Cracking of heavy oils by combination of hydrogen donor solvent with catalyst. (Part 3). Effects of catalytic activities on chemical hydrogen consumption.:Effects of Catalytic Activities on Chemical Hydrogen Consumption
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Chemical hydrogen consumption in upgrading hydrogen donor solvent and catalysts was studied with a small scale (0.1 BPD) pilot plant (Fig. 1).To clarify the catalyst effects on chemical hydrogen consumption, three different combinations of cracking reactor and hydrogenator, described below, were studied.cracking reactor hydrogenatorCase A without catalyst demetallization(thermal cracking type) catalyst (low activity)Case B demetallization demetallization(intermediate type) catalyst (low activity) catalyst (low activity)Case C desulfurization desulfurization(catalytic cracking type) catalyst (high activity) catalyst (high activity)Chemical hydrogen consumption, desulfurization and H/C (atomic ratio) were in the order of A<B<C, and the clear effects of the catalysts were observed (Table 1).The properties of the total liquid effluents and 545°C residues from the hydrogenator were analysed (Tables 2, 3). Carbon residues and asphaltenes were reduced in Case C in comparison with Case A and Case B.To make clear the hydrogen additions to the fractions, the yield of the fractions and hydrogen additions to the fractions were illustrated in Figs. 2, 3 and 4. From these figures, it can be concluded as follows:(1) In heavier fractions (325°C and heavier), hydrogen addition was in the order of, A<B<C.(2) In lighter fractions (325°C and lighter), the differences were not so clear, but the trend was in the order of, A, B>C.To make clear the above conclusions, component analyses and structural analyses using 1H-NMR were conducted for the three cases (Table 4, Figs. 5, 6). From these data, the following information were obtained:(1) Ha: A, B>Cthis trend was remarkable with asphaltenes(2) Hα: no clear tendency(3) Hβ, Hγ: A, B<C(4) n: A, B<C(5) σ: A, B<C (with asphaltenes)(6) fa: A, B>CFrom these information, it may be said that by increasing catalyst activities, the degree of hydrogenation of aromatic rings increased but the degree of cleavages of side chains decreased.Hydrogen consumption is a very important factor in heavy oil upgrading process from the economics viewpoint and, therefore, effective utilization of hydrogen should be given serious attention. It is well known that aromatic rings are condenced into heavier fractions, whereby, hydrogen chemically consumed is used to hydrogenate these aromatic rings, in the case of relatively high catalyst activities.In cracking heavy oils in the condition of a hydrogen donor solvent and a demetallization catalyst coexisting, cracking reactions may be considered to be substantially of thermal nature (details were discussed in the previous paper, Part 2), and that the catalyst serves to stabilize (hydrogenate) the free radicals, consequently restricting coke formation at lower chemical hydrogen consumption. This cracking, therefore, may be said to be an effective way to utilize hydrogen economically.
- 公益社団法人 石油学会の論文
公益社団法人 石油学会 | 論文
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