Process for the integrated production of H
The present invention addresses to a process for the integrated production of H 2 and aviation kerosene from renewable raw materials aiming at reducing CO 2 emissions and consequently bringing benefits to reduce the impact of global warming on the planet. The process involves a hydrotreatment section to obtain n-paraffins followed by a hydroisomerization section to produce isoparaffins. The water and light hydrocarbons obtained in the isoparaffin production process are used for the production of H 2 by the steam reforming process. An alcohol, such as ethanol or glycerin, with less than 6 carbon atoms, is fed into the hydrotreating section to make up the light hydrocarbon stream used in the production of renewable hydrogen.
1 . A process for integrated production of H 2 and aviation kerosene from a renewable raw material, the process comprising:
(a) reacting, in a hydrotreating section, in the presence of H 2 and a catalyst in a fixed bed, a mixture of renewable raw material and an oxygenated hydrocarbon of up to 6 carbon atoms diluted with a product to produce a stream containing n-paraffins and isoparaffins with 12 to 18 carbon atoms, and a stream of light products;
(b) hydroisomerizing and hydrocracking, in a hydroisomerization and hydrocracking section, at least a portion of the n-paraffins produced in the presence of H 2 and a fixed bed selective catalyst to produce a stream containing isoparaffins and the product;
(c) separating, in a separation section, the stream containing n-paraffins and isoparaffins with 12 to 18 carbon atoms and the stream of light products into an aqueous stream, a hydrocarbon stream with a chain size of up to 6 carbon atoms, a stream in a naphtha distillation range, a stream in a distillation range of the aviation kerosene, a stream in a distillation range of diesel and a heavy material stream;
(d) recycling a part of the heavy material stream to the hydrotreating section and a fraction of the diesel stream to the hydroisomerization and hydrocracking section;
(e) using the aqueous stream for generation of steam for production of hydrogen by steam reforming and the hydrocarbon stream with the chain size of up to 6 carbon atoms as charge, and optionally as fuel for the production of hydrogen by steam reforming;
(f) recycling at least a part of the hydrogen produced by steam reforming for producing n-paraffins in the hydrotreating section and for producing isoparaffins in the hydroisomerization and hydrocracking section.
2 . The process of claim 1 , wherein the renewable raw material is selected from vegetable oils, animal oils and fats, fatty acids, or a mixture thereof.
3 . The process of claim 2 , wherein the renewable raw material is vegetable oils with an iodine number less than 100 and with a concentration of fatty acids with a C12 to C16 hydrocarbon chain.
4 . The process of claim 1 , wherein the oxygenated hydrocarbon of up to 6 carbon atoms is selected from ethanol, glycerin, or a mixture thereof.
5 . The process of claim 1 , wherein a ratio between the oxygenated hydrocarbon and the renewable raw material is between 0.01:1 and 0.5:1 m/m.
6 . The process of claim 5 , wherein the ratio between the oxygenated hydrocarbon and the renewable raw material is between 0.05:1 and 0.2:1 m/m.
7 . The process of claim 1 , wherein the catalyst in the fixed bed is selected from nickel and molybdenum oxides supported on alumina, cobalt and molybdenum oxides supported on alumina, chromium oxides, copper oxides or mixtures thereof supported in aluminas or aluminas promoted by alkali metals, noble metals dispersed in a surface area support.
8 . The process of claim 1 , wherein the fixed bed selective catalyst comprises a zeolite phase and a metallic phase, selected from Pt, Pd, Ni or a combination of these elements, in contents between 0.2 and 2.0% w/w.
9 . The process of claim 8 , wherein the fixed bed selective catalyst comprises the zeolite phase and the metallic phase, selected from Pt, Pd, Ni, or a combination of these elements, in contents between 0.5 and 1.0% w/w.
10 . The process of claim 8 , wherein the fixed bed selective catalyst comprises at least 90% Beta zeolite containing 1 to 10% m/m phosphorus.
11 . The process of claim 1 , wherein reacting in the hydrotreating section is carried out at temperatures between 25° and 350° C., pressures between 20 and 100 kgf/cm 2 , space speeds on a volumetric basis between 0.5 and 4.0 h −1 , and H 2 /hydrocarbon ratios between 150 and 1000 Nm 3 /m 3 of charge.
12 . The process of claim 1 , wherein hydroisomerizing and hydrocracking is conducted at temperatures between 15° and 300° C., pressures between 20 and 100 kgf/cm 2 , space speeds on a volumetric basis between 0.5 and 4.0 h −1 , and H 2 /hydrocarbon ratios between 150 and 1000 Nm 3 /m 3 of charge.
13 . The process of claim 3 , wherein the fatty acids comprise palm oil, olive oil, or peanut oil.
14 . The process of claim 7 , wherein the noble metals comprise Pt or Pd, and wherein the surface area support comprises a transition alumina.