Ferrierites; their process of manufacture

Claim 2

A crystalline synthetic ferrierite 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 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.

Claim 3

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

Claim 4

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.

Claim 5

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: ______________________________________ Si.sup.IV /ΣT.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: 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.

Claim 6

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: ______________________________________ Si.sup.IV /ΣT.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: 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.

Claim 7

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: ______________________________________ 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. ______________________________________

Claim 8

A ferrierite according to claim 4, wherein the heating temperature of said reaction mixture is maintained within the range of 120°-260° C.

Claim 9

A ferrierite according to claim 4, wherein said crystals are roasted at a temperature within the range of about 500°-600° C.

Claim 10

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

Claim 11

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.

Claim 12

A crystalline synthetic ferrierite having: (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 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.

Claim 13

A crystalline synthetic ferrierite having: (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 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.

Claim 14

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

Claim 15

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

Claim 16

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.

Claim 17

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.

Claim 18

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: ______________________________________ Si.sup.IV /ΣT.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: 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.

Claim 19

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: ______________________________________ Si.sup.IV /ΣT.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: 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.

Claim 20

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: ______________________________________ PH 4.5-9 Si.sup.IV /ΣT.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. ______________________________________

Claim 21

A process according to claim 15, wherein the heating temperature of said reaction mixture is maintained within the range of 120°-260° C.

Claim 22

A process according to claim 15, wherein said crystals are roasted at a temperature within the range of about 500°-600° C.

Claim 23

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

Claim 24

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.

Claim 25

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.

Claim 26

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