Process for the selective desulphurization of olefinic gasolines, comprising a hydrogen purification step
a technology of olefinic gasoline and hydrogen purification step, which is applied in the direction of organic chemistry, chemistry apparatus and processes, and refining to eliminate heteroatoms, etc., can solve the problems of affecting the service life of catalysts, and achieve the effect of reducing the consumption of hydrogen and reducing the flow rate of hydrogen purification
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example 1
Comparative
[0041] A pilot unit constituted by a reactor with a capacity of 200 ml was charged with 100 ml of commercially available HR806S catalyst sold by AXENS. This catalyst is based on cobalt and molybdenum deposited on alumina and was supplied in the pre-sulphurized form and thus did not require a subsequent sulphurization step before contact with the feed. The treated feed was gasoline A from a catalytic cracking unit. This gasoline was depentanized to treat only the C6+ fraction by hydrodesulphurization. This feed contained 425 ppm of sulphur with 6 ppm of sulphur in the form of mercaptans and with a bromine index, measured using the ASTM D1159-98 method, of 49 g / 100 g. The cut points for this gasoline A were determined by simulated distillation: gasoline A had 5% by weight and 95% by weight cut points of 61° C. and 229° C. respectively.
[0042] Gasoline A was mixed with pure hydrogen and injected into the reactor. The pressure was kept at 2.1 MPa, the feed flow rate was 400 ...
example 2
Comparative
[0045] In order to measure the influence of CO and CO2 on catalyst performance, a cylinder of hydrogen containing 100 ppmv of CO and 350 ppmv of CO2 was used. This hydrogen was mixed with gasoline at flow rates identical to those of Example 1. The mixture thus formed had a CO content of 65 ppmv and a CO2 content of 228 ppmv. The operating conditions were identical to Example 1. Table 2 shows the results of the test.
TABLE 2Temperature° C.260280300Sulphur, testppm1032513IBr, testg / 100 g38.432.323.6Selectivity5.86.84.8
[0046] The presence of CO and CO2 in respective amounts of 65 ppmv and 228 ppmv in the mixture of hydrogen and gasoline A degrades the hydrodesulphurization activity of the catalyst. In contrast, the hydrogenating activity is virtually unaffected, causing a fall in selectivity.
example 3
In Accordance with the Invention
[0047] Example 3 was in accordance with the invention, i.e. the hydrogen containing CO and CO2 used in Example 2 was pre-treated to oxidize the CO to CO2. Oxidation was carried out by mixing hydrogen and oxygen and treating the mixture over an oxidation catalyst. The hydrogen was mixed with a stream of pure oxygen, the flow rate of which was adjusted so that the molar ratio between the oxygen and the CO was 1.1. The reactor was operated at a temperature close to ambient temperature (50° C.), at a pressure of 2.1 MPa.
[0048] The catalyst was prepared, for example, by co-precipitation of a solution containing HAuCL4.3H2O and Fe(NO3)3.9H2O and a solution containing sodium carbonate. These two solutions were gradually added to a precipitation reactor containing distilled water then vigorously stirred. The reaction mixture was maintained at 80° C. throughout addition of the two solutions, and during the entire operation the pH was maintained between 8 and...
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Abstract
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