Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefins and aromatic compounds
View Patent ↗Process for the hydrotreatment of a mixture of C4 to C8 hydrocarbon-based compounds, rich in olefins and monoaromatic compounds, by hydrogenation in the presence of a solid catalyst, characterized in that an ammonia precursor is introduced into the charge of hydrocarbon-based compounds and in that the catalyst comprises at least one transition metal supported on at least one refractory oxide.
1. A process for the hydrotreatment of an olefin-rich feedstock comprising:
(a) providing a reactor containing a solid hydrogenation catalyst comprising at least one transition metal supported on at least one refractory oxide;
(b) supplying hydrogen and an olefin-rich feedstock comprising a mixture of C 4 -C 8 hydrocarbon-based compounds rich in olefins and at least one monoaromatic compound into said reactor and into contact with said hydrogenation catalyst while maintaining said reactor under pressure and temperature conditions effective for the hydrogenation of said olefins; and
(c) incorporating into said olefin-rich feedstock an ammonia precursor which decomposes to release ammonia in said reactor which comes into contact with said catalyst.
2. The process of claim 1 wherein said ammonia precursor is incorporated into said olefin-rich feedstock in an amount of up to 1,000 ppm nitrogen molar equivalent weight.
3. The process of claim 2 wherein said ammonia precursor is incorporated into said feedstock in an amount within the range of 5-1,000 ppm nitrogen molar equivalent weight.
4. The process of claim 2 wherein said nitrogen precursor is incorporated into said feedstock in an amount within the range of 10-200 ppm nitrogen molar equivalent.
5. The process of claim 1 wherein said ammonia precursor comprises a nitrogen-containing compound capable of releasing ammonia gas under the temperature and pressure conditions in said reactor.
6. The process of claim 5 wherein said ammonia precursor has a decomposition temperature of less than 300° C.
7. The method of claim 6 wherein said ammonia precursor has a decomposition temperature of less than 180° C.
8. The process of claim 1 wherein said ammonia precursor is selected from the group consisting of linear and branched amines, polyamines, imines, and urea and its derivatives.
9. The process of claim 8 wherein said ammonia precursor is an amine or polyamine chosen from the group consisting of mono-, di- and trialkylamines containing from 1 to 10 carbon atoms per alkyl group, the alkyl groups being linear or cyclic, and polyalkylamines containing from 1 to 5 nitrogen atoms, each alkyl group containing from 1 to 6 carbon atoms in linear or branched form.
10. The process of claim 9 wherein said ammonia precursor is an alkyl amine or a polyalkylamine selected from the group consisting of from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylmine, heptylamine, cyclohexylamine, cycloheptylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, triemethylamine, triethylamine, tripropylamine, tributylamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, dimethylenetriamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetamine, tetracthylenepentamine, and tetrapropylenepentamine.
11. The process in claim 10 wherein said ammonia precursor is selected from the group consisting of cyclohexylamine, triethylamine and ethylenediamine.
12. The process of claim 1 wherein said reactor is operated at a temperature within the range of 50-400° C., a pressure within the range of 10 6 Pa-10 7 Pa, and a space velocity within the range of 0.5-10 h −1 .
13. The process of claim 12 wherein said ammonia precursor has a decomposition temperature which is less than the temperature at which the reactor is operated.
14. The process of claim 12 wherein said reactor is operated at a pressure within the range of 3×10 6 Pa-6×10 6 Pa.
15. The process of claim 1 wherein the support of said hydrogenation catalyst is selected from the group consisting of alumina, silica, zirconia, silicoaluminas, alumino-phosphates, zirconia, magnesia and titanium oxides, in rutile and anatase form, said oxides being present in amorphous or crystalline form.
16. The process of claim 15 wherein said transition metal is selected from the group consisting of nickel, cobalt, moldenum, vanadium, tungsten, and mixtures thereof.
17. The combination of claim 16 wherein said transition metal is nickel.
18. The process of claim 16 wherein said transition metal is selected from the group consisting of a nickel/molybdenum composite, a nickel/tungsten composite, and a cobalt/molybdenum composite.
19. The process of claim 1 wherein said reactor is operated under conditions to produce an excess of ammonia gas which is withdrawn from said reactor, and further comprising recycling said ammonia gas into the hydrogen supplied to said reactor.
20. The process of claim 1 wherein said feedstock comprises the product of a C 6 fraction produced from a catalytic reforming operation or a vapor reforming operation.