weight, and

(d) A Si^IV /T^III molar ratio of at least 4.75.

Claims

1. A crystalline synthetic ferrierite characterized by:

a) the following approximate formula;

space="preserve" listing-type="equation">M.sub.x/n (T.sup.III O.sub.2).sub.x (Si.sup.IV O.sub.2).sub.36-x

where T^III represents at least one element selected from the group of boron (B^III), aluminum (Al^III), gallium (Ga^III) and iron (Fe^III)

x ranges from 0.05 to 6.6

M is a compensation cation

n is the valence of M.

b) an X-ray diffraction diagram shown in Table 1B of the specification,

c) a fluorine content after synthesis ranging from 0.2 to 1.6% by weight, and

d) a Si^IV /T^III molar ratio of at least about 4.75.

2. A ferrierite according to claim 1, wherein the fluorine content is 0.20-1.0% by weight.

3. A catalyst containing by weight :

a) at least 3% by weight of ferrierite according to claim 1,

b) at most 97% by weight of a matrix selected from the group consisting of alumina, silica, magnesia, zirconia, titanium oxide, boron oxide, a clay or any combination of at least two of the above-mentioned compounds.

4. A ferrierite produced by a process consisting essentially of:

(a) preparing a reaction mixture in aqueous solution at a pH lower than about 10, comprising at least one source of silicon oxide, one source of at least one oxide of trivalent metal T selected from the group consisting of boron, gallium, aluminum and iron, one source of fluorine ion F^- and at least one organic structurizing agent supplying nitrogen-containing organic cations, selected from the group consisting of primary and secondary aliphatic monoamines, diamines, triamines and ammonium cations deriving by protonation from said mono-, di-, triamines, said agent having a total number of carbon and nitrogen atoms from 3 to 8, said mixture having a composition, in terms of molar ratios, ranging within the following intervals;

space="preserve" listing-type="tabular">______________________________________ Si.sup.IV /Σ

T.sup.III 2-400 (T.sup.III = B,Al,Ga,Fe) F.sup.- /Si.sup.IV 0.1-3 Organic structurizing agent/Si.sup.IV 0.1-4 H.sub.2 O/Si.sup.IV 4-200 ______________________________________

(b) maintaining said mixture at a heating temperature of at most 270°

C., so as to obtain crystals, and

(c) roasting said crystals at a temperature higher than 400°

C., whereby the resultant zeolite has;

(1) the following approximate formula;

space="preserve" listing-type="equation">M.sub.x/n (T.sup.III O.sub.2).sub.x (Si.sup.Iv O.sub.2)36-x

where T^III represents at least one element selected from the group of boron (B^III), aluminum (Al^III), gallium (Ga^III) and iron (Fe^III)

x ranges from 0.05 to 6.6

M is a compensation cation

n is the valence of M;

(2) an X-ray diffraction diagram shown in Table 1B;

(3) a fluorine content after synthesis ranging from 0.2 to 1.6% by weight; and

(4) a Si^IV /T^III molar ratio of at least about 4.75.

5. A ferrierite according to claim 4, wherein said mixture in aqueous solution has a pH and a composition, in terms of molar ratios, rangiing within the following intervals:

space="preserve" listing-type="tabular">______________________________________ pH 4.5-9 Si.sup.IV /Si.sup.T 4-150 (T.sup.III --B,A,1,Ga,Fe) F.sup.- /Si.sup.IV 0.25-2.5 Organic structurizing agent 0.25-2.5 H.sub.2 O/Si.sup.IV 6-80. ______________________________________

6. A ferrierite according to claim 4, wherein the heating temperature of said reaction mixture is maintained within the range of 120°

-260°

C.

7. A ferrierite according to claim 4, wherein said crystals are roasted at a temperature within the range of about 500°

-600°

C.

8. A ferrierite according to claim 4, wherein said crystals are roasted in the presence of a molecular oxgen-containing gas.

9. A ferrierite according to claim 4, wherein at least a part of the original cations is replaced by ion exchange, with a cation or mixture of cations selected from groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the periodic classification of elements.

10. A crystalline synthetic ferrierite having:

(a) the following approximate formula;

space="preserve" listing-type="equation">M.sub.x/n (T.sup.III O.sub.2).sub.x (Si.sup.IV O.sub.2).sub.36-x

where T^III represents at least one of boron (B^III), aluminum (Al^III), gallium (Ga^III) and iron (Fe^III)

x ranges from 0.05 to 6.6

M is a compensation cation

n is the valence of M;

(b) an X-ray diffraction diagram shown in Table 1B of the specification;

(c) a fluorine content after synthesis ranging from about 0.01 to 1.6% by weight; and

(d) a Si^IV /T^III molar ratio of at least about 32.

11. A ferrierite according to claim 10, characterized in that the Si^IV /T^III molar ratio is at least about 100.

12. A ferrierite according to claim 10, characterized in that the Si^IV /T^III molar ratio is at least about 40.

13. A catalyst containing by weight:

a) at least 3% by weight of ferrierite according to claim 12,

b) at most 97% by weight of a matrix selected from the group consisting of alumina, silica, magnesia, zirconia, titanium oxide, boron oxide, a clay or any combination of at least two of the above-mentioned compounds.

14. A catalyst containing by weight:

a) at least 20% by weight of ferrierite according to claim 12,

b) at most 80% by weight of a matrix selected from the group consisting of alumina, silica, magnesia, zirconia, titanium oxide, boron oxide, a clay or any combination of at least two of the above-mentioned compounds.

15. A process for manufacturing a crystalline synthetic ferrierite consisting essentially of the steps of:

(a) preparing a reaction mixture in aqueous solution at a pH lower than about 10, comprising at least one source of silicon oxide, one source of at least one oxide of trivalent metal T selected from the group consisting of boron, gallium, aluminum and iron, one source of fluorine ion F^- and at least one organic structurizing agent supplying nitrogen-containing organic cations, selected from the group consisting of primary and secondary aliphatic monoamines, diamines, triamines and ammonium cations deriving by protonation from said mono-, di-, triamines, said agent having a total number of carbon and nitrogen atoms from 3 to 8, said mixture having a composition, in terms of molar ratios, ranging within the following intervals;

space="preserve" listing-type="tabular">______________________________________ Si.sup.IV /Σ

T.sup.III 2-400 (T.sup.III = B,Al,Ga,Fe) F.sup.- /Si.sup.IV 0.1-3 Organic structurizing agent/Si.sup.IV 0.1-4 H.sub.2 O/Si.sup.IV 4-200 ______________________________________

(b) maintaining said mixture at a heating temperature of at most 270°

C., so as to obtain crystals, and

(c) roasting said crystals at a temperature higher than 400°

C., whereby the resultant zeolite has;

(1) the following approximate formula;

space="preserve" listing-type="equation">M.sub.x/n (T.sup.III O.sub.2).sub.x (Si.sup.IV O.sub.2).sub.36-x

where T^III represents at least one element selected from the group of boron (B^III), aluminum (Al^III), gallium (Ga^III) and iron (Fe^III).

x ranges from 0.05 to 6.6

M is a compensation cation

n is the valence of M;

(2) an X-ray diffraction diagram shown in Table 1B of the specification;

(3) A fluorine content after synthesis ranging from about 0.01 to 1.6% by weight; and

(4) a Si^IV /T^III molar ratio of at least about 32.

16. A process according to claim 15, wherein said mixture in aqueous solution has a pH and a composition, in terms of molar ratios, ranging within the following intervals:

space="preserve" listing-type="tabular">______________________________________ PH 4.5-9 Si.sup.IV /Σ

T.sup.III 4-150 (T.sup.III = B,Al,Ga,Fe) F.sup.- /Si.sup.IV 0.25-2.5 Organic structurizing agent 0.25-2.5 H.sub.2 O/Si.sup.IV 6-80. ______________________________________

17. A process according to claim 15, wherein the heating temperature of said reaction mixture is maintained within the range of 120°

-260°

C.

18. A process according to claim 15, wherein said crystals are roasted at a temperature within the range of about 500°

-600°

C.

19. A process according to claim 15 wherein said crystals are roasted in the presence of a molecular oxygen-containing gas.

20. A process according to claim 15, wherein at least a part of the original cations is replaced, by ion exchange, with a cation or mixture of cations selected from groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the periodic classification of elements.

21. A process according to claim 15, wherein the source of fluorine ions replaces OH^- ions in said solution to provide mobility to silica ions of silica forming ferrierite tetrahedrons.

22. A process according to claim 21, wherein the fluorine ion compound is ammonium fluoride or difluoride.