Catalyst hydroperiod and how hydroperiod oil and coking raw material with its use

 

(57) Abstract:

The invention relates to catalysts for Hydrotreating and hydrogenation of oil and coke raw material and method of its use. Catalyst hydroperiod contains the oxide of cobalt and/or Nickel oxide, molybdenum oxide, phosphorus oxide, copper oxide, zinc oxide and aluminum oxide in the following ratio of components (wt. %): oxides of cobalt and/or Nickel oxide - 2-4; molybdenum oxide - 10-14; phosphorus oxide is 0.5 - 5; copper oxide is 0.05 to 0.5; zinc oxide of 0.05-0.5; -aluminum oxide - rest. How hydroperiod oil and coke feedstock is carried out at a temperature of 300-400oC, a pressure of 3.0-5.0 MPa, the space velocity of the raw material 0,5-4,0 h-1, the ratio of H2/raw 500-1000 nm3/m3. 2 S. p. f-crystals, 5 PL.

The invention relates to catalysts for Hydrotreating and hydrogenation of oil and coke raw material and method of its use. In particular, catalysts for hydrodesulphurization unit straight and secondary gasoline fractions, hydrodesulphurization unit and dearomatization diesel fractions, and hydrodesulphurization unit and hydrogenation of aliphatic unsaturated hydrocarbons benzene-toluene-xylene (BTX) fractions koksohimicheskom-fractions of pyrolysis condensate fraction (the content of aromatic hydrocarbons 75-80% of the iodine number 20-40 g I2/100 g, a sulfur content of 0.02-0.03 wt.). Such catalysts are widely used in industry aluminoborosilicate catalysts AKM (CoO content is 4 wt. MoO312 wt.) [1] and alumonickelsilicate catalysts AMN: TH-30-7, AMN-5, KGO-5, ST-70 (NiO content of 3.5-5 wt. MoO312-20 wt.) [2]

These catalysts are used in both petrol and diesel Hydrotreating of distillates and Hydrotreating BTK-fraction of coke production. At a temperature of 350-400oC, a pressure of 4-5 MPa, the space velocity of the raw materials 3 h-1catalysts provide for the removal of sulfur compounds from BTK-fraction [1, 2] from 350 ppm to 1.5-2.0 ppm (degree of desulfurization rate of 99.0-99.6%) and decrease in iodine number of from 20-30 up to 0.05-0.8 g J2/100 g by reducing the content of aromatic hydrocarbons by hydrogenation over 5% on the ACME and 6-20% for ASM-catalysts.

In the hydrofining process of middle distillates, as well as mixtures of middle distillates gasoline fractions at a pressure of 3-3,5 MPa, a temperature of 350-380oC, space velocity of the feedstock 2-2,5 h-1these catalysts to reduce the sulfur content from 10000-13000 ppm up to 1500-2000 ppm, and iodine number of from 5-10 g I2/100 g 2-3 g I2/100 g [3]

These known the raw materials (BTK-fraction) with a sulfur content of 550 ppm and above catalysts are not high enough gidroobesserivaniya activity: the degree hydrodesulphurization unit ceteris paribus decreases sharply with 99.0-99.6% of up to 95-96% While the volumetric feed rate is reduced from 3 to 1 h-1.

When the diesel Hydrotreating of distillates to reduce the sulphur content of less than 0.10 wt. we have to drastically reduce the volumetric rate and raise the temperature of the process, which reduces the service life of the catalyst and restricts the production of environmentally friendly diesel fuels containing less than 0.05% (500 ppm) sulfur.

Due to a lack of high hydrogenating activity is not to reduce the content in diesel distillates aromatic hydrocarbons up to 20% even on AMN-catalysts.

These problems are partially solve new Hydrotreating catalysts [4] containing P2O5. The catalyst contains up to 5 wt. P2O5in the conventional alumnirelations matrix (Nickel oxide 2-4% molybdenum oxide 10-14% alumina rest). The active catalyst in the Hydrotreating process of the vacuum distillate at a temperature of 360oC, a pressure of 5.0 MPa, the space velocity of the feedstock is not less than 1 h-1.

Closest to the proposed technical solution is the catalyst for Hydrotreating a mixture of diesel and the gasoline-kerosene fraction containing (wt.): Nickel oxide or cobalt 1,0-6,0, molybdenum oxide 8,0-18,0, the oxide phosphors hydroperiod, carried out at T 260-360oC, P, 1,05 - 5,6 MPa, zsss of 0.1-10 h-1, the ratio of H2/raw 35,6-1780 nm3/m3in the presence of Co(Ni)Mo-containing catalysts in sulfide form [5]

The disadvantages of this catalyst is the impossibility of obtaining it in standard conditions of Hydrotreating environmentally friendly diesel fuels, as well as insufficient dearomatizing activity of the catalyst.

The present invention is aimed at improving gidroobesserivaniya activity of the catalyst hydroperiod, its hydrogenation activity relative to the aliphatic unsaturated hydrocarbons and selectivity of this process, as well as dearomatizing activity in the processing of diesel fractions (in the case of Ni-containing catalysts).

Applying the catalyst hydroperiod containing the oxide of cobalt and/or Nickel oxide, molybdenum oxide, phosphorus oxide, copper oxide, zinc oxide and aluminum oxide in the following ratio of components (wt.):

The oxide of cobalt and/or Nickel oxide 2-4

Molybdenum oxide 10-14

The phosphorus oxide is 0.5-5

The copper oxide of 0.05-0.5

Zinc oxide of 0.05-0.5

-alumina Rest

The catalyst of this composition can be used the MPa, space velocity of the raw material 0,5-4,0 h-1, the ratio of H2/raw 500-1000 nm3/m3.

As raw materials can be used straight or secondary gasoline fraction with a sulfur content of up to 6000 ppm or diesel fraction when the content of sulfur compounds to 12000 ppm, or a hydrocarbon fraction containing up to 99 wt. aromatic hydrocarbons (in particular BTK-fraction of coke production) when the content of sulfur compounds to 3000 ppm. The content of sulfur compounds in the products Hydrotreating gasoline and BTK-fractions on the catalyst is not more than 5 ppm (degree hydrodesulphurization unit at least 99.8%), diesel fractions less than 500 ppm (degree hydrodesulphurization unit not less than 95 wt.). The content of aromatic hydrocarbons in diesel fractions decreases with about 25-28. to less than about 20. (the degree of dearomatization not less than 30%).

When processing GTK-fraction content of nitrogen compounds is reduced from 500 ppm in raw materials up to 15-20 ppm in the product, iodine number from 21.3 to 0.3-0.5 g of I2/100, this delivers high selectivity of the hydrogenation of unsaturated aliphatic hydrocarbons, reducing the content of aromatic hydrocarbons of the ' technical effect of improving gidroobesserivaniya the activity of the catalyst, hydrogenating activity in relation to the aliphatic unsaturated hydrocarbons selectivity of this process, and hydrogenating activity towards aromatic hydrocarbons diesel fractions (in the case of Ni-containing catalysts) due to the introduction of the Al-Ni-Mo and Al-Co-Mo compositions together oxides of phosphorus, copper and zinc.

With equal content hydrogenating components in the samples prepared according to the prototype (Ni-Mo-P-REE-Cu-Al and Co-Mo-P-REE-Cu-Al) and the samples prepared according to the present invention (Ni-Mo-P-Cu-Zn-Al, Co-Mo-P-Cu-Zn-Al, Ni-Co-Mo-P-Cu-Zn-Al), the latter under the same conditions provide a greater degree of removal of sulfur compounds, increased hydrogenation activity relative to the aliphatic unsaturated hydrocarbons selectivity of this process, and improved hydrogenating activity towards aromatic hydrocarbons diesel fractions (in the case of Ni-containing catalysts).

Below are examples of the preparation of the catalysts according to the invention, and the prototype and the results of comparative tests in the Hydrotreating process of various kinds of raw materials.

Characteristics of the gasoline feedstock is shown in table.1.

Characterstream sulfur 12000 ppm

The density of 843 kg/m3< / BR>
Iodine number 1-3 g I2/100 g

The content of aromatic hydrocarbons of about 28.

Fractional composition,oC

N. To. 190

10% 240

30% 265

50% 290

90% 350

96% 365

Description BTK-fraction of coke production

Aliphatic and naphthenic hydrocarbons, wt. 1,90

Benzene, wt. 68,31

Toluene, wt. 23,06

Ethylbenzene + pair - and metaxylene, wt. 6,17

Ortho-Xylene + C9-aromatics, wt. 0,56

The total content of aromatic hydrocarbons, wt. 98,10

The sulfur content, ppm 2500

The content of nitrogen compounds, ppm 500

Iodine value, g I2/100 g 21,3

Example 1

It is 87.4 g (dry substance) of aluminum hydroxide are added 0.5 g (calculated at the P2O5) concentrated phosphoric acid, suspended for 2 h at 80-90oC, peptizer nitric acid, add 1 ml of a solution of zinc nitrate (solution concentration for ZnO 50 g/l) and 1 ml of a solution of copper nitrate (solution concentration on CuO 50 g/l). The mass is stirred for 2 h at 80-90oC, zamalchivaut to pH 6-8, cooled to room temperature, dried to a moisture content of 55-60 wt. and formed into extrudates with a diameter of C for 4 h Then the granules impregnated with the moisture absorption by a solution of nitrate of cobalt and paramolybdate ammonium in 14% ammonia solution with the aim of applying granules 2 g of CoO and 10 g MoO3. The obtained pellets of the catalyst is dried at 120oC for 6 h and calcined at 400oC for 4 h obtain 100 g of a catalyst of the following composition (wt.):

CoO 2

MoO310

P2O50,5

CuO 0,05

ZnO 0,05

g-Al2O3Else

Example 2

The catalyst prepared according to example 1, but take 76,0 g (dry substance) of aluminum hydroxide, 5 g of phosphoric acid (calculated at the P2O5), 10 ml solutions of zinc nitrate and copper nitrate (concentration in ZnO and CuO 50 g/l). Granules applied 4 g CoO and 14 g MoO3. Get 100 g of the catalyst composition (wt.):

CoO 4

MoO314

P2O55

CuO 0,5

ZnO 0,5

g-Al2O3Else

Example 3

The catalyst prepared according to example 1, but take and 82.2 g (dry substance) of aluminum hydroxide, 2.5 g of phosphoric acid (calculated at the P2O5), 5 ml of the solutions of zinc nitrate and copper nitrate (concentration in ZnO and CuO 50 g/l). Granules applied 3 g CoO and 12 g MoO3. Get 100 g catO3Else

Example 4

The catalyst prepared according to example 1, but instead of the solution of nitrate of cobalt take a solution of Nickel nitrate. Get 100 g of the catalyst composition (wt.):

NiO 2

MoO310

P2O50,5

CuO 0,05

ZnO 0,05

g-Al2O3Else

Example 5

The catalyst prepared according to example 2, but instead of the solution of nitrate of cobalt take a solution of Nickel nitrate. Get 100 g of the catalyst composition (wt.):

NiO 4

MoO314

P2O55

CuO 0,5

ZnO 0,5

g-Al2O3Else

Example 6

The catalyst prepared according to example 3, but instead of the solution of nitrate of cobalt take a solution of Nickel nitrate. Get 100 g of the catalyst composition (wt.):

NiO 3

MoO312

P2O52,5

CuO 0,25

ZnO 0,25

g-Al2O3Else

Example 7

The catalyst prepared according to example 3, but instead of 3 g CoO granules put together 1.5 g CoO and 1.5 g of NiO. Get 100 g of the catalyst composition (wt.):

NiO 1,5

CoO 1,5

MoO312,0

P2O52,5

CuO 0,25

ZnO 0,25

g-Al2O3Else

Example 8 (prototype)

The catalyst prepared according to example 3, but instead of 0.25 g of ZnO on katalizatorov (wt.):

CoO 3

MoO312

P2O52,5

(REE)2O32,5

CuO 0,25

g-Al2O3Else

Example 9 (comparison)

The catalyst prepared according to example 3, but a solution of zinc nitrate is added. Get 100 g of the catalyst composition (wt.):

CoO 3

MoO312

P2O52,5

CuO 0,25

g-Al2O3Else

Example 10 (prototype)

The catalyst prepared according to example 8, but instead CoO granules applied NiO. Get 100 g of the catalyst composition (wt.):

NiO 3

MoO312

P2O52,5

(REE)2O32,5

CuO 0,25

g-Al2O3Else

Example 11 (for comparison)

The catalyst prepared according to example 9, but instead CoO granules applied NiO. Get 100 g of the catalyst composition (wt.):

NiO 3

MoO312

P2O52,5

CuO 0,25

g-Al2O3Else

In table.2 shows the chemical compositions of the samples of the catalysts prepared according to examples 1-11. The samples prepared in examples 1-3 and 7-9, tested in the Hydrotreating gasoline. Test conditions: temperature 300oC, pressure 3 MPa, the volumetric feed rate to 4 h-1the ratio of H2s are given in table. 3. The same table shows the results of tests of the catalysts prepared according to examples 4-7 and 10-11 in the process hydrofining petroleum coking. Test conditions: temperature 400oC, a pressure of 3.5 MPa, the volumetric feed rate of 0.8 h-1the ratio of H2/raw 800 nm3/m3. The catalyst loading in the reactor 100 cm3.

As can be seen from the table.3, the catalysts prepared according to the invention, have the best gidroobesserivaniya properties than the comparison samples, during hydrofining virgin and secondary gasoline (compare examples 3 and 7 with examples 8 and 9 and examples 6 and 7 with examples 10 and 11). In addition, all samples of the catalysts prepared according to the invention, in the above conditions provide a sulfur content in the hydrotreated gasoline fractions to not more than 5 ppm (degree of Hydrotreating at least 99.8).

The samples prepared in examples 1-3 and 8-9, tested in the Hydrotreating process BTK-fraction of coke production. Test conditions: temperature 350oC, a pressure of 4.0 MPa, the volumetric feed rate of the raw material 1 h-1the ratio of H2/raw 800 nm3/m3. The catalyst loading in the reactor 100 cm3. Rainnie in accordance with the invention, provide the degree of Hydrotreating BTK-fraction of coke production but less and 99.8 wt. when a shallow depth of hydrogenation of the aromatic hydrocarbons (0,1-0,2%) and a high degree of hydrogenation of olefinic hydrocarbons (98,1-99,0%), as well as a high degree of removal of nitrogen compounds (at least of 96.5 wt.).

Catalysts containing ZnO (catalysts according to examples 8 and 9), in the same conditions provide the degree of Hydrotreating BTK-fraction of coking benzene but more 99,48 wt. when the depth of hydrogenation of aromatic hydrocarbons 1.3 to 1.7% and the degree of hydrogenation of olefinic hydrocarbons 96.7-97,2% (determined by the change of the iodine number), and the degree of removal of nitrogen compounds is 95.6-96,0%

Thus, the introduction of the well-known Hydrotreating catalyst ZnO instead of (REE)2O3leads to an increase in the degree of removal of sulfur compounds from 99,48% to 99.8% or more nitrogen compounds with 95,6-96,0% to 96.5% or more, the degree of hydrogenation of olefinic hydrocarbons with 97,2-97,7% to 98.1-99,0% depth of hydrogenation of the aromatic hydrocarbons is reduced from 1.3 to 1.7% 0.1-0.2%

Samples prepared according to examples 4-7 and 10-11, tested in the Hydrotreating process of straight distillate 3 h-1the ratio of H2/raw material 300 nm3/m3. The catalyst loading in the reactor 100 cm3. The results of the tests of the catalysts are given in table.5.

As follows from this table that the catalysts prepared in accordance with the invention (samples 4-7), have the best gidroobesserivaniya and dearomatization properties than the comparison samples. All samples of the catalysts prepared according to the invention, in the above conditions provide a sulfur content in the hydrogenation product is not more than 500ppm (0.05 wt.) and aromatic hydrocarbons of less than about 20. (the degree of dearomatization not less than 45%).

This shows that the catalyst prepared according to the present invention, shows its properties in the process of hydroperiod of crude oil (virgin and secondary gasoline fractions, diesel fractions and coke raw material under the conditions: temperature of 300-400oC, a pressure of 3-5 MPa, the volumetric feed rate of 0.5 to 6.0 h-1the ratio of H2/raw 500-1000 nm3/m3.

Sources of information

1. A. D. Berent, I. X. Mechitov, I. I. Hamburg, L. I. Lakhman, C. I. Mashinsky, V. A. Rogozin. Hydrotreating BTK-fractions of pyrolysis condensate fraction on allocability the summer Palace Berent, I. I., Sadko. Hydrotreating BTK-fractions of pyrolysis condensate fraction on alumonickelsilicate catalysts. Refining and petrochemicals, No. 5, 1986, S. 20-22.

3. L. N. Osipov and other operating Experience Hydrotreating diesel fuel L-24-5. Chemistry and technology of fuels and oils, 1988, No. 6, S. 31.

4. M. C. Landau, Y. K. Weill, A. A., Kricka, L. D. Konovalchik, B. K. Nefedov, V. S. Milutin, C. A. Vaskov. A new generation of catalysts for Hydrotreating. Chemistry and technology of fuels and oils 1991, No. 2, S. 2-4.

5. RF patent N 2039788, C 10 G 45/08; B. I. N 20, 1 1995 (prototype).

1. Catalyst hydroperiod containing the oxide of cobalt and/or Nickel oxide, molybdenum oxide, phosphorus oxide, copper oxide and aluminum oxide, wherein the catalyst additionally contains zinc oxide in the following ratio, wt.

The oxide of cobalt and/or Nickel oxide 2 4

Molybdenum oxide 10 14

The phosphorus oxide 0,5 5,0

The copper oxide 0,05 0,5

Zinc oxide 0,05 0,5

-alumina Rest

2. How hydroperiod oil and coke feedstock at elevated temperature, a pressure of 3.0 to 5.0 MPa, the space velocity of the raw material of 0.5 to 4.0 h-1, the ratio of H2/ raw materials 500 1000 nm3/m31 and the process is conducted at 300 to 400oC.

 

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