The catalyst for hydrodesulphurization unit oil fractions

 

(57) Abstract:

The invention relates to catalysts for purification of oil fractions from sulfur compounds and can be used in the refining and petrochemical industries. The catalyst for the desulfurization of petroleum fractions has high activity. The catalyst contains, wt%: the oxide of molybdenum or tungsten 10,0-20,0, cobalt oxide or Nickel 2,0-6,0, the carrier 100. As the carrier is used, the composition of the oxides of aluminum, boron, titanium or zirconium, manganese when the mass ratio of the components Al2O3: B2O3: TiO2(ZrO2) : MnO2: 0,005-0,053 : 0,002-0,042 : 0,0004-0,0016. In addition, the carrier may contain 1-10 wt.% silicon oxide. 3 S. p. f-crystals , 1 table.

The invention relates to catalysts for purification of oil fractions from sulfur compounds and can be used in refining and petrochemical industries.

Known catalyst for Hydrotreating petroleum product in which the active components deposited on the active alumina (D. I. Orochko, A. D. Sulimov, L. L. Osipov. Hydrogenation processes in oil refining. M.: Chemistry, 1971, S. 74).

The disadvantage of the holding of 0.98 wt.% sulfur, at a pressure of 3.0 MPa, a temperature of 380oC, space velocity of the raw materials 2.5 h-1and circulating the hydrogen-containing gas (hydrogen-rich) 400 nm3/m3raw materials on the catalyst composition, wt.%:

The cobalt oxide - 4,0

Molybdenum oxide - 14,0

Aluminum oxide 82 - 82,0

the degree hydrodesulphurization unit is 90,2%.

Known catalyst hydrodesulphurization unit hydrocarbons containing active components supported on a carrier containing aluminum oxide and 0.5-7.0 wt.% oxide of rare earth elements (REE) /U.S. patent N 4177163, B 01 J 23/10, 21/04, 1979/.

The disadvantage of this catalyst is its low activity. For example, during the Hydrotreating of vacuum gas oil containing 2,12 wt.% sulfur, at a temperature of 380oC, a pressure of 2.7 MPa, the space velocity of the raw material 1 h-1the ratio of circulating SIV 1500 nm3/m3raw materials on the catalyst composition, wt.%:

The cobalt oxide is 3.5

Molybdenum oxide - 10,0

Media containing 1.5 wt.% oxide REE and to 98.5 wt.% aluminum oxide is 86.5

the degree hydrodesulphurization unit was 56.5%.

The closest in technical essence and the achieved effect is the catalyst for hydrodesulphurization unit vacuum gasoil oxides of aluminum and titanium.

The disadvantage of this catalyst is its low activity.

For example, when the vacuum gasoil hydrodesulphurization unit at a pressure of 2.8 MPa, a temperature of 380oC, space velocity of the raw material 1 h-1the ratio of circulating SIV 1500 nm3/m3raw materials on the catalyst composition, wt.%:

Molybdenum - 8,4

Nickel - 2,8

Media containing 8.2 wt.% titanium oxide and 91.8 wt.% aluminum oxide and 88.8

the degree hydrodesulphurization unit is 56,1%.

The proposed catalyst contains oxides of metals of the VIII and VIB groups on a medium composed of a mixture of oxides of aluminum, boron, titanium or zirconium and manganese at the following mass ratio of Al2O3:B2O3:TiO2(ZrO2): MnO2= 1:(0,005-0,053):(0,002-0,042):(0,0004-0,0016).

In this case, the finished catalyst has a composition, wt.%:

Molybdenum oxide or tungsten oxide - 10,0-20,0

The cobalt oxide or Nickel oxide - 2,0-6,0

The carrier is a mixture of oxides of aluminum, boron, titanium or zirconium and manganese in their mass ratio: 1:(0,005-0,053):(0,002-0,042):(0,0004-0,0016) - 100

In addition, as the carrier of the catalyst for Hydrotreating petroleum fractions, you can use a mixture of oxides of aluminum, boron, Titus is:MnO2= 1: (0,005-0,053): (0,002-0,042): (0,0004-0,016) and from 1 to 10 wt.% silicon oxide, and the catalyst has the following ratio of components, wt.%:

Molybdenum oxide or tungsten oxide - 10,0-20,0

The cobalt oxide or Nickel oxide - 2,0 - 6,0

Media 100

The hallmark of the catalyst is part of the media. This catalyst has a high activity.

The catalyst was prepared as follows. At a temperature of 50-60oC and a pH of 6.5 to 8.0 lead deposition of a mixture of hydrates of aluminum, titanium or zirconium and manganese from sodium aluminate and hydrolysis of salts of titanium or zirconium and manganese in the presence of nitric acid. The precipitate is subjected to aging at 60-102oC, pH 9.0 to 9.5 V for 2 h, then washed, filtered, peptizer boric acid, and then nitrogen and molded. The extrudates are dried at 120oC 6 h and calcined in a stream of dry air at 500-550oC for 4 h and cooled. If necessary, before patsatsia add silicon oxide. The extrudates are impregnated with the active components, they are then dried and calcined under the same conditions as the media.

The resulting catalysts were tested in pilot conditions when gidroobesserivaniya gasoline, diesel and gasolene by Engler,oC N. K. - 105

10% vol. - 116

50% vol. - 128

90% vol. - 149

K. K. - 172

sulfur content, wt.% - 0,5

diesel fraction 150-365oC N. K. - 150

50% vol. - 273

96% vol. - 357

K. K. - 365

sulfur content, wt.% - 0,72

iodine value, g iodine/100 g - 1,8

the vacuum gas oil fraction:

density, g/cm3- 0,918

fractional composition,oC

10% vol. - 405

50% vol. - 462

K. K. - 550

sulfur content, wt.% - 2,81

Obtaining and proposed activity of the catalysts is illustrated by the following examples.

Example 1

In a container with a stirrer were placed 764,92 g of sodium aluminate solution containing 13 wt.% aluminum oxide, 2.6 g of titanium trichloride, 0.11 g of manganese nitrate, a nitric acid solution to pH 7.0 and stirred. The temperature of the solution was raised to 55oC and maintained until complete precipitation. The precipitate was subjected to aging for 2 h at 95oC and a pH of 9.2. Then the sludge decantation, washed, filtered, added to 0.89 g of boric acid, 2.4 ml of nitric acid and extrudible. The extrudates were dried for 6 h at 120oC and progulivali in a stream of dry air for 4 h at 530oC. the Cooled extrudates were placed in 85 ml of an aqueous solution of ammonia containing 20,42 g musili and progulivali under the same conditions, as the media.

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

Molybdenum oxide - 15,0

The cobalt oxide - 4,0

Media - 81,0

While the media had a composition, wt.%:

The boron oxide - 0,5

The titanium oxide - 2,0

Manganese oxide - 0.04

Alumina - 97,46

The resulting catalyst was tested in the process of diesel hydrodesulphurization unit fractions at a pressure of 3.0 MPa, a temperature of 380oC, space velocity of the raw materials 2.5 h-1and the multiplicity of circulating SIV 400 nm3/m3of raw materials. The test results presented in the table.

Example 2

The catalyst was prepared according to example 1 with the difference that took 0.26 g of titanium trichloride, of 0.41 g of manganese nitrate, and 8.9 g of boric acid, and nitric acid was added to pH 8.0. The deposition of the media was carried out at 50oC aging at 60oC and a pH of 9.5. Impregnating solution contained 13,61 g of ammonium molybdate and 23.3 g of cobalt nitrate.

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

Molybdenum oxide - 10,0

The cobalt oxide - 6,0

Media - 84,0

While the media had a composition, wt.%:

The boron oxide - 5,0

The titanium oxide - 0,2

Manganese oxide - 0,16

Alumina - 96,64

Received to the>C, space velocity of the raw material 5 h-1and the multiplicity of circulating SIV 500 nm3/m3of raw materials. The test results presented in the table.

Example 3

The catalyst was prepared according to example 1 with the difference that took 8.6 g of titanium nitrate, 0.27 g of manganese nitrate, 1.6 g of boric acid, and nitric acid was added until a pH of 6.5. The deposition of the media was carried out at 60oC, aged at 102oC and pH 3.0. Impregnating solution contained 15,26 g ammonium wolframalpha and 8.7 g of Nickel nitrate.

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

Tungsten - 12,6

Nickel oxide - 3,56

Media - 83,84

While the media had a composition, wt.%:

The boron oxide - 0,9

The titanium oxide - 4,0

Manganese oxide - 0,1

Alumina - 95,0

The resulting catalyst was tested in the process of vacuum gasoil hydrodesulphurization unit at a pressure of 2.7 MPa, a temperature of 380oC, space velocity of the raw material 1 h-1the ratio of circulating SIV 1500 nm3/m3of raw materials. The test results presented in the table.

Example 4

The catalyst was prepared according to example 1 with the difference that in the preparation of the carrier took 5.5 g of oxinitride zirconium, and propietor had the following composition, wt.%:

Tungsten - 20,0

Nickel oxide - 2,0

Media - 78,0

While the media had a composition, wt.%:

The boron oxide - 0,5

Zirconium oxide - 2,0

Manganese oxide - 0.04

Alumina - 97,46

The catalyst was tested in the process of diesel hydrodesulphurization unit fractions as in example 1. The test results presented in the table.

Example 5

The catalyst was prepared according to example 2 with the difference that for the preparation of the carrier took 0.55 g oxinitride Zirconia.

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

Molybdenum oxide - 14,0

Nickel oxide - 5,0

Media - 81,0

While the media had a composition, wt.%:

The boron oxide - 0,5

Zirconium oxide is 0.2 to

Manganese oxide - 0,16

Alumina - schedule rate is now 99.14

The catalyst was tested in the process of diesel hydrodesulphurization unit fractions as in example 1. The test results presented in the table.

Example 6

The catalyst was prepared according to example 3 with the difference that for the preparation of media were taken between 6.08 g of zirconium sulfate. While the media had the following composition, wt.%:

The boron oxide - 0,9

Zirconium oxide - 4,0

Manganese oxide - 0,1

Alumina - 95,0,

and the catalyst of Imamura 3. The test results presented in the table.

Example 7

The catalyst was prepared according to example 1 with the difference that in the media prior to moulding was added 1.01 g of silicon oxide. While the media had a composition, wt.%:

The silicon oxide - 1,0

The boron oxide - 0,49

The titanium oxide - 1,98

Manganese oxide - 0.04

Alumina - 96,49,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 8

The catalyst was prepared according to example 1 with the difference that in the media prior to moulding was added 6,36 g of silicon oxide. While the media had a composition, wt.%:

The silicon oxide - 6,0

The boron oxide - 0,462

The titanium oxide - 1,88

Manganese oxide - 0,038

Alumina - 91,62,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 9

The catalyst was prepared according to example 1 with the difference that in the media prior to moulding was added 11 g of silicon oxide. While the media had a composition, wt. %:

The silicon oxide - 10,0

The boron oxide - 0,45

The titanium oxide - 1,82

Manganese oxide - being 0.036

Alumina - ITE presented in the table.

Example 10 (comparative)

The catalyst was prepared according to example 1 with the difference that the amount of boric acid in the extrudable mixture is equal to 0.71, While the media had a composition, wt.%:

The boron oxide - 0,4

Ooked titanium - 2,0

Manganese oxide - 0.04

Alumina - 97,06,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 11 (comparative)

The catalyst was prepared according to example 2 with the difference that the amount of boric acid in the extrudable mixture 9,26, While the media had a composition, wt.%:

The boron oxide - 5,2

The titanium oxide - 0,2

Manganese oxide - 0,15

Alumina - 94,45,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 12 (comparative)

The catalyst was prepared according to example 1 with the difference that in the preparation of media were taken of 0.13 g of titanium trichloride. While the media had a composition, wt.%:

The boron oxide - 0,5

The titanium oxide - 0,1

Manganese oxide - 0.04

Alumina - 99,36,

and the catalyst had the same composition as in example 1 and was tested in which talization was prepared according to example 3 with the difference, when preparing media took 0,46 g of titanium trichloride. While the media had a composition, wt.%:

The boron oxide - 0,9

The titanium oxide - 4.2V

Manganese oxide - 0,1

Alumina - 94,8,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 2. The test results presented in the table.

Example 14 (comparative)

The catalyst was prepared according to example 4 with the difference that in the preparation of the carrier took 0.08 g of manganese nitrate. While the media had a composition, wt.%:

The boron oxide - 0,5

The titanium oxide - 2,0

Manganese oxide - 0,03

Alumina - 97,47,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 15 (comparative)

The catalyst was prepared according to example 2 with the difference that in the preparation of the carrier took to 0.48 g of manganese nitrate. While the media had a composition, wt.%:

The boron oxide - 5,0

The titanium oxide - 0,2

Manganese oxide - 0,18

Alumina - 94,62,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

stage took 0.27 g of oxinitride zirconium. While the media had a composition, wt.%:

The boron oxide - 0,5

Zirconium oxide is 0.1 to

Manganese oxide - 0.04

Alumina - 99,45,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 17 (comparative)

The catalyst was prepared according to example 13 with the difference that instead of the titanium trichloride took 11,55 g oxinitride zirconium. While the media had a composition, wt.%:

The boron oxide - 0,9

Zirconium oxide - 4.2V

Manganese oxide - 0,1

Alumina - 94,8,

and the catalyst had the same composition as in example 1 and was tested under the conditions of example 1. The test results presented in the table.

Example 18 (prototype)

100 g of calcined alumina grinded and prepared from it aqueous suspension, which was mixed with a solution of titanium trichloride in a 14% solution of a hydroxide of an Ammonite. The amount of titanium trichloride corresponded to 8.2 wt.% titanium oxide. To the mixture was added a solution of ammonium hydroxide to maintain alkaline pH level of 9.3. The homogeneous mixture is then dried for extruding. The extrudates were dried at 121oC for 16 h and was progulivali 2 h in technolibrary ammonium and 8,71 g of Nickel nitrate. The catalyst was dried and progulivali under the same conditions as the media.

The finished catalyst had a composition, wt.%:

Nickel oxide - 3,56

molybdenum oxide - 12,6

media containing, wt.%: - 83,84

the titanium oxide - 8,2

alumina - 91,8

The catalyst was tested under the conditions of example 3. The test results presented in the table.

Thus, the proposed catalyst has high activity in the process of oil hydrodesulphurization unit fractions (examples 1-9). However, this is only possible in the claimed limits of the ratio of carrier components. As shown by comparative examples 10-17 reduction and enlargement ratios of the components of the medium leads to a decrease in the activity of the catalyst. The catalyst prepared according to the method prototype (sample No. 18), also has a lower activity than suggested.

1. The catalyst for hydrodesulphurization unit oil fractions containing the oxides of metals of the VIII and VIB groups on the alumina carrier, characterized in that the medium contains the composition of the oxides of aluminum, boron, titanium or zirconium and manganese at the following weight ratio:

Al2O3: B2O3: TiO2(ZrO2) : MnO2 is the oxide of molybdenum or tungsten and cobalt oxide or Nickel on alumina carrier, characterized in that the medium contains the composition of the oxides of aluminum, boron, titanium or zirconium and manganese at the following mass ratio of Al2O3: B2O3: TiO2(ZrO2) : MnO2= 1 : 0,005 - 0,053 : 0,002 - 0,042 : 0,0004 - 0,016,

and the catalyst has the following ratio of components, wt.%:

Molybdenum oxide or tungsten oxide - 10,0 - 20,0

The cobalt oxide or Nickel oxide - 2,0 - 6,0

Media 100

3. The catalyst for hydrodesulphurization unit oil fractions containing the oxide of molybdenum or tungsten and cobalt oxide or Nickel on alumina carrier, characterized in that the medium contains the composition of the oxides of aluminum, boron, titanium or zirconium, manganese and silicon in the following mass ratios:

Al2O3: B2O3: TiO2(ZrO2) : MnO2= 1 : 0,005 - 0,053 : 0,002 - 0,042 : 0,0004 - 0,016,

and contains 1 to 10 wt.% of silicon oxide, the catalyst has the following ratio of components, wt.%:

Molybdenum oxide or tungsten - 10,0 - 20,0

The oxide of cobalt or Nickel - 2,0 - 6,0

Media - Up To 100

 

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