A catalyst for hydrotreating petroleum fractions and method thereof

 

(57) Abstract:

A catalyst for Hydrotreating petroleum fractions, comprising the oxides of cobalt and/or Nickel, molybdenum trioxide, native oxide of aluminum, silicon, the carrier further comprises at least one of modifying a combination of metals selected from the group: sodium, iron, lanthanum, cerium, zinc, copper, tungsten, and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, and the catalyst has the following composition, wt.%: NiO and/or COO 1-5 Moo38-15, the medium comprising: SiO20.01 to 50, modifying the connection metals from 0.01 to 5 and/or the connection of nonmetals 0.5 to 10, alumina rest. The precursor of aluminium oxide is x-ray amorphous layered compound of aluminium of the formula Al2O3nH2Oh, where n= 0.3 to 1.5. Proposed also a method of producing catalyst for Hydrotreating petroleum fractions, comprising forming by extrusion of aluminum hydroxide containing the modifying compound, drying, calcination, impregnation with a solution of compounds active components of Nickel and/or cobalt, molybdenum, followed by drying and calcining, as aluminum hydroxide use the product rehydration rentention or in the full amount of the modifier metal compounds, selected from the group of sodium, iron, lanthanum, cerium, zinc, copper, tungsten, in an amount of 0.01-5 wt.%, and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, in the amount of 0.5-10 wt. %. The proposed catalyst in contrast to the known has high activity and high mechanical strength. 2 S. p. f-crystals, 2 ill., table 2.

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

Known methods of preparation of the catalyst, based on the aluminosilicate obtained by mixing aluminum hydroxide with a compound of silicon, followed by impregnation of the obtained modified oxide or aluminum hydroxide aqueous solutions of ammonium molybdate and Nickel nitrate or cobalt, drying, and calcination, as the silicon compound used gidroksilirovanii silica with a diameter of micelles and a specific surface area of 150-400 m2/g (and. C. the USSR 825135, IPC B 01 J 23/88; B 01 J 37/02, 1981).

The disadvantage of the catalyst is not sufficiently high strength of the catalyst.

Known Hydrotreating catalyst (U.S. patent 4255282, IPC B 01 J 27/14; 10 45/04, 1981), which contains the l, pre-calcined at a temperature of 745oWith, mixed with the above components and re-calcined.

However, the catalyst has a low level.

A method of obtaining catalysts for Hydrotreating of hydrogels (application EPO 0309045, IPC B 01 J 27/188, With 10 G 45/08, 1989), in which to obtain high catalytic activity of catalysts for Hydrotreating in a substrate of phosphated (optional) hydrogel of alumina is injected element, such as Nickel and/or cobalt and a heavy metal, such as molybdenum and/or tungsten, together with a stabilizing amount of phosphorus. Obtained after calcining the catalyst has a specific surface area of not less than 300 m2/year of the total volume of pores of not less than 20% of the pores of diameter greater than 35 nm and less than 20% for pores with a diameter of less than 7 nm.

The disadvantage of the catalyst is its lack of activity.

Known catalyst for Hydrotreating of crude oil supplies. St. 1657226, IPC B 01 J 23/88, 37/02), which consists wt.%: Moo310-16, Nickel oxide 3-6, tin oxide 0,2-0,6, fluorine 0,2-0,6, aluminum oxide, up to 100%. In this case, the catalyst provides increased hydrogenating and tx2">

Famous new catalyst for Hydrotreating petroleum fractions (RF patent 2147256, IPC B 01 J 23/883, 37/04, 2000), containing oxides of molybdenum, Nickel and/or cobalt and aluminum, molded in the form of hollow cylindrical granules with a certain ratio of the outer diameter to the inner diameter. The catalyst additionally contains silicon oxide in the following ratio, wt.%:

Molybdenum oxide - 4-8

Oxide of Nickel and/or cobalt - 1-3

The silicon oxide - 4-18

Alumina - Rest

The catalyst has a ratio of the outer diameter to the inner diameter of 2.7 to 6.0.

The catalyst has high strength, however, is not a high activity of the catalyst in the Hydrotreating process.

The closest technical solution is the catalyst for hydrofining petroleum fractions (RF patent 2142337, IPC B 01 J 23/88, 37/02, 1999), which contains Nickel oxide, molybdenum oxide, tungsten oxide, silicon oxide, aluminium oxide, the catalyst has the following ratio of components, wt.%:

Nickel oxide - 4,0-6,0

Molybdenum oxide - 6,0-8,0

Tungsten - 6,0-8,0

The silicon oxide - 4,6-14,0

Alumina - Rest

The catalyst was prepared by academiana, drying, calcination and impregnation of the active components. As modifying additives used aluminosilicate, containing 5-15 wt. % zeolite type Y.

The disadvantage of the catalyst is not sufficiently high activity.

The problem solved by the invention is the obtaining of a Hydrotreating catalyst with high mechanical strength and high activity in reactions hydrodesulphurization unit petroleum distillates and designing method thereof.

The problem is solved at the expense of catalyst for Hydrotreating petroleum fractions which comprises the oxides of cobalt and/or Nickel, molybdenum trioxide, native oxide of aluminum, silicon. The precursor of aluminium oxide is x-ray amorphous layered compound of aluminium of the formula Al2O3nH2O, where n= 0.3 to 1.5, and the carrier further comprises at least one of modifying a combination of metals selected from the group: sodium, iron, lanthanum, cerium, zinc, copper, tungsten, and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, and the catalyst has the following composition, wt.%:

NiO and/or COO - 1-5

Moo3- 8-15

The media, the Association of non-metals - 0,5-10

Alumina - Rest

For the preparation of the catalyst used x-ray amorphous layered compound of aluminium of the formula Al2ABOUT3mo2O, where n=0.3 to 1.5, obtained by any known method, for example by rapid dehydration of the three-hydrate of aluminum, are described in patents 2064435, 2148017.

Under the aluminum oxide x-ray amorphous structure is a aluminum oxide, which radiographic analysis does not detect any lines, characteristic of any crystalline phase.

In Fig.1 and 2 show pictures of the particles of compound Al2ABOUT3mo2O, where n= 0.3 to 1.5, at different magnification. In Fig.1 increased 600 times, and Fig. 2 - 2000 times. In Fig.1 and 2 is visible layered nature of the structure of compound Al2ABOUT3mo2O, where n=0.3 to 1.5. This compound has high reactivity, which becomes possible intercalation compounds - catalyst components in the interlayer space between alyumogidroksidnykh packages.

This connection may contain additional modifying compounds from the group of Na, Fe, La, CE, Zn, Cu, W in an amount of 0.01-5 wt. % and/or compounds of non-metals is similar to that of aluminum hydroxide before rapid dehydration by any known means: impregnation, mixing, or after it.

To obtain catalyst for Hydrotreating x-ray amorphous layered compound of aluminium of the formula Al2ABOUT3mo2O, where n=0,3-1,5 podvergaut rehydrated by adding water to a pasty mass.

When the heat treatment of the granules of the catalyst on the basis of such a hydrated aluminum compounds containing the modifying metal connection and the connection of the nonmetal, is the formation of the catalyst on the modified surface of the carrier that provides the formation of a strong connection of the carrier with active component and the formation of active centers in order to increase the flow of the process of hydrogenation and desulfurization at lower process temperatures than known catalysts.

This set of tools task allows you to get a positive effect, which is to obtain high activity and durability of the catalyst, long life.

The problem is solved by the method of producing catalyst for Hydrotreating petroleum fractions which comprises forming by extrusion of silicon oxide, aluminum hydroxide, steriade is whether cobalt, molybdenum, followed by drying and calcining. As aluminum hydroxide use the product rehydration x-ray amorphous layered aluminum compounds of the formula Al2O3mo2O, where n=0.3 to 1.5, which contains the full or partial amount of the modifier metal compounds selected from the group: sodium, iron, lanthanum, cerium, zinc, copper, tungsten and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, and the catalyst has the following composition, wt.%:

NiO and/or COO - 1-5

Moo3- 8-15

The media, which included:

SiO2of 0.01-50

modifying the connection metal is 0.01-5

and/or

the connection of the non - 0,5-10

Alumina - Rest

The method of producing catalyst for Hydrotreating petroleum fractions is as follows.

Take the product obtained by the rapid dehydration of the three-hydrate of aluminum, rehydrating it, add concentrated nitric acid, silicon dioxide, water and the required amount of the modifier metal compounds and compounds of non-metals. Connection of reactive metals can be made to the media in full of the required number or in part, in granules. Then air-dried for 6 hours, then at 110oWith 4 hours, 700oWith 6 hours. Next, the resulting carrier impregnated on capacity sequentially solutions paramolybdate ammonium and nitrate solution of cobalt (or Nickel), dried at a temperature of 110oC, calcined at a temperature of 500oC for 6 h.

Composition and physico-chemical properties of the obtained catalyst is determined as follows:

- the Co, Mo and others - x-ray fluorescence method;

the distribution of the pore radii method mercury porometry on paramere 2000 company "Carlo Erba (Italy);

the crushing strength is determined on the instrument MP-9C;

- test activity performed during the testing of the catalyst in the mode of deep Hydrotreating at a fraction of the catalyst is 0.5-1.0 mm in 20 cm3, the hydrogen pressure of 40 ATM, flow rate of the raw material - 4 h-1the ratio of circulation of hydrogen containing gas to the raw material 500 ml /g of raw material.

The phase composition of the obtained aluminum compounds were determined using x-ray diffractometer DRON MIND 1 in Cu-K-monochromatic radiation with the use of differential discrimination and monochromator.

Example 1

Take obtained by rapid dehydration of the three-hydrate aluminum product formula Al2O30,75 H2O having a layered x-ray amorphous structure and containing Fe2O30.1 wt.% and Na2O 0.3 wt.%, rehydration it by adding water to obtain a pasty mass, add SiO2in the amount of 3 wt.% and HNO3mix in the mixer 20-30 minutes before getting plastic capable of molded pulp, molded by extrusion into pellets. Then air-dried for 6 h, then at 110oWith 4 hours at 700oWith 6 hours.

Next, take 100 g obtained in the media containing Na2O 0.3 wt.%; Fe2O30.1 wt.%; SiO23 wt.%, impregnate on capacity 18,65 g paramolybdate ammonium, dissolved in 50 ml of N2O.

Next, the resulting sample is impregnated with a solution of nitrate of cobalt (18.6 g of Co(NO3)26N2O in 50 ml of N2O).

The sample is dried at a temperature of 110oC, calcined at 500oC for 6 h.

Example 2

The catalyst is prepared analogously to example 1, and the catalyst has the following composition, wt.%: La2ABOUT30,01;2O31,0; SiO210; NiO 1,0; NGO315,0. Connection lanter 3

The catalyst is prepared analogously to example 1, and the catalyst has the following composition, wt. %: Ce2ABOUT30,1; ZnO 0,8; F2O30,5; SiO220; Soo 3,5; NGO314,0. The connection of zinc deposited by impregnation.

Example 4

The catalyst is prepared analogously to example 1, and the catalyst has the following composition, wt.%: CuO 0,5; SiO25; NiO 5,0; NGO38,0, only the connection of Nickel introduced into the catalyst by mixing the layered x-ray amorphous aluminum compounds with silicon oxide and Nickel nitrate.

Example 5

The catalyst is prepared analogously to example 1, and the catalyst has the following composition, wt.%: WO35; Soo 3,2; NGO314; P2ABOUT51; SiO23.

Example 6

Similar to example 1, and the catalyst has the following composition, wt.%: WO30,8; CuO 0,8; SiO250; NiO 2,0; Soo 2,0; NGO312, 0MM;2ABOUT30,1, only layered x-ray amorphous compound of aluminum contained 0.02 wt.% CuO, and the rest of the number entered by the impregnation of a salt of copper.

Example 7

Similar to example 1, and the catalyst has the following composition, wt.%: Na20.5; Ce2ABOUT30,3; P2O510,0; SiO25; NiO 4,0; Soo 1,0; NGO315,0, characterized in that the connection P2O1, and the catalyst has the following composition, wt.%: Fe2ABOUT30,1; ZnO 0,5; SiO20,01; NiO 3,2; MoO 10,0.

Example 9 (prototype)

500 g of precipitated aluminum hydroxide with a moisture content of 78 wt.% peptizer under continuous stirring by the addition of 1.9 ml of 56% nitric acid to pH 5, then enter 11,7 g paramolybdate ammonium, mix, add to 12.3 ml cremaboldrini acid with a concentration of 890 g/l (the content of WO3in cremaboldrini acid is wt.% 85), mix, then add to 25.8 g fraction of 0.02-0.1 mm calcined aluminosilicate with a moisture content of 10 wt.%, containing 5 wt.% type zeolite and 95 wt.% amorphous aluminosilicate.

Completely dry the aluminosilicate has the following chemical composition, wt.%:

The silicon oxide - 92,75

Alumina - 7,25

The resulting mass is stirred for 30 minutes, evaporated to a moisture content of 55-60 wt.%, molded by extrusion into pellets. The carrier is dried in air at room temperature for 24 hours, then at 110oWith 4 hours at 150oWith 2 hours, calcined at 550oWith 4 hours.

103 g of calcined carrier is placed in 150 ml of impregnating solution containing a 40.5 g of uranyl nitrate Nickel. The impregnation is carried out in the course of 2 hours at 60-70oC. P is live at 400-550oWith 4 hours.

The catalyst has the following composition, wt.%:

Nickel oxide - 4,0

Molybdenum oxide - 6,0

Tungsten - 6,0

The silicon oxide - 14,0

Alumina - Rest

As seen from the above examples, the proposed catalyst in contrast to the known has high activity and high mechanical strength.

1. A catalyst for Hydrotreating petroleum fractions, comprising the oxides of cobalt and/or Nickel, molybdenum trioxide, native oxide of aluminum, silicon, characterized in that the precursor of aluminium oxide is x-ray amorphous layered compound of aluminium of the formula Al2O3mo2Oh, where n= 0.3 to 1.5, and the carrier further comprises at least one of modifying a combination of metals selected from the group: sodium, iron, lanthanum, cerium, zinc, copper, tungsten, and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, and the catalyst has the following composition, wt. %:

NiO and/or COO - 1 - 5

Moo3- 8 - 15

The media, which included:

SiO2of 0.01 - 50

Modifying the connection metal is 0.01-5

and/or

The connection of the non - 0,5 - 10

Alumina - Osti of silicon oxide, the aluminum hydroxide containing the modifying compound, drying, calcination, impregnation with a solution of compounds active components of Nickel and/or cobalt, molybdenum, followed by drying and calcining, wherein as aluminum hydroxide use the product rehydration x-ray amorphous layered aluminum compounds of the formula Al2O3mo2Oh, where n= 0.3 to 1.5, which contains the full or partial amount of the modifier metal compounds selected from the group: sodium, iron, lanthanum, cerium, zinc, copper, tungsten and/or at least one connection of non-metals, selected from the group of phosphorus, fluorine, boron, and the catalyst has the following composition, wt. %:

NiO and/or COO - 1 - 5

Moo3- 8 - 15

The media, which included:

SiO2of 0.01 - 50

Modifying the connection metal is 0.01 - 5

and/or

The connection of the non - 0,5 - 10

Alumina - Rest

 

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