Method of preparing petroleum product hydrofining catalysts

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

 

The present invention relates to catalysis, in particular to methods of preparation of catalysts for Hydrotreating of petroleum products, and can be used in the refining and petrochemical industries.

A method of obtaining alumnirelations catalyst for Hydrotreating gasoline by mixing a mixture of fractions and 10-40 40-200 microns powder of aluminum oxide (the ratio of fractions of 1:0.25 to 2,33) with ammonium molybdate (heptamolybdate ammonium (GMA) - (NH4)6Mo7O24·4H2O) and Nickel nitrate (nitrate of Nickel (NN)-Ni(NO3)2·6N2O) in the presence of patinator (aqueous solution of nitric acid) with subsequent forming, the crop has wilted, drying and calcining [A.S. USSR № 701700, CL 01 J 37/02, 1979]. The main disadvantage of this method is the low mechanical strength of the resulting catalyst.

Closest to the invention on the achieved effect is a method for preparing a catalyst for Hydrotreating of petroleum products, which consists in obtaining a mixture comprising natural aluminosilicate, zatvorenii prepared mixture shuts fluid with subsequent forming, heat treatment of the obtained granules (drying and calcination), by impregnation of the support with solutions of salts of hydrogenating active metal and the final t is Moorabool. Increasing the mechanical strength of the catalyst is achieved by obtaining a high-strength carrier by mixing aluminum hydroxide with 10-30% natural aluminosilicate. The resulting carrier in two stages impregnated with solutions of the active metals: solution heptamolybdate ammonium in the first phase and solution of nitrate of cobalt or of Nickel nitrate on the second intermediate outputs and final heat treatments including drying and calcining at 200-500° C for 2-10 h [RF Patent № 2100079, CL 01 J 37/04, 37/16, 23/883 // (01 J 23/883, 101:34, 101:62), 1997]. The main disadvantage of this method is low gidroobesserivaniya and hydrogenating activity, which limits the possibility of using the catalyst in Hydrotreating processes of liquid petroleum products, for example, with a high content of unsaturated compounds (so-called secondary raw materials). Insufficient gidroobesserivaniya activity of the catalyst used in this method does not allow to obtain a motor fuel that meets the latest environmental requirements (for example, sulphur in diesel fuel less than 0.05 wt.%).

The technical problem solved by the invention is the development of the method of preparation of the catalyst in the Hydrotreating of petroleum products with high gidroobesserivaniya and hydrogenating activity.

This technical problem is solved SPO is obom the preparation of the catalyst Hydrotreating of petroleum products by two-stage impregnation of the pre-calcined carrier with a solution of heptamolybdate ammonium in the first phase and solution of nitrate of cobalt and/or nitrate Nickel on the second intermediate heat treatment between stages at a temperature of 100-200° and the final heat treatment comprising drying at a temperature of 100-200° and calcining at a temperature amounts to 400-650° C. the resulting catalyst has the following composition, wt.%:

Moo3- 3,0-25,0

COO and/or NiO - 1,0-8,0

media - the rest.

As a catalyst carrier use aluminum oxide or silicon oxide, or silicon oxide.

Common features of the invention and of the prototype is a two-step impregnation of the pre-calcined carrier with a solution of heptamolybdate ammonium in the first phase or solution of active metals on the second intermediate outputs and final heat treatments including drying and calcining.

The main distinctive feature of the present invention is that the second stage impregnation of the carrier use a solution of nitrate of cobalt and/or Nickel nitrate, intermediate heat treatment is carried out at a temperature of 100-200° and the final heat treatment comprising drying and calcining, carried out respectively at a temperature of 100-200° and amounts to 400-650° C.

Additional distinctive features are:

the composition of the obtained catalyst, wt.%:

Moo3- 3,0-25,0

COO and/or NiO - 1,0-8,0

media - rest

- use as a carrier OK the IDA aluminum, or silicon oxide, or titanium oxide.

The proposed set of features of the method of preparation of the catalyst Hydrotreating of petroleum products meets the condition of patentability "Inventive step", on the basis of the following. The prior art on the filing date for the invention was not known that the proposed set of features leads to the solution of the above tasks. In result, it becomes possible not only to obtain in the process of Hydrotreating of petroleum products from sulfur and unsaturated compounds environmentally friendly motor fuels, but also to engage in the processing of raw materials with a higher content of sulfur and unsaturated hydrocarbons.

The proposed method is illustrated by the following examples.

Example 1.

67 g of the granules pre-calcined carrier of active alumina - pour 75 ml of an aqueous solution of GMA with a concentration of 300 g of Moo3/l and incubated for the time required to obtain the intermediate product, containing 27 wt.% Moo3, is dried at a temperature of 150° C for 6 hours and Then dried semi-finished product is impregnated with 30 ml of an aqueous solution of cobalt containing 31.1 grams of cobalt nitrate (NC), dried at a temperature of 150° C for 6 h and calcined at 550° C for 4 hours

As the carrier used active aluminum oxide is I mark the AOA-1 (GOST 8136-85) with the following characteristics: diameter - 5.0 mm; mechanical tensile splitting knife 0.1 mm) - 1.1 kg/mm; bulk density of 0.55 g/cm3; pore volume (water absorption) - 0.8 cm3/year

The finished catalyst has the following composition, wt.%:

Moo3- 25,0

Soo - 8,0

Al2About3- the rest.

Example 2.

82 g of the granules of the carrier - active aluminum oxide is impregnated with 50 ml of an aqueous solution GMA containing 17,2 g GMA, and dried at a temperature of 150° C for 6 hours and Then dried semi-finished product is impregnated with 30 ml of an aqueous solution of cobalt containing 15.6 g NK, dried at a temperature of 150° C for 6 h and calcined at 550° C for 4 hours

As the carrier used active alumina mark an-2/S (TU 2163-004-47317879-2000 with am.1) with the following characteristics: diameter 2.0 mm; mechanical tensile splitting knife 0.1 mm) - 1.5 kg/mm; bulk density - 0.65 g/cm3; pore volume (water absorption) - 0,61 cm3/year

The finished catalyst has the following composition, wt.%:

Moo3- 14,0

Soo - 4,0

Al2About3- the rest.

Analogously to example 1, varying the composition of the active components, the obtained catalysts according to examples 4 and 7, and similarly to example 2, varying the composition of the active components and the nature of the medium, the obtained catalysts according to examples 3, 5, 6, 8-11.

Example 12 (prototype).

To 500 g of the powder of aluminum hydroxide was added 100 g nature is underwater aluminosilicate and mixed in a mixing machine for 5-10 min until a homogeneous mixture, then poured 180 ml of 10% phosphoric acid and stirred for 1 h the resulting mass ekstragiruyut through a die plate with a hole diameter of 2 mm Obtained granules are dried first at a temperature of 180° and then calcined at 550° within 24 hours Calcined granules pour a 17.5% solution of GMA (based on 1.5 volume of solution to 1 volume of medium) and incubated in the solution for 4 hours and Then the excess solution is drained, and the impregnated granules are dried and calcined at a temperature of 500° With over 3 hours

After cooling, the pellets are placed in a solution of nitrate of cobalt concentration of 10% , and the rate of 1.5 volume of solution to 1 volume of the pellet and incubated in the solution for 3 hours Then carry out the drying and calcination at 500° C for 3 hours

The finished catalyst has the following composition, wt.%:

Moo3- 14,0

Soo - 4,0

Al2About3- SiO2- the rest.

Example 13 (prototype).

To 500 g of the powder of aluminum hydroxide was added 100 g of natural silicate and mixed in a mixing machine for 5-10 min until a homogeneous mixture, then poured 180 ml of 10% phosphoric acid and stirred for 1 h the resulting mass ekstragiruyut through a die plate with a hole diameter of 2 mm Obtained granules are dried first at a temperature of 180° and then calcined pri° C for 24 h Calcined granules pour a 17.5% solution of GMA (based on 1.5 volume of solution to 1 volume of medium) and incubated in the solution for 4 hours and Then the excess solution is drained, and the impregnated granules are dried and calcined at a temperature of 300° C for 3 hours

After cooling, the pellets are placed in a solution of Nickel nitrate concentration of 10%, and the rate of 1.5 volume of solution to 1 volume of the pellet and incubated in the solution for 3 hours Then carry out the drying and calcination at 500° C for 3 hours

The finished catalyst has the following composition, wt.%:

Moo3- 14,0

NiO - 4,0

Al2O3-SiO2- the rest.

The composition obtained in examples 1-13 catalysts and characterization of their conditions of heat treatment are given in table. 1

Table 1

The composition and characteristics of the conditions of the heat treatment of the catalysts
SampleComposition, wt%MediaTemperature, °
 Moo3SooNiO intermediate heat treatmentthe final heat treatment
       dryingcalcination
Example 125,08,0-Al2About3150150550
Example 214,04,0-Al2About3150150550
Example 33,01,0-Al2About3150150550
Example 425,0-8,0Al2About3100100400
Example 514,0-4,0Al2O3100100400
Example 63,0-1,0Al2About3100100400
Example 725,04,04,0Al2About3200200500
Example 814,02,02,0Al2O3200200 600
Example 93,00,50,5Al2About3200200650
Example 1014,0-4.0SiO2200200500
Example 1114,04,0-Tio2200200600
Example 12 (prototype)14,04,0-Al2About3-SiO2500200500
Example 13 (prototype)14,0-4,0Al2About3-SiO2300200500

Prepared according to the proposed method, the catalysts according to examples 2, 5, 8 and catalysts according to the prior art (examples 12 and 13) were tested in the Hydrotreating process mixture model (toluene - 80,0% , hexene-1 - 19,0% and thiophene - 1,0%) at a temperature of 350° C, pressure of 2.0 MPa, the space velocity of the raw material 3,0 h-1and the ratio of N2raw 300 nm3/m3. The important point Hydrotreating of this mixture is to maximize the removal of sulfur (thiophene) and olefins (hexene) with minimal hydrogenation of toluene is. Gidroobesserivaniya activity of the catalysts was determined by the content in the hydrogenation product of thiophene (column 6), and hydrogenating activity was determined by the decrease in the hydrogenation product mass fraction of hexene (graph 1).

The results of catalytic tests (for 20 h) are shown in table 2.

Table 2
CatalystMass fraction of the component section of hydrogenated feed, %
 hexenehexanetoluenecyclohexanethiophene
123465
Example 20,118,9791,0650,0020
Example 50,0518,9578,51,5980,0030
Example 80,0518,9579,5of 0.5330,0010
Example 100,0918,9179,80,2130,0045
Example 110,0718,9379,70,3200,0040
Example 12 (prototype)0,15 18,8579,60,4260,0055
Example 13 (prototype)0,1218,8879.80,2130,0060

As can be seen from table 2, the catalysts of the proposed method (examples 2, 5, 8, 10 and 11) gidroobesserivaniya and hydrogenating activities exceed the catalysts according to the prior art (examples 12 and 13). You should pay attention to the fact that the catalyst according to example 8, containing 2.0% COO and 2.0% NiO, shows the greatest activity in the removal of thiophene and in the hydrogenation of hexene at least the hydrogenation of toluene.

The catalysts of examples 1, 2 and 13 (prototype), as well as industrial catalysts ST-70 and ST-86 were tested at pilot plant in the Hydrotreating process of straight-run diesel fraction: fraction of 180-360° s; density - 842 kg/m3; the sulfur content is 1.0% . The process conditions: temperature of 340 and 360° C; pressure of 20 ATM.; the volumetric feed rate to 4 h-1; the ratio of N2:raw - 500 nm3/m3. Gidroobesserivaniya activity of the catalysts was determined by the decrease in the hydrogenation product mass fraction of sulfur (columns 2 and 3) and was calculated as the degree of conversion (columns 4 and 5) according to the formula:

K(%)=(Cwith-Cp)· 100/Swith,

where Cwithand Cpthe sulphur content in raw materials and products is the (hydrogenation product), % , respectively.

The results of catalytic tests (72 h) are shown in table 3.



Table 3
CatalystMass fraction of sulfur in the hydrogenation product, %The degree of conversion %
 340°360°340°360°
12345
Example 10,0650,03493.596,1
Example 20,0700,04093,095,5
Example 13 (prototype)0,1470,07985,3to 92.1
TH-700,1650,085to 83.591,5
TH-860,1450,08085,592,0

As can be seen from table 3, the catalysts of the proposed method on gidroobesserivaniya and hydrogenating activities surpass the catalyst according to the prior art (example 13) and industrial catalysts ST-70 and ST-86.

The catalysts according to examples 2, 3, 5, 6, 8, 9, 12 (the prototype) and 13 (prototype) were tested in the pilot is the situation in the Hydrotreating process, the benzene-toluene-xylene fraction of the pyrolysis condensate fraction: the content of styrene and sulfur, respectively, 1,3 and 0.06% . Conditions of catalytic tests: t - 230 and 270° S; R - 5.0 MPa; v 2 h-1; N2:raw - 1000 nm3/m3. The duration of the test catalyst at a temperature of the run was 24 hours

The results of catalytic tests are shown in table 4.



Table 4
CatalystMass fraction of sulfur in the hydrogenation product, %Mass fraction of styrene in the hydrogenation product, %
 230°270°230°270°
12345
Example 20,00250,00200,10,1
Example 30,00300,00250,20,1
Example 50,00200,00150,10,1
Example 60,0250,00180,20,1
Example 80,00150,00100,10,1
Example 90,00270,00120,20,1
Example 11,0026 0,00110,10,1
Example 12 (prototype)0,00350,00250.30,2
Example 13 (prototype)0,00400,00300,30,2

As can be seen from table 4, the catalysts of the proposed method on gidroobesserivaniya (columns 2 and 3) and hydrogenating (columns 4 and 5) activities exceed the catalysts according to the prior art (examples 12 and 13).

1. The preparation method of catalyst for Hydrotreating of petroleum products by two-stage impregnation of the pre-calcined carrier with a solution of heptamolybdate ammonium in the first phase or solution of active metals on the second intermediate outputs and final heat treatments including drying and calcination, wherein the second stage impregnation of the carrier use a solution of nitrate of cobalt and/or Nickel nitrate and intermediate heat treatment is carried out at a temperature of 100-200°and the final heat treatment comprising drying and calcining, carried out respectively at a temperature of 100-200°and amounts to 400-650°C.

2. The method according to claim 1, characterized in that the catalyst has the following composition, wt.%:

Moo33,0-25,0

COO and/or NiO 1,0-8,0

The media and the Rest

3. The method according to claim 1, characterized in that as wear the El uses aluminum oxide, or silicon oxide, or titanium oxide.



 

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