Method of production of diesel fuel with improved ecological performances

FIELD: petroleum refining industry.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.

EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 ex

 

The invention relates to the refining, in particular to methods for environmentally friendly diesel fuels.

A method of obtaining environmentally friendly diesel fuel with a sulfur content of not more than 500 ppm, in accordance with which the diesel fraction is subjected to Hydrotreating using a catalytic system consisting of alumnirelations catalyst activated with ethyl mercaptan, and aluminoborosilicate catalyst, activated elemental sulfur (U.S. Pat. RF 2103324, from 27.01.98).

Also known is a method of obtaining low-sulfur diesel by Hydrotreating at elevated temperature and pressure in the presence of catalysts, pre-activated in the environment of the hydrogen-containing gas to elemental sulfur or a raw material at a temperature of 350-400°C, characterized in that to increase the depth of hydrofining in the package catalysts is from about 1 to 0.1. share aluminoborosilicate catalyst ST-70 and/or TH-86, provided that the activation package is elemental sulfur, taken in an amount of not more than 30% wt. the total weight of the catalytic package, or distillate oil fraction with a sulfur content of S(C+N)/S, where S is the sulfur content in the feedstock Hydrotreating, wt. Percent; - the share of catalysts ST-70 and/or TH-86 in the catalytic package; H - share and Montelibano catalyst in the catalytic package (U.S. Pat. RF 2074877, from 10.03.97).

The closest way to the same destination to the claimed invention on the totality of symptoms is the way to obtain low-sulfur diesel fuels by Hydrotreating diesel fractions, characterized in that use package catalysts containing 30-80% by weight. aluminoborosilicate catalyst in the upper part of the reactor and 20-70% wt. alumnirelations catalyst at the bottom in the direction of the raw material layer, provided that the activation of the catalysts is carried dimethyl disulfide, taken in the amount of [0,2-K/(K+N)] kg per 1 kg of the catalyst system, where the content aluminoborosilicate catalyst package (kg), N - content alumnirelations catalyst package (kg), followed by goosemeyer catalytic composition of the raw material at a temperature of 330 to 340° (U.S. Pat. RF 2140963, 10.11.99).

The proposed invention the problem of obtaining environmentally friendly diesel fuels is solved by improving the composition of the catalytic system and method of making the member catalysts without taking into account the integrated nature of the technology for production of clean fuels from raw materials containing biodegradable sulfur compounds. For this reason, the known methods do not allow to obtain diesel fuel with sulfur content less than 350 ppm of a mixture of direct the Noah fractions and distillates secondary origin, containing up to 1.3 wt.%. sulfur at low temperatures and long meregenerasikan cycle.

The conditions for achieving the above technical result, that is, to produce low-sulfur product from raw materials containing stable dibenzothiophene patterns are not only in achieving high catalytic activity, but also to ensure optimal contact conditions of each catalyst pellet with Gutseriev mixture, creating the conditions for minimum drag gatserelia thread, how activation of the catalyst and install on the operating mode.

The OBJECTIVE of the INVENTION is the obtaining of diesel fuel with sulfur content less than 350 ppm of raw materials, in addition to containing straight-run fractions, distillates coking and catalytic cracking.

This object is achieved as follows. In the hydrotreater unit load method the dense packing of successively from bottom to top:

- layer Co-Mo/Al2About3catalyst with a diameter of 4.5-5.0 mm, and the height of the layer is 0,06-0,12 internal diameter of the reactor,

- main layer Co-Mo/Al2About3catalyst with a diameter of 2.0-2.8 mm, a specific surface area of 250-290 m2/g, pore volume of 0.45-0.6 cm3/g, in which not less than 80% parametricheskogo volume formed through the internal pores mainly Zilin the historical shape with a diameter of 4.0-14,0 nm,

- layer Co-Mo/Al2About3catalyst pre-treatment of raw materials with a diameter of 4.5-5.0 mm, and the height of the layer is 0,06-0,12 internal diameter of the reactor,

- protective layer broad porous low-Ni-Mo/Al2About3catalyst molded in the form of a hollow cylinder, and the height of the layer is 0.12 to 0.25 internal diameter of the reactor.

The movement of raw materials is carried out from top to bottom.

In the upper part of the reactor is mounted switchgear to ensure thorough mixing of the gas and liquid phases and uniform distribution Gutseriev mixture over the cross section of the reactor.

The loaded catalyst activate straight-run diesel fraction in two stages with the addition of easily degradable organic compounds. Dosing sulfur-containing compounds and temperature rise in the reactor are based on the gradual increase of the concentration of hydrogen sulfide in the reactor exit from 1000 to 3000 ppm in the temperature range 180-240°to 15000-20000 ppm in the temperature range 240-320°C. At a temperature of 320°and hydrogen sulfide concentration at the reactor exit 15000-20000 ppm make the shutter speed (without changing the temperature within 2-4 hours.

After activation of the catalyst duty cycle begin on virgin raw materials at low temperature, raising her no more than n is 1-3° S/day to achieve the desired residual content of sulfur, stabilize temperature and gradually add the raw material of secondary origin.

The Hydrotreating a mixture of straight-run fraction of diesel fuel and distillate coking and catalytic cracking is carried out at a temperature of 330-370°C, partial pressure of hydrogen in the reaction zone of at least 2.4 MPa, the space velocity of the raw material is not more than 2.5 h-1.

DISTINCTIVE features of the proposed method are:

dense packing of the catalyst layers with a gradual increase in activity and minimal resistance gatserelia stream,

- optimal porous structure of the basic catalyst is not less than 80% parametricheskogo volume formed through the internal pores predominantly cylindrical shape with a diameter of 4.0-14,0 nm,

- application of a protective layer broad porous low-Ni-Mo/Al2About3catalyst molded in the form of a hollow cylinder,

- activation of the catalyst of straight-run diesel fraction in two stages with the addition of easily degradable sulfur compounds

- start installation on virgin raw materials at low temperature process with a subsequent rise of temperature by 1-3°s/day to achieve the desired residual content of sulfur and gradual addition of Aria secondary origin.

The TECHNICAL RESULT of the proposed invention is the obtaining of a diesel fuel with sulfur content less than 350 ppm of a mixture of straight-run fractions and distillates secondary origin containing up to 1.3 wt.%. sulfur, low stiffness of the process and long meregenerasikan cycle.

Methods of obtaining environmentally friendly diesel fuel with the use of complex technologies is unknown. Thus, this solution meets the criteria of “NOVELTY” and “INVENTIVE step”.

EXAMPLES of EXECUTION of the INVENTION

Example 1 (prototype). The hydrotreatment was subjected to a mixture of straight-run diesel fraction 180-360° (79,9%), oil coking (8.7%) and catalytic cracking (11,4%)containing 1.3% by weight. sulfur, in the presence of catalytic package consisting of 50% aluminoborosilicate catalyst (lower layer) and 50% alumnirelations catalyst (upper layer). The catalyst was activated straight-run diesel fraction with the addition of dimethyl disulfide.

The Hydrotreating of this material in the presence of the activated catalyst package was carried out at temperatures 320-380°C, partial pressure of hydrogen in the reaction zone of 2.4 MPa, the space velocity of the raw materials 2.5 hours-1.

Indicators Hydrotreating process according to the method specified in the prototype,are presented in table 1.

Table 1
IndicatorsTemperature, °
320330340350360370
The output section of hydrogenated feed, wt. -%97,096,896.696,396,095,7
The sulfur content in the hydrogenation product, ppm1061842694564425345

Example 2. In accordance with the invention in industrial Hydrotreating reactor with a diameter of 2.6 m by the method of the dense packing of loaded sequentially from bottom to top:

the layer height of 0.25 m-Mo/Al2About3catalyst with a diameter of 5.0 mm,

- main layer Co-Mo/Al2About3catalyst with a diameter of 2.5 mm, a specific surface area of 250 m2/g, pore volume of 0.45 cm3/g, in which 80% parametricheskogo volume formed through the internal pores predominantly cylindrical shape with a diameter of 4.0-14,0 nm,

the layer height of 0.25 m-Mo/Al2About3catalyst with a diameter of 5.0 mm,

- protective layer with a height of 0.5 m broad porous low-Ni-Mo/Al2About3catalyst, form the bath in the form of a hollow cylinder.

The movement of raw materials is carried out from top to bottom.

In the upper part of the reactor was mounted switchgear.

The catalyst was dried in a stream of hydrogen-containing gas at a temperature of 150°C. When a temperature of 160°C for two hours gave straight-run diesel fraction 180-360°With, then conducted the first stage of sulfatirovnie. When the temperature of 180-240°they dosaged With dimethyl disulfide to hydrogen sulfide concentration at the outlet of the reactor 1000 ppm. The second stage of sulfatirovnie conducted at temperatures 240-320°With the amount of dimethyl disulfide regulated, maintaining the concentration of hydrogen sulfide in the reactor exit 15000-20000 ppm, and then at a temperature of 320°did the shutter speed (without changing temperature) for 2 hours.

After activation of the catalyst was served straight-run diesel fraction 180-360°when the temperature in the reactor 315°With a subsequent rise of temperature on 3°in the day. At a temperature of 330°received hydrogenation product with a sulfur content of 315 ppm and then gradually added light oil coking (up 8.7%) and catalytic cracking (up to 11.4%), containing up to 1.3 wt.%. sulfur. The process is conducted in the temperature range of 330-370°With, at a partial pressure of hydrogen in the reaction zone of 2.4 MPa and space velocity of the raw materials 2.5 hours-1. The process indicators are shown in table 2.

Table 2
IndicatorsTemperature, °
320330340350360370
The output section of hydrogenated feed, wt. -%97,597,3to 97.196,996,796,5
The sulfur content in the hydrogenation product, ppm525342308275251230

Table 2 shows that, compared with the prototype application of the proposed method to obtain environmentally friendly diesel fuel with sulfur content less than 350 ppm at a relatively low temperature of the Hydrotreating process.

Thus, the proposed method is environmentally friendly diesel fuel meets the criterion of “INDUSTRIAL APPLICABILITY”.

1. The method of obtaining diesel fuel with improved environmental characteristics, including Hydrotreating a mixture of straight-run diesel fractions and raw materials secondary origin in the presence of layers of catalysts, characterized in that the mixture of straight-run diesel fraction distillates coking and catalytic cracking are subjected guide is outisde in the presence of layers of catalysts, which download method, the dense packing of sequentially: layer Co-Mo/Al2About3catalyst with a diameter of 4.5-5.0 mm, and the height of the layer is 0,06-0,1 inner diameter of the reactor; the core layer Co-Mo/Al2About3catalyst with a diameter of 2.0-2.8 mm, a specific surface area of 250-290 m2/g, pore volume of 0.45-0.6 cm3/g, in which not less than 80% parametricheskogo volume formed through the internal pores predominantly cylindrical shape with a diameter of 4.0-14,0 nm; a layer of Co-Mo/Al2About3catalyst pre-treatment of raw materials with a diameter of 4.5-5.0 mm, and the height of the layer is 0,06-0,1 inner diameter of the reactor; a protective layer broad porous low-Ni-Mo/Al2O3catalyst molded in the form of a hollow cylinder, and the height of the layer is 0.12 to 0.25 internal diameter of the reactor.

2. The method according to claim 1, characterized in that the layers of catalysts arranged with a gradual increase in activity and minimal resistance gatserelia stream.

3. The method according to claim 1, characterized in that the upper part of the reactor is mounted switchgear designed for thorough mixing of the gas and liquid phases and uniform distribution of the mixture over the cross section of the reactor.

4. The method according to claim 3, characterized in that the change softwarepersonal phase at any point on the diameter of the reactor is not more than 2%.

5. The method according to claim 1, characterized in that the activation of the catalyst is carried out straight-run diesel fraction in two stages with the addition of easily degradable organic sulfur-containing compounds.

6. The method according to claim 5, characterized in that the dosing of sulfur-containing compounds and temperature rise in the reactor are based on the conditions of gradual increase of the concentration of hydrogen sulfide in the reactor exit to 1000-3000 ppm in the temperature range 180-240°and to 15000-20000 ppm in the temperature range 240-320°C.

7. The method according to claim 5, characterized in that at a temperature of 320°and hydrogen sulfide concentration at the reactor exit 15000-20000 ppm doing exposure for 2-4 hours



 

Same patents:

The invention relates to oil fuel for gas turbines and more specifically to a method of obtaining fuel oil for gas turbines used for power generation gas turbine, to generate electricity using fuel oil for gas turbines and oil fuel for gas turbines

The invention relates to the refining, in particular to methods of Hydrotreating petroleum fractions

The invention relates to the field of oil refining, particularly to a method of Hydrotreating the oil distillers

The invention relates to methods of producing low-sulfur diesel by Hydrotreating of the feedstock and can be used in the refining industry

The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.

EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.

3 cl, 4 tbl, 13 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

The invention relates to the refining and can be used when cleaning the cracking of gasoline from sulfur and unsaturated compounds

The invention relates to catalysts containing on the surface of the carrier compounds of molybdenum and/or tungsten, with or without additives compounds of one or more transition metals, processes for their preparation and may find wide application in the processes of hydroperiod hydrocarbons of petroleum or coal origin
The invention relates to the refining industry, specifically to a method for diesel fuel

The invention relates to the refining and petrochemical industries, in particular to catalysts for Hydrotreating of petroleum distillates

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

Up!