Start of section
Production, amateur
Radio amateurs
Aircraft model, rocket-model
Useful, entertaining 		Stealth Master
Electronics
Physics
Technologies
Inventions 		Secrets of the cosmos
Secrets of the Earth
Secrets of the Ocean
Tricks
Map of section
Start
Forum
Use of the site materials is allowed subject to the link (for websites - hyperlinks)

Navigation: =>

Home / Patent catalog / Catalog section / Back /

USEFUL ADDITIVES FOR PETROL AND OTHER MOTOR FUELS
INVENTION
Patent of the Russian Federation RU2044031

A METHOD FOR OBTAINING ENVIRONMENTALLY CLEAN DIESEL FUEL

A METHOD FOR OBTAINING ENVIRONMENTALLY CLEAN DIESEL FUEL

The name of the inventor: Dvinin VA; Komarov A.N .; Fedorov AP; Usmanov RM; Prokopyuk SG; Khabibullin SG; Egorov I.V.
The name of the patent holder: Ufa Oil Refinery
Address for correspondence:
Date of commencement of the patent: 1992.10.15

Use: petrochemistry. Essence: a straight-run petroleum fraction or a mixture thereof with a fraction of catalytic cracking products boiling at 150 365 ° C., with a final 5,0 5,0,0 wt. Hydroprocessing in the first stage in the presence of a catalyst containing oxides of molybdenum, cobalt or nickel, and aluminum. In the second stage, the products of the first stage or the latter after the preliminary separation are subjected to hydroprocessing. The catalyst of the second stage contains, wt. Platinum and / or palladium 0.2 2.0, or a mixture of platinum and / or palladium and rhenium, including rhenium 0.05-0.25 wt. 0.25-2.25; Chlorine 0.1 1.5 or chlorine and fluorine 0.15 1.5; Heat-resistant carrier rest. As a carrier, a mixture of aluminosilicate with silicate module 5 35 and zeolite V with a silicate module 3 7 with a degree of exchange of hydrogen ions with metal ions of 2.0 50.0% is used, with a content of the latter being 1.0 11.0% by weight. On an alumina matrix at a weight ratio of alumina to a mixture of 30 to 70. In the first stage, a catalyst containing, Molybdenum oxide 7.0 18.0; Cobalt or nickel oxide 2.0 9.5; Alumina remaining or molybdenum oxide 8.0 16.0; Cobalt oxide 2.0 6.0; Phosphorus oxide 3.0 5.0; Iron oxide 0.01 0.05; Alumina remaining.

DESCRIPTION OF THE INVENTION

The invention relates to methods for producing environmentally friendly motor fuels with a low content of aromatic hydrocarbons and sulfur from middle distillate hydrocarbon feedstocks and can be used in refineries, gas processing and petrochemical industries.

A method is known for the production of diesel fuels with a low sulfur content (0.15-0.20% by weight) [1] by hydrotreating diesel fractions on alumi- cobalt and alumino-nickel-molybdenum catalysts at a pressure of 3.0-4.0 MPa and a temperature of 350-410 ° C .

A disadvantage of the known method is the low quality of the fuel produced (sulfur content of 0.2% by weight). In addition, for the production of environmentally friendly fuels according to the known method, a feedstock with a low aromatic hydrocarbon content is required to be hydrotreated.

The closest in terms of technical essence and achieved effect is the method of obtaining jet fuel [2] by two-stage hydroprocessing of middle distillate hydrocarbon fractions.

According to the prototype method, the first stage (hydrotreating) is carried out at a temperature of 315 ° C, a pressure of 6.3 MPa on an alumo-cobalt-molybdenum catalyst, a second stage (hydrogenation of aromatic hydrocarbons) is carried out at a temperature of 385 ° C, pressure of 6 MPa on an alumina platinum-prene catalyst.

The disadvantage of the prototype method is the impossibility of obtaining environmentally friendly diesel fuel, since the expansion of the boiling range of the raw material leads to a rapid coking of the hydrogenation catalyst. Diesel fuel produced by this method has 0.04 wt. Sulfur and 28.5 wt. Aromatic hydrocarbons.

The object of the invention is to improve the efficiency of the process by improving the quality of the diesel fuel produced.

The object of the invention is to provide a method for producing environmentally friendly diesel fuel from middle distillate hydrocarbon fractions at elevated temperature and pressure by a two-stage hydrotreatment using a first stage catalyst containing molybdenum oxide, cobalt or nickel oxide and alumina, and in the second stage, halide, metals VIII and VII groups and a heat-resistant carrier is achieved by using a straight-flow oil fraction or a mixture thereof with a fraction of a catalytic cracking product boiling in the range of 150-365 ° C., with a content of 5-50% The products of the first stage after separation or without it are sent to a second stage, which is carried out on a catalyst composition, Platinum or palladium 0.2-2.0

Or a mixture of platinum and / or palladium and rhenium 0.25-2.25

(Including rhenium 0.05-0.25% by weight) Chlorine 0.1-1.5 Or chlorine and fluorine 0.15-1.5 Heat-resistant carrier up to 100 A As a heat-resistant carrier, use a mixture of aluminosilicate with a silicate module 5-35 and zeolite V with a silicate module of 3-7 in the NRZE form with a degree of exchange of hydrogen ions for metal ions of 2-50% with a content of the latter of 1.0-11.0 wt. On an alumina matrix with an alumina / mixture ratio of 30:70, and the hydroprocessing products are subjected to fractionation with the release of environmentally friendly diesel fuel. The aim is achieved by the fact that the process is carried out at a pressure of 2.0-5.0 MPa and the temperature in the first stage is 180-420 ° C, in the second stage 250-380 ° C, the first stage is carried out on a catalyst composition, Molybdenum oxide 7.0-18.0

Cobalt or nickel oxide 2.0-9.5 Aluminum oxide up to 100 or on a catalyst additionally containing phosphorus and iron oxides at the following component ratio, Molybdenum oxide 8.0-16.0 Cobalt oxide 2.0-6.0 Phosphorus oxide 3.0-5.0 Iron oxide 0.01-0.05 Aluminum oxide up to 100

Distinctive features of the proposed process are: feedstock, process flow diagram, catalyst composition of the second stage of hydroprocessing.

In the proposed method, hydrogenolysis of sulfur-, nitrogen- and oxygen-containing compounds occurs with the formation of hydrogen sulfide, ammonia, water and light hydrocarbons in the first stage of hydroprocessing, and the hydrogenation of unsaturated hydrocarbons to form saturated hydrocarbons results in partial hydrogenation of poly- and monoaromatic hydrocarbons; In the second stage of hydroprocessing, mono- and polyaromatic hydrocarbons are subjected to hydrogenation to form naphthenic hydrocarbons. The change in the scheme of the method (possible separation of products of the first stage) makes it possible to improve the quality of the target product by deeper hydrogenation of aromatic hydrocarbons.

The process is carried out in the following way: a straight-run hydrocarbon fraction boiling in the range of 150-365 ° C, or a mixture thereof with a fraction of catalytic cracking products boiling within 150-365 ° C, with a content of 5-50% Are subjected to a two-stage hydroprocessing at a pressure of 2.0-5.0 MPa and at a temperature of 180-420 ° C in the first stage, 250-380 ° C in the second stage, a feed rate of 1.0-5.0 h -1 at the first stage Stage and multiplicity of the hydrogen-containing gas circulation 200-800 nm 3 / m 3 of raw material, in the second stage of the volumetric feed rate of 0.5-4.0 h -1 , the circulation frequency of 600-1500 nm 3 / m 3 of raw material, the products of the first stage of hydrotreatment Are sent to the second stage after preliminary separation or without it.

The first hydroprocessing step is carried out on a catalyst composition, Molybdenum oxide 70-18.0

Cobalt or nickel oxide 2.0-9.5 Aluminum oxide up to 100 or catalyst composition, wt. Molybdenum oxide 8.0-16.0 Cobalt oxide 2.0-6.0 Phosphorus oxide 3.0-5.0 Iron oxide 0.01-0.05 Aluminum oxide up to 100 The second hydroprocessing step is carried out on a catalyst composition, Platinum and / or palladium 0.2-2.0 Or a mixture of platinum and / or palladium and rhenium 0.25-2.25

(Including rhenium 0.05-0.25% by weight) Chlorine 0.1-1.5 Or chlorine and fluorine 0.15-1.5 Heat-resistant carrier up to 100 A As a heat-resistant carrier, a mixture of aluminosilicate with silicate Module 5-35 and zeolite V with a silicate module 3-7 in the NRZE form with a degree of exchange of hydrogen ions for metal ions of 2-50% with a content of the latter of 1.0-11.0% by weight. On an alumina matrix at a weight ratio of alumina to a mixture of 30:70.

The catalyst of the second hydroprocessing stage is prepared as follows: the starting industrial aluminosilicate with silicate module 5-35 in the form of a microsphere is thoroughly mixed with a predetermined amount of powdered zeolite V in an HPPE with a silicate module 3-7 and moistened with water. The resulting wet mixture of aluminosilicate and zeolite V is treated with a 0.5% solution of hydrofluoric acid or without treatment, separated from the solution, dried at a temperature of 130-150 ° C, calcined in a stream of dry air at a temperature of 470-500 ° C. On the calcined mixture Aluminosilicate and zeolite V, platinum is applied from a solution of chloroplatinic acid and / or palladium from a solution of palladium chloride in the presence of a hydrochloric acid counterpart or platinum and / or palladium and rhenium from a mixture of solutions of chloroplatinic acid, rhenic acid or ammonium perrhenate or from a mixture of solutions of palladium chloride And rhenic acid or ammonium perrhenate in the presence of hydrochloric acid. Platinum and palladium are applied separately with intermediate drying and calcination of the catalyst under the conditions indicated above. A mixture of aluminosilicate and zeolite V with the supported metals is combined with a matrix of U -alumina. To do this, 35 kg of this mixture is taken 15 kg of dry powdered aluminum hydroxide (calculated as pure alumina) and mixed thoroughly. Then, 30 dm 3 of a 6.5% solution of chemically pure nitric acid are gradually added to the powder mixture with stirring. The mixture is stirred until a plastic mass is obtained, which is then extruded on a molding machine. The crude extrudates are kneaded in the open air for 24 hours, then dried and calcined in a stream of dry air at a temperature of 500 ° C. and an air feed rate of 1000 volumes per volume of catalyst per hour. The resulting hydrogenated hydrogenate is subjected to rectification with the release of environmentally friendly diesel fuel.

Example 1 . Direct-quality hydrocarbon fraction of quality:

Fractional composition, о С:

  • N.c. 150
  • 10% 203
  • 50% 273
  • 96% 357
  • C.k. 365
  • Cetane number 46

Content, wt.

  • Sulfur 0.72
  • Aromatic hydrocarbons 28.7

Iodine number, g iodine per 100 g 1.8, is subjected to a two-stage hydrotreatment at a temperature of 330 ° C, a pressure of 4.0 MPa, a volume feed rate of 2.5 h -1 in the first stage and 2.0 h -1 in the second stage, The circulation of the hydrogen-containing gas is 400 nm 3 / m 3 of raw material in the first stage and 900 nm 3 / m 3 of raw materials in the second stage.

The first stage of hydrotreatment (see Table 1) is carried out on a catalyst composition, Molybdenum oxide 12.0 Cobalt oxide 60, Aluminum oxide up to 100 A second hydroprocessing step (see Table 2) is carried out in the presence of a catalyst composition, Platinum 1.0 Chlorine 0.8 Thermostable carrier up to 100 and a mixture of aluminosilicate with a silicate module 20, zeolite V with a silicate module 5 in an NRZE form with a degree of exchange of hydrogen ions with metal ions of 30 at a content of the last 8 wt. On a matrix of <N> gamma <N> -alumina with a mixing ratio of 70: 30 and alumina, and in the fractionation of hydrogenate, ecologically clean diesel fuel is released, the characteristic of which is given in Table. 3.

Example 2 . The straight-run hydrocarbon fraction, the quality of which is exemplified in Example 1, is mixed in a weight ratio of 95: 5 with a fraction of catalytic cracking products of quality:

Fractional composition, о С:

  • N.c. 150
  • 10% 212
  • 50%. 279
  • 96% 348
  • C.k. 365
  • Cetane number 29
  • Iodine number, g iodine per 100 g 7.4

Content, wt.

  • Sulfur 0.78
  • Aromatic hydrocarbons 81.5

And subjected to the processing of Example 1, with the difference that the process is carried out at a pressure of 5.0 MPa, a temperature of 250 ° C., a volume feed rate of 1.0 h -1 in the first stage and 0.5 h -1 in the second stage, The first step is carried out on a catalyst composition, Molybdenum oxide 18.0 Nickel oxide 9.5 Aluminum oxide up to 100 at a circulation frequency of 800 MW 3 / m 3 of raw material, and the second stage is carried out at a circulation multiplicity of 600 MW 3 / m 3 of feed in the presence of a catalyst composition, Platinum 1.0 Palladium 0.5 Chlorine 1.0 Heat-resistant carrier up to 100 and a mixture of aluminosilicate with a silicate module 35 and zeolite V with a silicate module 3 in an NRZE form with a degree of exchange of hydrogen ions for metal ions 2 with a content of The last 8 wt. On an alumina matrix with a mixture ratio of 70.30 alumina.

When fractionating the hydrogenate, ecologically clean diesel fuel is released, the characteristic of which is given in Table. 3.

Example 3 . The straight-run hydrocarbon fraction of the quality given in Example 1 is mixed in a weight ratio of 70:30 with the fraction of the catalytic cracking products of Example 2 and is hydrotreated in Example 1, with the difference that the first hydroprocessing step is carried out in the presence of a catalyst composition, Wt. Molybdenum oxide 7.0 Cobalt oxide 2.0 Aluminum oxide up to 100 at a temperature of 420 ° C, a pressure of 2.0 MPa, a volumetric feed rate of 5.0 h -1 , a circulation rate of the WSG of 800 nm 3 / m 3 of raw material, hydroprocessing products Of the first stage is subjected to a separation into a circulating hydrogen-containing gas and a liquid hydrogenate which is subjected to a second hydroprocessing step at a pressure of 2.0 MPa, a temperature of 380 ° C., a feed rate of 4.0 hr -1 , a WASH circulation rate of 1500 nm 3 / m 3 of raw material In the presence of a catalyst composition, Palladium 2.0 Chlorine 1.5 Thermostable carrier up to 100 A A mixture of aluminosilicate with a silicate module 5 and a zeolite V with a silicate module 7 in a NRZE form with a degree of exchange of hydrogen ions with metal ions of 50 at a content of the last 8 wt. On an alumina matrix with a mixture ratio of 70.30 alumina. When fractionating the hydrogenate, ecologically clean diesel fuel is released, the characteristic of which is given in Table. 3.

Example 4 . The straight-run hydrocarbon fraction of the quality given in Example 1 and the fraction of catalytic cracking products of the quality given in Example 2 are mixed in a 50:50 weight ratio and processed as in Example 1 with the difference that the first hydroprocessing step is carried out at a pressure of 5.0 MPa , A temperature of 380 ° C, a feed rate of 2.0 hr -1 , a fold width of 600 MHW 3 / m 3 of feed in the presence of a catalyst composition, Molybdenum Oxide 16.0 Cobalt Oxide 6.0 Phosphorus Oxide 5.0 Iron Oxide 0.05 Aluminum Oxide up to 100 hydroprocessing products are separated and fractionated, giving a light fraction of n-150.degree. C. and a heavy fraction of 150.degree. to. The latter is subjected to a second hydroprocessing step at a pressure of 5.0 MPa, a temperature of 330 ° C, a feed rate of 0.5 h -1 , a circulation rate of the WSG of 1200 nm 3 / m 3 of raw material on a catalyst composition, Platinum 0.2 Palladium 2.0 Rhenium 0.05 Chlorine 1.5 Heat-resistant carrier up to 100 A As a heat-resistant carrier, a mixture of aluminosilicate and zeolite V of the quality of Example 1, containing 1 wt. Of the latter, on the alumina matrix of Example 1.

At fractionation of hydrogenate, diesel fuel is ecologically clean, the characteristic of which is given in Table. 3.

Example 5 . The hydrocarbon fraction, the quality of which is exemplified in Example 1, is subjected to the processing of Example 4 with the difference that the first hydroprocessing step is carried out at a temperature of 180 ° C on a composition catalyst, Molybdenum oxide 8.0 Cobalt oxide 2.0 Phosphorus oxide 3.0 Iron oxide 0.01 Aluminum oxide up to 100 and the second stage is carried out on a catalyst composition, Platinum 0.2 Rhenium 0.2 Chlorine 0.3 Thermostable carrier up to 100 A As a heat-resistant carrier, the carrier of Example 4 is used with a mass content of 11% zeolite on the alumina matrix of Example 4.

At fractionation of hydrogenate, diesel fuel is ecologically clean, the characteristic of which is given in Table. 3.

Example 6 . The process is carried out according to Example 1 with the difference that the catalyst of the first hydroprocessing step has a composition, Molybdenum Oxide 12.0 Cobalt Oxide 4.0 Phosphorus Oxide 4.0 Iron Oxide 0.003 Aluminum Oxide up to 100 and a second hydroprocessing step is carried out on a catalyst composition, Platinum 0.2 Chlorine 0.1

A heat-resistant carrier (of the quality of Example 1) to 100 on an alumina matrix of Example 1, and in the fractionation of hydrogenate, ecologically clean diesel fuel is released, the characteristic of which is given in Table. 3.

Example 7 . The process is carried out according to Example 1 with the difference that the catalyst of the second hydroprocessing stage has a composition, Palladium 1.0 Rhenium 0.25 Chlorine 1.1 Thermostable carrier up to 100 on the alumina matrix of Example 1.

The quality of the diesel fuel produced is presented in Table. 3.

Example 8 . The process is carried out according to Example 1 with the difference that the catalyst of the second hydroprocessing stage has a composition, Platinum 0.2 Rhenium 0.05 Chlorine 0.1 Heat resistant carrier up to 100 on an alumina matrix of Example 1.

The quality of the diesel fuel produced is presented in Table. 3.

Example 9 . The process is carried out as in Example 3, with the difference that the second hydroprocessing catalyst contains 1.0% of chlorine and 0.5% of fluorine. The quality of diesel fuel is given in Table. 3.

Example 10 The process is carried out as in Example 1 with the difference that the catalyst of the second hydroprocessing stage contains 0.2% of platinum, 0.1% of chlorine and 0.05% of fluorine. The quality of diesel fuel is given in Table. 3.

Example 11 . The process is carried out as in Example 1, with the difference that the catalyst of the second stage contains 1.0% of platinum and 1.0% of chlorine and 0.1% of fluorine. The quality of diesel fuel is given in Table. 3.

Example 12 . The process is carried out as in Example 1 with the difference that the second stage catalyst contains 0.3% platinum, 1.0% palladium, 0.1% rhenium, 0.6% chlorine and 0.3% fluorine. The quality of diesel fuel is given in Table. 3.

Example 13 . The process is carried out as in Example 1 with the difference that the second stage catalyst contains 0.2% of platinum, 0.1% of rhenium, 0.2% of chlorine and 0.1% of fluorine. The quality of diesel fuel is given in Table. 3.

Example 14 . The process is carried out as in Example 1 with the difference that the second stage catalyst contains 1.0% palladium, 0.2% rhenium, 0.8% chlorine and 0.2% fluorine. The results of the experiment are given in Table. 3.

Example 15 (comparative) . The process is carried out as in Example 4, with the difference that the raw material mixture is a straight-run fraction and fractions of the catalytic cracking products in a ratio of 45:55. The results of the experiment are given in Table. 3.

Example 16 (comparative) . The process is carried out according to Example 1 with the difference that the second stage catalyst consists of a carrier with the active components of Example 1 and a matrix of alumina in a 68:32 ratio, respectively. The results of the experiment are given in Table. 3.

Example 17 (comparative) . The process is carried out according to Example 1 with the difference that pure aluminosilicate is used as the catalyst carrier of the second hydroprocessing step. The results of the experiment are given in Table. 3.

Example 18 (comparative) . The process is carried out according to Example 1, with the difference that a mixture of aluminosilicate and zeolite V in the ratio of 88:14 is used as the catalyst carrier of the second hydroprocessing step. The results of the experiment are given in Table. 3.

Example 19 (comparative) . The process is carried out according to Example 1, with the difference that the second stage catalyst has a composition, Platinum 0.05 Palladium 0.07 Rhenium 0.04 Chlorine 0.1

A heat-resistant carrier (according to example 1) to 100

The results of the experiment are given in Table. 3.

Example 20 (comparative) . The process is carried out according to Example 7 with the difference that the second stage catalyst contains 0.4% rhenium. The results of the experiment are given in Table. 3.

Example 21 (comparative) . The process is carried out as in Example 1 with the difference that the catalyst of the second hydroprocessing stage contains 1.7% of chlorine. The results are given in Table. 3.

Example 22 (comparative) . The process is carried out according to Example 6 with the difference that the catalyst of the second stage contains 0.08 wt. Chlorine. The results of the experiment are given in Table. 3.

Example 23 (comparative) . The process is carried out according to Example 6 with the difference that the catalyst of the second stage contains 0.05% chlorine and 0.03% fluorine. The results of the experiment are given in Table. 3.

Example 24 (comparative) . The process is carried out as in Example 6, with the difference that the catalyst of the second stage contains 0.15% of platinum. The results are given in Table. 3.

Example 25 (comparative) . The method is carried out according to Example 3 with the difference that the aluminosilicate has a silicate module 3 and the zeolite V silicate module 2. The results of the experiment are shown in Table. 3.

Example 26 (comparative) . The process is carried out according to Example 2 with the difference that the aluminosilicate has a silicate module 37, and the zeolite V silicate module 9. The results of the experiment are shown in Table. 3.

Example 27 (comparative) . The process is carried out as in Example 1, with the difference that the straight-run oil fraction used to produce the jet fuel is of the following quality:

Fractional composition, о С:

  • N.c. 180
  • 10% 196
  • 50% 218
  • 90% 255
  • C.k. 270

Content, wt.

  • Sulfur 0.15
  • Aromatic hydrocarbons 23.0

The results of the experiment are given in Table. 3.

Example 28 (prototype) . The raw material is the straight-run quality fraction given in Example 1. This feedstock is hydrotreated on a catalyst containing, Cobalt oxide 2.8 Molybdenum oxide 8.5 Aluminum oxide up to 100 at a temperature of 315 ° C, pressure 6.3 MPa.

The hydrogenated hydrogenate is fed to the second stage, which is carried out on a catalyst composition, Platinum 0.37 Rhenium 0.35 Chlorine 0.7 Aluminum oxide up to 100 at a temperature of 385 ° C and a pressure of 6.0 MPa. The quality of the obtained diesel fuel is given in Table. 3.

Example 29 (prototype) . The process is carried out according to Example 28 with the difference that the feed is a mixture of straight-run oil and fractions of catalytic cracking products boiling at 150-365 ° C in a weight ratio of 70 to 30. The quality of the product obtained is shown in Table 1. 3.

As examples 1 to 14 show, the proposed process makes it possible to produce environmentally friendly diesel fuels, which include fuels with low aromatic hydrocarbons and sulfur content. The proposed scheme of processing and composition of the catalyst of the second stage of hydroprocessing allow not only to improve the quality of the target diesel fuel, but also to expand the raw material base to involve up to 50% of the catalytic cracking gas oil into processing to produce environmentally friendly diesel fuel, and to increase the yield of the target product. However, the production of environmentally friendly diesel fuel with high yield and high stability of the second stage hydroprocessing catalyst is possible only in a certain range of catalyst components. For example, a decrease in the yield of the desired product is observed with an increase in the halogen content (Example 21), rhenium (Example 20) or zeolite V (Example 18). The stability of the catalyst decreases when the halogen content (examples 22, 23) or the zeolite V (Example 17) is not sufficient in the catalyst, as well as with the low silicate modulus of aluminosilicate and zeolite V (example 25) and the processing of raw materials with a gas oil content of more than 50% (Example 15 ). In addition, as shown in Examples 19, 24, with small amounts of active metals in the catalyst, the content of aromatic hydrocarbons in diesel fuel increases, and the introduction of large amounts of active components is impractical due to economic considerations. In addition, as follows from Example 16, the activity of the catalyst falls sharply as the amount of alumina forming the catalyst matrix increases, while the low limiting content of the alumina decreases the strength of the catalyst. When the content of the fraction of catalytic cracking products in the feedstock is increased, more than 50 wt. The content of aromatic hydrocarbons in the target product increases, which can not meet the requirements for environmentally friendly diesel fuel (example 15). With a high silicate module of aluminosilicate and zeolite V, the cracking activity of the second stage catalyst is observed, which leads to a decrease in the yield of the desired product (example 16). With a low silicate module of aluminosilicate and zeolite V, the stability of the catalyst of the second stage in the hydrogenation of aromatic hydrocarbons is reduced (example 25). In Example 27, a proposed process is provided that is applied to a feedstock with narrower boiling limits, commonly used to produce jet fuel. The results of the experiment showed that the jet fuel obtained by the proposed method is not inferior in quality to the fuel obtained by the prototype method. In Examples 28 and 29, experiments were carried out under the conditions and catalysts of the prototype method, but using the claimed raw materials with broader boiling limits. As can be seen from Table. 3, diesel oil from straight-run oil fraction (example 28) does not meet the requirements for diesel fuel environmentally friendly, and when using raw materials with the addition of gas oil catalytic cracking, hydrogenation of aromatic hydrocarbons in the second stage is sharply reduced.

CLAIM

1. A METHOD FOR OBTAINING ENVIRONMENTALLY CLEAN DIESEL FUEL FROM A MIDDID DILUTE HYDROGEN FACTOR by hydrotreating a first stage feedstock in the presence of a catalyst containing molybdenum oxide, cobalt or nickel oxide, aluminum oxide at elevated temperature and hydrotreatment in a second stage in the presence of a catalyst comprising halogen, metals VIII And VIIB groups, a heat-resistant carrier at an elevated temperature, characterized in that the raw material is a straight-flow oil fraction or a mixture thereof with a fraction of catalytic cracking products boiling within 150 to 365 ° C with a content of the last 5.0 to 50.0 wt. In the second hydroprocessing stage, directly the products of the first stage or the latter, after the preliminary separation, are subjected to hydrotreatment in the second stage in the presence of a catalyst containing platinum and / or palladium as the Group VIII metal as the Group VIIB metal rhenium, as halogen-chlorine or Chlorine and fluorine, as a heat-resistant carrier, a mixture of an aluminosilicate with a silicate module 5 35 and a zeolite V with a silicate module 3 7 in an NRZE form with a degree of exchange of hydrogen ions with metal ions of 2.0 50.0% with a content of the latter of 1.0 11, 0 wt. On a matrix of alumina at a weight ratio of alumina: a mixture equal to 30 to 70, with the following component ratio,

  • Platinum and / or palladium 0.2 2.0
  • A mixture of platinum and / or palladium and rhenium, including rhenium 0.05-0.25 wt. 0.25 2.25
  • Chlorine 0.1 1.5 or Chlorine and fluorine 0.15 1.5
  • Heat-resistant medium

2. A process according to claim 1, characterized in that, in the first hydroprocessing step, a catalyst is used containing,

  • Molybdenum oxide 7.0 18.0
  • Cobalt or nickel oxide 2.0 9.5
  • Aluminum oxide Other

Or a catalyst, further comprising phosphorus oxide, iron oxide, at the following component ratio,

  • Molybdenum oxide 8.0 16.0
  • Cobalt oxide 2.0 6.0
  • Phosphorus oxide 3.0 5.0
  • Iron oxide 0.001 0.05
  • Aluminum oxide Other

With the process in the first stage at a pressure of 2.0 5.0 MPa, a temperature of 180-420 ° C., in the second stage at a temperature of 250-380 ° C.

print version
Date of publication 07.04.2007gg