Claims
- 1. A process for the preparation of a high-octane gasoline, which comprises contacting a light hydrocarbon containing one or more paraffins and/or olefins, each having 2 to 7 carbon atoms, with a crystalline silicate catalyst, characterized in that said catalyst comprises an aluminogallosilicate with its skeleton comprised of SiO .sub.4, AlO.sub.4 and GaO.sub.4 tetrahedra, that said alumino-gallosilcate has the following formula:
- aM.sub.2/n O.multidot.bAl.sub.2 O.sub.3 .multidot.Ga.sub.z O.sub.3 .multidot.cSiO.sub.2 .multidot.dH.sub.z O
- wherein M is a metal selected from an alkali metal, an alkaline earth metal and a mixture thereof, n is the valence of said metal, a is a positive number of (b +1).sup.+ 3.0, b is between 1 and 6, c is between 80 and 490, d is between 1 and 200, c/(b+1) is between 40 and 70, and c/b is between 46.7-140, and that said contacting is performed at a temperature of 350.degree.-650 .degree. C. under a hydrogen partial prssure of not higher than 5 kg/cm.sup.2.
- 2. A process according to claim 1, wherein the amounts of aluminum and gallium in the skeletal structure of said aluminogallosilicate range from 0.1 to 5.0 % by weight and from 0.1 to 10.0% by weight, respectively.
- 3. A process according to claim 1, wherein said light hydrocarbon contains one or more paraffins and/or olefins having 5 to 7 carbon atoms in an amount of at least 50 % by weight.
- 4. A process according to claim 1, wherein said light hydrocarbon contains one or more paraffins and/or olefins having 2 to 4 carbon atoms in an amount of at least 50 % by weight and the molar ratio of the gallium to the aluminum contained in the skeletal structure of said aluminogallosilicate is lower than 1 in terms of gallia and alumina.
- 5. A process according to claim 1, wherein said aluminogallosilicate is a product obtained by hydrothermally treating an aqueous mixture comprising a source of alumina and a source of gallia at a temperature and for a period of time sufficient to form crystals of said aluminogallosilicate.
- 6. A process according to claim 1, wherein said aluminogallosilicate is a product obtained by inserting gallium or aluminum each into the skeletal structure of a crystalline aluminosilicate or a crystalline gallosilicate.
- 7. A process according to claim 1, wherein at least a portion of said metal is replaced with hydrogen.
- 8. A process according to claim 1, wherein said catalyst further includes one or more of metal components of Groups IIa, IIIa, IVa, Va, VIa, VIIa, Ib, IIb, IIIb, IVb, Vb, VIb and VIII carried on said aluminogallosilicate.
- 9. A process according to claim 8, wherein said metal component is Ca, Mg, La, Mn, Re, Ir, Pt, Zn, In, Se, Pd, Ni or V.
- 10. A process according to claim 1, wherein the highoctane gasoline has an octane number of at least 95, when determined by the research method, and contains aromatic hydrocarbons having 6-8 carbon atoms as a major component.
- 11. The process of claim 1 wherein c/(b+1) is 45-60.
- 12. The process of claim 1 wherein c/(b+1) is 45-65.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 61-2658 |
Jan 1986 |
JPX |
|
Parent Case Info
This application is a continuation-in-part of U.S. Ser. No. 001,370 filed Jan. 8, 1987, and now abandoned.
The present invention relates to a novel crystalline aluminogallosilicate and to a process for the preparation of a high-octane gasoline blending stock containing an aromatic hydrocarbon as a major constituent, which uses the crystalline aluminogallosilicate as a catalyst.
Heretofore, the catalytic reforming of naphtha using a platinum aluminum catalyst is extensively employed for the preparation of a highoctane gasoline. Naphtha to be used as a raw material is usually from fractions having boiling points in the range from 70.degree. C. to 180.degree. C., when intended to be used for the preparation of gasoline for use with automobiles and from fractions having boiling points in the range from 60.degree. C. to 150.degree. C., when intended to be used for the preparation of BTX. Accordingly, it is difficult to produce a high-octane gasoline from a light hydrocarbon containing a paraffin and/or an olefin having each carbon atoms ranging from 2 to 7 because a rate for the conversion to aromatic hydrocarbons may be decreased to remarkably low levels as the number of carbon atoms is decreased. At the present time, light hydrocarbons are used in very limited ranges as raw materials in the field of petrochemistry and for the preparation of city gases. Therefore, a technology designed to be applied to produce high-octane gasolines from light hydrocarbons draws high attention in terms of an increase in an addition to a value of light hydrocarbons and increase in gasoline consumption.
As techniques relating to the preparation of high-octane gasoline blending stock are known various processes which involve, for example, the catalysis with a crystalline silicate, particularly the ZSM-5 silicate and those of the ZSM-5 type. Japanese Patent Early Publication No. 98,020/-1984 discloses a process which comprises converting each of n-butane and propane to aromatic compounds by using a calcined product of a crystalline gallium silicate from a gel having the composition represented by the following formula:
In accordance with the present invention, there is provided a process for the preparation of a high-octane gasoline, which comprises contacting a light hydrocarbon containing one or more paraffins and/or olefins, each having 2 to 7 carbon atoms with a crystalline silicate catalyst characterized in that said catalyst comprises an aluminogallosilicate with its skeleton comprised of SiO.sub.4, A10.sub.4 and GaO.sub.4 tetrahedra, and in that said contacting is performed at a temperature of 350.degree.-650 .degree. C. under a hydrogen partial pressure of not higher than 5 kg/cm.sup.2.
In another aspect, the present invention provides a crystalline aluminogallosilicate having the skeleton comprised of SiO.sub.4, A10.sub.4 and GaO.sub.4 tetrahedra and having the following formula:
The present invention will be described more in detail by referring to the drawings appended hereto. In the drawings,
FIG. 1 is a graph showing the relationships of SiO.sub.2 /T.sub.2 O.sub.3 (T: Al or Ga) vs. conversion and aromatics yield of an aluminosilicate and a gallosilicate for comparison uses;
FIG. 2 is a graph showing the relationships of SiO.sub.2 /Ga.sub.2 O.sub.3 vs, conversion and aromatics yield of the aluminogallosilicate of the present invention and the comparing gallosilicate;
FIG. 3 is a graph showing the relationship of SiO.sub.2 /Al.sub.2 O.sub.3 vs. aromatics yield of the comparing aluminosilicate;
FIG. 4 is a graph showing the relationships of the gallium concentrations and aromatics yields of the H-form aluminogallosilicate according to the present invention with those of the comparing H-form aluminosilicate carried with gallium;
FIG. 5 is a graph showing the relationships of reaction temperatures vs. conversion and aromatics yields of the aluminogallosilicate according to the present invention and the comparing aluminosilicate and gallosilicate;
FIG. 6 is a graph showing the relationships of times vs. conversion and aromatics yields of the H.sub.2 -treated and untreated aluminogallosilcates according to the present invention; and
FIG. 7 is a graph showing the relationships of regeneration cycles vs. conversion, aromatics yields and hydrogen yields of the aluminogallosilicate according to the present invention during the repetition of the reaction and regeneration cycles.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
|
4605805 |
Chang et al. |
Aug 1986 |
|
Foreign Referenced Citations (4)
| Number |
Date |
Country |
| 0107875 |
Oct 1983 |
EPX |
| 0124271 |
Mar 1984 |
EPX |
| 0107876 |
May 1984 |
EPX |
| 8403879 |
Oct 1984 |
WOX |
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
1370 |
Jan 1987 |
|
Patent Grant
4861934
