The way to obtain environmentally friendly diesel fuel

 

(57) Abstract:

The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates. When hydrogenation refining distillates and mixtures thereof with the remnants happens piling and deactivation of catalysts, ORGANOMETALLIC compounds and deposition of coke. To increase the service life of the catalyst and increase their activity proposed 2-stage method of Hydrotreating, where under hydroptherapy serves the catalyst in the following ratio, wt. %:

The molybdenum trioxide - 10-15

Oxide of Nickel and cobalt - 2-5

Phosphate of aluminum is 1.5-10

Iron phosphate is 0.5 to 2.0

Alumina - Rest

table 4.

The invention relates to a method for hydrogenation refining of crude oil in the presence of a catalyst and hydrogen and can be used in the oil industry.

When hydrogenation refining of petroleum distillates and mixtures thereof with the remnants happens piling and deactivation of catalysts, ORGANOMETALLIC compounds of vanadium, Nickel, iron and coke deposits.

For HC the weave of crude oil. There is a method of Hydrotreating of petroleum fractions /1/ in which to increase the stability and lifetime of the catalyst in the Hydrotreating process is carried out in two stages with the preliminary preparation of raw materials. The depth of vacuum gasoil hydrodesulphurization unit in such a process is not less than 80,0 and diesel fraction at least 90

The closest to the proposed invention is a method hydroperiod /2/, which is carried out with the prior hydropedological raw materials at two different catalysts hydroptherapy and Hydrotreating.

The process of hydroperiod preliminary hydropedological vacuum gasoil 350-560oC (sulfur 1.68 wt. the nitrogen of 0.14 wt. coking ability to 0.7 wt. the total content of vanadium, Nickel and iron 3.8 g/t) is carried out at a pressure of 5 MPa, a temperature of 360-400oC and various space velocities of hydroptherapy and Hydrotreating.

As catalysts for Hydrotreating use catalysts based on aluminum oxide-modified additives and promoted with metals of IV-VIII groups.

The depth of vacuum gasoil hydrodesulphurization unit in such a process is not less than 89,0 and diesel fractions up to 96

The aim of the invention is to improve the processing of crude oil, including preliminary hydroptherapy catalyst containing molybdenum trioxide, Nickel oxide or cobalt, aluminum oxide, aluminum phosphate and iron phosphate at a molar ratio of aluminum phosphate to phosphate from 3:1 to 5:1 and stage Hydrotreating when the ratio of the catalysts is from 1:1 to 1:20 at elevated temperature and pressure with a ratio of catalyst components of hydroptherapy, wt.

The molybdenum trioxide 10,0-15,0

Oxide of Nickel or cobalt 2,0-5,0

Phosphate of aluminium 1,5-10,0

Iron phosphate is 0.5-2,00

Alumina Else

The major difference of the proposed method is the use of being hydroptherapy catalyst additionally containing aluminum phosphate and iron phosphate at a molar ratio from 3:1 to 5:1, the modifying oxide of aluminum and allowing increasing the level of treatment, and the effectiveness of the proposed method.

The process is performed at a pressure of 3-10 MPa, a temperature of 330-420oC, flow rate in the zone of hydroptherapy raw materials 2-15 h-1and in the Hydrotreating zone 1-10 h-1when the ratio of the catalysts in the area of hydroptherapy and Hydrotreating from 1:1 to 1:20, the circulation of the hydrogen-containing gas 300-1000 nm3/luminia, the modified zeolite or pjatiokisi phosphorus and iron phosphate or oxide of cerium, europium and zirconium or titanium oxide promoted with metals IV or VIII group.

Comparison of the proposed method with the prototype shows that it is used in the catalyst composition of hydroptherapy phosphate of aluminum, which meets the criterion of "novelty".

A comparison of the proposed technical solutions with other known in the art solutions shows that the use of under hydroptherapy catalyst containing from 1.5 to 10.0 phosphate of aluminum and from 0.5 to 2.0 phosphate at a molar ratio of from 3 to 5 unknown and selected by the authors due to the fact that the combination in one catalyst of aluminum phosphate and iron phosphate along with Ni, Co, mo, and alumina, as shown by the authors, not only increases gidroobesserivaniya activity, but also significantly increases the activity of removal of nitrogen compounds, especially for removing basic nitrogen, which has a positive impact on the subsequent stage of Hydrotreating and thereby ensures high stability of the catalyst and increases the degree of purification of the target product, improve the techno-eco is the criteria of "significant differences".

Example 1. Raw diesel distillate (FR. 180-360oC) straight-in a mixture with diesel distillate Orenburg gas condensate has the following characteristics: a density of 860 kg/m3the sulfur 18000 ppm, a content of aromatic hydrocarbons 20% of the nitrogen content of 300 ppm. Hydroptherapy diesel distillate is carried out at a temperature of 340oC, a pressure of 4 MPa, space velocity of 3.0 HR-1the circulation of the hydrogen-containing gas 300 nm3/m3.

The molar ratio of aluminum phosphate to phosphate 3. The ratio of catalysts I and II stage 1:20. In table. 1 shows the results of the hydrotreatment on offer (example 1) and by a known method.

Example 2. As raw materials use of vacuum gasoil 350-540 oWith West-Siberian oil containing 19000 ppm sulfur, 1300 ppm of nitrogen, including 400 ppm primary, 1 g/t metals (V+Ni) and having a coking ability to 0.97 wt. Hydroperiod vacuum gasoil performed at a pressure of 5.0 MPa, a temperature of 370oC, flow rate of feed of 1.0 h-1the circulation of the hydrogen-containing gas 500 nm3/m3the catalysts taken in the ratio of 1:8 and having the following composition, wt. (see tab. 2).

The molar ratio of the Foz method (example 2). The comparison shows that in the case of application of the method with the described catalyst degree of Hydrotreating to remove sulfur and nitrogen compounds above.

Example 3. As raw materials use of vacuum gasoil 350-500oC in a mixture with oil. Used mixture has the following characteristics: sulfur content 19000 ppm nitrogen total 1350 ppm, including the main 600 ppm, cocking behavior 1,0 wt. the metal content (V+Ni) 10 g/T. Hydroperiod feedstock is carried out at a pressure of 5.0 MPa, a temperature of 380oC, flow rate of feed of 1.0 h-1and circulation of hydrogen containing gas 500 nm3/m3when the mass ratio of catalyst 1:1 and having the following composition, wt. (see tab. 3). The molar ratio of aluminum phosphate to phosphate 5. In table. 3 shows the results of the experiences described and the known methods. In case of application of the proposed method with the described system catalysts degree of desulfurization is 92,8 the degree of diazotoluene 36,2 Obtained hydrogenation product to meet demand for low-sulfur raw materials for the catalytic cracking of the residual sulfur (not more than 300 ppm), the concentration of heavy metals (not what the use of the proposed method with the known method, shows that the degree of purification increases in the case of Hydrotreating diesel fraction, especially aromatic and nitrogen compounds (it is necessary to improve the stability of diesel fuel), and the result is an environmentally friendly diesel fuel with sulfur content below 500 ppm and aromatic hydrocarbons below about 20. which corresponds to THE 38.1011348-90 in environmental diesel fuel, vacuum gas oil 350-540 oC 5.5 (example 2); and when the Hydrotreating a mixture of vacuum gas oil fuel oil (example 3) you can get a product that meets the requirements of raw material for installation type D-43-107 or CT-1. The degree of Hydrotreating and diazotoluene above. The application of this method in relation to the installation of the L-24-5 will allow you to get environmentally friendly diesel fuel and according to preliminary data, the economic effect from implementation of this invention will be about $ 500,000 per year.

The way to obtain environmentally friendly diesel fuel in two stages by means of preliminary preparation of the feedstock in the first stage at elevated temperature and pressure in the presence of a catalyst containing molybdenum trioxide, Nickel oxide or cobalt, aluminum oxide, and Hydrotreating floor is a, containing molybdenum trioxide and the oxide of Nickel or cobalt, characterized in that in the first stage using the catalyst additionally containing aluminum phosphate and iron phosphate with a molar ratio of aluminum phosphate to phosphate 3 5 in the following ratio, wt.

The molybdenum trioxide 10 15

Oxide of Nickel or cobalt 2 5

Phosphate of aluminium 1,5 10,0

Iron phosphate 0,5 2,0

Alumina Else

and the method is carried out at a mass loading of the catalysts of the first and second stages of 1:1 to 1:20.

 

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