High charge density silicometallophosphate molecular sieves

Patent metadata

Field	Value
Publication number	US-10449528-B2
Application number	US-201715446343-A
Country	US
Kind code	B2
Filing date	Mar 1, 2017
Priority date	Mar 4, 2016
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

A new family of crystalline microporous high charge density silicometallophosphates has been synthesized. These silicometallophosphate are represented by the empirical formula of:

R p+ r M m + E x PSi y O z

where M is an alkali metal such as potassium, R is any quaternary ammonium cation such as ethyltrimethylammonium and E is a trivalent framework element such as aluminum or gallium. This family of high charge density silicometallophosphate molecular sieves has catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

First claim

The invention claimed is:

1. A microporous crystalline silicometallophosphate material having a three-dimensional framework of [EO 4/2 ] − and [PO 4/2 ] + and SiO 4/2 tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of:
R p+ r M m + E x PSi y O z
where R is at least one of any quaternary ammonium cation, diquaternary ammonium cation triquaternary cation, quatroquaternary cation and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.2 to about 3.0, “p” is the weighted average valence of R and varies from 1 to 4, M is an alkali metal such as Li + , Na + , K + , Rb + and Cs + and mixtures thereof, “m” is the mole ratio of M to P and varies from 0.2 to 3.0, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is mole ratio of E to P and varies from 1.25 to about 4.0, “y” is the mole ratio of Si to P and varies from 0.25 to about 4.5, “y”≥“x”−1, and “z” is the mole ratio of 0 to P and has a value determined by the equation:
z =( m+p·r+ 3· x+ 5+4· y )/2

and is characterized by a specific x-ray diffraction pattern and the material is thermally stable to at least 450° C.

2. The silicometallophosphate material of claim 1 where R is at least one quaternary ammonium cation selected from the group consisting of tetramethylammonium (TMA + ), ethyltrimethylammonium (ETMA + ), propyltrimethylammonium (PTMA + ), isopropyltrimethylammonium, diethyldimethylammonium (DEDMA + ), trimethylbutylammonium (TMBA + ), methyltriethylammonium (MTEA + ), propylethyldimethylammonium (PEDMA + ), N,N-dimethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium, dipropyldimethylammonium (DPDMA + ), diethylmethylpropylammonium, trimethylpentylammonium (TMPA + ), dimethyldiisopropylammonium, tetraethylammonium (TEA + ), hexyltrimethylammonium (HTMA + ), methylethyldipropylammonium, triethylpropylammonium, dibutyldimethylammonium, benzyltrimethylammonium (BzTMA + ), diethyldipropylammonium, octyltrimethylammonium, tetrapropylammonium (TPA + ), decyltrimethylammonium, adamantyltrimethylammonium, methyltributylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, and tetrabutylammonium (TBA + ).

3. The silicometallophosphate material of claim 1 where R is at least one diquaternary ammonium cation selected from the group consisting of methylene-bis-(trimethylammonium), bis-1,2-(trimethylammonium) ethylene, bis-1,3(trimethylammonium)propane, bis-1,3-(trimethylammonium)-2-propanol, bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane (i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e., hexamethonium, HM 2+ ), bis-1,8-(trimethylammonium)octane, bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane (i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e., hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene, bis-α,α′-(dimethylethylammonium)-m-xylene, bis-α,α′-(dimethylethylammonium)-o-xylene, bis-α,α′-(trimethylammonium)-p-xylene, bis-α,α′-(trimethylammonium)-m-xylene, bis-α,α′-(trimethylammonium)-o-xylene, bis-1,5-(N-methylpiperidinum)pentane, bis-1,6-(N-methylpiperidinum)hexane, N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium, N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium, N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium, N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium, and N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium; where R is at least one triquaternary ammonium cation selected from the group consisting of tris-1,3,5-(triethylammoniomethyl)benzene, tris-1,3,5-(trimethylammoniomethyl)benzene, and tris-1,3,5-(dimethylethylammoniomethyl)benzene or where R is at least one quatroquaternary ammonium cation selected from the group consisting of [(C 6 H 5 CH 2 )(Me 2 )N(—CH 2 CH(OH)CH 2 N(Me 2 )—) 3 CH 2 C 6 H 5 ] 4+ (i.e., dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene, tetrakis-1,2,4,5-(triethylammoniomethyl)benzene and tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene.

4. The silicometallophosphate material of claim 1 in where “y”>“x”.

5. The silicometallophosphate material of claim 1 where the silicometallophosphate material is thermally stable up to a temperature of at least 500° C.

6. A stable, calcined form of the crystalline microporous silicometallophosphate of claim 1 , comprising a three-dimensional framework of [EO 4/2 ] + and [PO 4/2 ] + and SiO 4/2 tetrahedral units characterized in that it has the specific x-ray diffraction pattern related to the diffraction pattern of the as-synthesized material.

7. A process for preparing microporous crystalline silicometallophosphate material having a three-dimensional framework of [EO 4/2 ] + and [PO 4/2 ] + and SiO 4/2 tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of:
R p+ r M m + E x PSi y O z
where R is at least one of any quaternary ammonium cation, diquaternary ammonium cation, triquaternary cation, quatroquaternary cation and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.2 to about 3.0, “p” is the weighted average valence of R and varies from 1 to 4, M is an alkali metal such as Li + , Na + , K + , Rb + and Cs + and mixtures thereof, “m” is the mole ratio of M to P and varies from 0.2 to 3.0, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is mole ratio of E to P and varies from 1.25 to about 4.0, “y” is the mole ratio of Si to P and varies from 0.25 to about 4.5, “y”≥“x”−1, and “z” is the mole ratio of O to P and has a value determined by the equation:
z =( m+p·r+ 3· x+ 5+4· y )/2

and is characterized by a specific x-ray diffraction pattern and the material is thermally stable to at least 450° C. the process comprising forming a reaction mixture containing reactive sources of R, E, P, M and Si, and heating the reaction mixture at a temperature of about 60° C. to about 200° C. for a time of about 1 day to 28 days to form the silicometallophosphate molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
a R 2/p O: b M 2 O:E 2 O 3 :c P 2 O 5 :d SiO 2 :e H 2 O

where “a” has a value of about 2.5 to about 20, “b” has a value of about 0.125 to about 1.5, “c” has a value of about 2 to about 8, “d” has a value of about 0.25 to about 8, and “e” has a value from 50 to 1000.

8. The process of claim 7 where the initial reaction mixture is a clear solution before digestion.

9. The process of claim 7 where a source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts, hydroxide salts and mixtures thereof.

10. The process of claim 7 where the source of E is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH) 3 , alkali aluminate salts, aluminum metal, aluminum halide salts, aluminum sulfate salts, aluminum nitrate salts, precipitated gallium oxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof.

11. The process of claim 7 where the silicon source is selected from the group consisting of tetraethylorthosilicate, silicon alkoxides, fumed silica, colloidal silica, alkali silicate salts and precipitated silica.

12. The process of claim 7 where the reaction mixture is reacted at a temperature of about 125° C. to about 185

Assignees

• Uop Llc

Inventors

• Lewis Gregory J
• Knight Lisa

Classifications

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C10G45/12

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• B01J29/82

  Phosphates {(B01J29/005 takes precedence)} · CPC title

• C10G50/00

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title

• C10G47/16

  Crystalline alumino-silicate carriers · CPC title