Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams
First Claim
1. A process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from fossil hydrocarbon streams contaminated with said compounds, the process comprising the following steps:
- a) Providing a pulverized raw iron oxide;
b) Providing at least one acid c) Providing at least one peroxide;
d) Oxidizing unsaturated compounds as well as sulfur and nitrogen contaminants by admixing, under atmospheric pressure and equal or higher than ambient temperature, under agitation, said organic acid and said hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds and then said peroxide, so as to obtain a peracid, the molar amount of peroxide and organic acid relative to the sum of the nitrogen and sulfur contents present in the hydrocarbon stream being at least 3.0, at pH between 2.0 and 6.0, for the required period to obtain a hydrocarbon stream where the unsaturated, sulfur and nitrogen contaminants have been partially oxidized;
e) Further oxidizing said unsaturated compounds as well is sulfur and nitrogen contaminants in the presence of oxidant hydroxyl radicals generated by adding to said partially oxidized hydrocarbon stream, under atmospheric pressure and equal or higher than ambient temperature, the higher than ambient temperature being generated by the process itself, under agitation, a catalytic amount of said pulverized iron oxide so as to obtain a slurry of iron oxide, hydrocarbon stream and oxidized unsaturated, sulfur and nitrogen compounds, the reaction conditions being kept during 1-2 hours and an acidic pH between 2.0 and 6.0;
f) After the end of the reaction, filtrating the reaction medium containing an aqueous phase and an oily hydrocarbon phase, and separating the spent iron oxide catalyst;
g) Decanting in order to separate the organic-rich aqueous phase;
h) Correcting the pH of the resulting hydrocarbon phase to values between 6.1 and 9.0 and recovering the oil phase;
i) Post-treating the oil phase to extract the oxidized products at the desired level; and
j) Recovering the post-treated hydrocarbon phase having sulfur compounds in the range of 0.01 weight % and 0.2 weight % and nitrogen compounds in the range of 0.001 weight % to 0.15 weight %, the final olefin content being up to 50% of the original olefin content.
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Abstract
A process for the catalytic oxidation of sulfur and nitrogen contaminants as well as unsaturated compounds present in a hydrocarbon fossil oil medium is described, the process comprising effecting the oxidation in the presence of at least one peroxide, at least one acid and a pulverized raw iron oxide. The process shows an improved oxidation power towards the contaminants typically present in a fossil oil medium, this deriving from the combination of the peroxy-acid and the hydroxyl radical generated in the reaction medium due to the presence of an iron oxyhydroxide such as a limonite clay, which bears a particular affinity for the oil medium. The process finds use in various applications, from a feedstock for refining until the preparation of deeply desulfurized and deeply denitrified products.
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Citations
43 Claims
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1. A process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from fossil hydrocarbon streams contaminated with said compounds, the process comprising the following steps:
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a) Providing a pulverized raw iron oxide;
b) Providing at least one acid c) Providing at least one peroxide;
d) Oxidizing unsaturated compounds as well as sulfur and nitrogen contaminants by admixing, under atmospheric pressure and equal or higher than ambient temperature, under agitation, said organic acid and said hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds and then said peroxide, so as to obtain a peracid, the molar amount of peroxide and organic acid relative to the sum of the nitrogen and sulfur contents present in the hydrocarbon stream being at least 3.0, at pH between 2.0 and 6.0, for the required period to obtain a hydrocarbon stream where the unsaturated, sulfur and nitrogen contaminants have been partially oxidized;
e) Further oxidizing said unsaturated compounds as well is sulfur and nitrogen contaminants in the presence of oxidant hydroxyl radicals generated by adding to said partially oxidized hydrocarbon stream, under atmospheric pressure and equal or higher than ambient temperature, the higher than ambient temperature being generated by the process itself, under agitation, a catalytic amount of said pulverized iron oxide so as to obtain a slurry of iron oxide, hydrocarbon stream and oxidized unsaturated, sulfur and nitrogen compounds, the reaction conditions being kept during 1-2 hours and an acidic pH between 2.0 and 6.0;
f) After the end of the reaction, filtrating the reaction medium containing an aqueous phase and an oily hydrocarbon phase, and separating the spent iron oxide catalyst;
g) Decanting in order to separate the organic-rich aqueous phase;
h) Correcting the pH of the resulting hydrocarbon phase to values between 6.1 and 9.0 and recovering the oil phase;
i) Post-treating the oil phase to extract the oxidized products at the desired level; and
j) Recovering the post-treated hydrocarbon phase having sulfur compounds in the range of 0.01 weight % and 0.2 weight % and nitrogen compounds in the range of 0.001 weight % to 0.15 weight %, the final olefin content being up to 50% of the original olefin content. - View Dependent Claims (5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43)
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2. A process for the removal of sulfur, nitrogen and unsaturated compounds from fossil hydrocarbon streams contaminated with said compounds through catalytic oxidation, wherein said process comprises the following steps:
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a) Providing a pulverized raw iron oxide;
b) Providing at least one acid;
c) Providing at least one peroxide;
d) Oxidizing unsaturated compounds as well as sulfur and nitrogen contaminants by admixing, under atmospheric pressure and equal or higher than ambient temperature, under agitation, said organic acid and said hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds and then said peroxide, so as to obtain a peracid, the molar amount of peroxide and organic acid relative to the sum of the nitrogen and sulfur contents present in the hydrocarbon stream being at least 3.0, at pH between 2.0 and 6.0, for the required period to obtain a hydrocarbon stream where the unsaturated, sulfur and nitrogen contaminants have been partially oxidized;
e) Further oxidizing said unsaturated compounds as well as sulfur and nitrogen contaminants in the presence of oxidant hydroxyl radicals generated by adding to said partially oxidized hydrocarbon stream, under atmospheric pressure and equal or higher than ambient temperature, the higher than ambient temperature being generated by the process itself, under agitation, a catalytic amount of said pulverized raw iron oxide so as to obtain a slurry of iron oxide, hydrocarbon stream and oxidized unsaturated, sulfur and nitrogen compounds, the reaction conditions being kept during 1-2 hours and an acidic pH between 2.0 and 6.0;
f) After the end of the reaction, filtrating the reaction medium containing an aqueous phase and an oily hydrocarbon phase, and separating the spent iron oxide catalyst;
g) Decanting in order to separate the organic-rich aqueous phase;
h) Correcting the pH of the resulting hydrocarbon phase to values between 6.1 and 9.0 and recovering the oil phase;
i) Post-treating the oil phase to extract/remove the oxidized products at the desired level; and
j) Recovering the post-treated hydrocarbon phase having sulfur compounds in the range of 0.01 weight % and 0.2 weight % and nitrogen compounds in the range of 0.001 weight % to 0.15 weight %, the final olefin content being up to 50% of the original olefin content.
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3. A process for obtaining a hydrocarbon stream suitable for refining processes through the catalytic oxidation of same hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds, wherein said process comprises the following steps:
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a) Providing a pulverized raw iron oxide;
b) Providing at least one acid;
c) Providing at least one peroxide;
d) Oxidizing unsaturated compounds as well as sulfur and nitrogen contaminants by admixing, under atmospheric pressure and equal or higher than ambient temperature, under agitation, said organic acid and said hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds and then said peroxide, so as to obtain a peracid, the molar amount of peroxide and organic acid relative to the sum of the nitrogen and sulfur contents present in the hydrocarbon stream being at least 3.0, at pH between 2.0 and 6.0, for the required period to obtain a hydrocarbon stream where the unsaturated, sulfur and nitrogen contaminants have been partially oxidized;
e) Further oxidizing said unsaturated compounds as well as sulfur and nitrogen contaminants in the presence of oxidant hydroxyl radicals generated by adding to said partially oxidized hydrocarbon stream, under atmospheric pressure and equal or higher than ambient temperature, the higher than ambient temperature being generated by the process itself, under agitation, a catalytic amount of said pulverized raw iron oxide so as to obtain a slurry of iron oxide, hydrocarbon stream and oxidized unsaturated, sulfur and nitrogen compounds, the reaction conditions being kept during 1-2 hours and an acidic pH between 2.0 and 6.0;
f) After the end of the reaction, filtrating the reaction medium containing an aqueous phase and an oily hydrocarbon phase, and separating the spent iron oxide catalyst;
g) Decanting in order to separate the organic-rich aqueous phase;
h) Correcting the pH of the resulting hydrocarbon phase to values between 6.1 and 9.0 and recovering the oil phase;
i) Post-treating the oil phase to extract the oxidized products at the desired level; and
j) Recovering the post-treated hydrocarbon phase suitable for further refining having nitrogen compounds less than 0.1 weight % and mass balance yields of the order of 80-90 weight %.
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4. A process for obtaining a deeply desulfurized and deeply denitrified product through the catalytic oxidation of a hydrocarbon stream containing sulfur, nitrogen and unsaturated contaminants, wherein said process comprises the following steps:
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a) Providing a pulverized raw iron oxide;
b) Providing at least one acid;
c) Providing at least one peroxide;
d) Oxidizing unsaturated compounds as well as sulfur and nitrogen contaminants by admixing, under atmospheric pressure and equal or higher than ambient temperature, under agitation, said organic acid and said hydrocarbon stream contaminated with sulfur, nitrogen and unsaturated compounds and then said peroxide, so as to obtain a peracid, the molar amount of peroxide and organic acid relative to the sum of the nitrogen and sulfur contents present in the hydrocarbon stream being at least 3.0, at pH between 2.0 and 6.0, for the required period to obtain a hydrocarbon stream where the unsaturated, sulfur and nitrogen contaminants have been partially oxidized;
e) Further oxidizing said unsaturated compounds as well as sulfur and nitrogen contaminants in the presence of oxidant hydroxyl radicals generated by adding to said partially oxidized hydrocarbon stream, under atmospheric pressure and equal or higher than ambient temperature, the higher than ambient temperature being generated by the process itself, under agitation, a catalytic amount of said pulverized raw iron oxide so as to obtain a slurry of iron oxide, hydrocarbon stream and oxidized unsaturated, sulfur and nitrogen compounds, the reaction conditions being kept during 1-2 hours and an acidic pH between 2.0 and 6.0;
f) After the end of the reaction, filtrating the reaction medium containing an aqueous phase and an oily hydrocarbon phase, and separating the spent iron oxide catalyst;
g) Decanting in order to separate the organic-rich aqueous phase;
h) Correcting the pH of the resulting hydrocarbon phase to values between 6.1 and 9.0 and recovering the oil phase;
i) Post-treating the oil phase to extract the oxidized products at the desired level; and
j) Recovering the post-treated, deeply desulfurized and deeply denitrified product having sulfur compounds less than 0.015 weight % (150 ppm) and nitrogen compounds less than 0.001 weight % (10 ppm), the final olefin content being up to 50% of the original olefin content and mass balance yields of the order of 50 weight %.
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Specification