Petroleum fraction hydrofining catalyst

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

 

The invention relates to the field of oil refining, in particular for catalysts intended for use in the process of Hydrotreating petroleum fractions.

Famous (Ed. mon. The USSR 1547122, class B 01 J 37/02, 29/04, 1986) catalyst for hydrofining of petroleum raw materials of the following composition, wt.%: the zeolite in the form of MoO3NH4NaY - 5-20; NiO - 3,5-5,0; NGO3- 10-20; P2About5- 1,5-3,0;2About3- 2,0-10,0; Al2About3- the rest.

The catalyst provides the depth of removal of sulfur compounds at the level of 90%.

From patent No. 2102146 (IPC RU701 J 37/04, publ. 20.01.98, bull. 2) a well-known catalyst for Hydrotreating petroleum fractions, which has the following composition, wt.%:

NiO3,0-4,5
Moo310,0-12,0
Na2O0,02-0,08
P2O50.5 to 1.5
In2O31,0-3,0
Al2About3the rest of it.

The method of obtaining this catalyst comprises a mixture of alumina carrier with boric acid and molybdenum salt solution, followed by shaping, drying and calcining the pellets. Received lumbrokinase composition is impregnated with a solution of Nickel nitrate in the Pris is under phosphoric acid at a pH of 3.6 to 4.5.

The degree of desulfurization in the Hydrotreating of diesel fuel at a temperature of 335°is 91,9%, and at 342° - 92,8%.

When the Hydrotreating benzene-toluene-xylene fraction degree of desulfurization at a temperature of 250°is 75,0%, while due to coking of catalyst needed in year 3 or 4 of the hydrogen treatment to activate the catalyst.

The closest (prototype) to the technical essence and the achieved result the catalyst, is known from the patent No. 2197323 (EN, 01 J 23/88, publ. 27.01.03.), is the 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, and boron. 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 Al2About3·nH2Oh, where n=0.3 to 1.5.

There is described a method with which otopleniya catalyst, which includes extrusion molding 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.

The disadvantage of this catalyst is the complexity of the technology of its preparation.

The present invention is directed to the development of the method of preparation of the catalyst with high gidroobesserivaniya activity during the processing of crude oil containing large amounts of unsaturated hydrocarbons.

Applying the catalyst for Hydrotreating petroleum fractions, comprising the oxides of cobalt, molybdenum, sodium, lanthanum, phosphorus, boron, aluminum, which, according to the invention, has the following composition, wt.%:

Soo2,5-4,0
Moo38,0-12,0
Na2O0,01-0,08
La2About31,5-4,0
P2O52,0-5,0
In2O30,5 - 3,0
Al2About3the rest of it.

Comparative analysis of the prototype and the present invention shows that commonality is the composition of the catalyst to the second includes the oxides of cobalt, molybdenum, sodium, lanthanum, phosphorus, boron, aluminum.

The difference between the claimed catalyst from the well-known is the quantitative content of components, wt.%:

Soo2,5-4,0
Moo38,0-12,0
Na2O0,01-0,08
La2About31,5-4,0
P2O52,0-5,0
In2O30,5 - 3,0
Al2About3the rest of it.

The proposed catalyst provides a more effective Hydrotreating of crude oil, containing increased amounts of unsaturated hydrocarbons.

The following are specific examples of implementation of the proposed technical solution.

Example 1.

The media is prepared by mixing aluminum hydroxide (pellet pseudoboehmite and bemani structure consisting of a 60-40 wt.% pseudoboehmite and 40-60 wt.% boehmite. The composition includes up to 0.10 wt.% Na2O) in an amount of 40 kg 0.7 kg of boric acid and a nitric acid solution of lanthanum carbonate. The resulting mass is stirred at a temperature of 30°C for 15 minutes. Once smooth add the 1.5 DM325%aqueous ammonia and the mass stirred at 80°in the course is e 20 minutes. Ready weight with a dry matter content of 50% formed into pellets with a diameter of 1.7 mm Molded pellets are dried for 5 hours at a temperature of 120-200°and then calcined at a temperature of 450°C for 5 hours.

At the same time preparing an impregnating solution. The solvent is poured 400 DM3water, add 40 DM3orthophosphoric acid and load 170 kg of cobalt nitrate with continuous stirring at a temperature of 40°C. To the resulting solution with a concentration of 50 g/DM3COO at pH 3.5 load 120 kg paramolybdate ammonium to obtain a solution with a concentration of 200 g/DM3Moo3.

Then hold the carrier impregnated with the active compounds of components, which is as follows. In the capacity of the load estimated number obtained as described above medium, then from the dipstick add the estimated amount of the impregnating solution (40°C, pH 3.5)containing cobalt nitrate, paramolybdate of ammonia and phosphoric acid.

Saturated compounds active component carrier is dried at a temperature of 150°and calcined at a temperature of 450°C.

The finished catalyst contains the following ratio of components, wt.%:

Soo4,0
Moo3 to 12.0
Na2O0,08
La2O34,0
P2O52,0
In2O33,0
Al2O3the rest of it.

The catalyst has an index of strength of 2.3 kg/mm diameter pellets. Test it with the Hydrotreating of diesel fuel at a temperature of 335°provides 92,5%depth of removal of sulfur compounds. Use it during hydrofining benzene-toluene-xylene fraction at 230°provides for reduction of sulfur compounds by 82% (mass.). This mainegenealogy period is 11 months, after 2 years of work required hydrogen treatment of the catalyst after 6 months.

Example 2.

The media is prepared by mixing aluminum hydroxide (pellet pseudoboehmite and bemani structure consisting of a 60-40 wt.% pseudoboehmite and 40-60 wt.% boehmite. The composition includes up to 0.10 wt.% Na2O) in an amount of 40 kg 0.6 kg of boric acid and a nitric acid solution of lanthanum carbonate. The resulting mass is stirred at a temperature of 30°C for 15 minutes. Once smooth add the 1.5 DM325%aqueous ammonia and the mass stirred at 80°C for 20 minutes. Ready weight with the content of dry substances is TBA 50% formed into pellets with a diameter of 1.7 mm These granules are dried for 5 hours at a temperature of 120-200°and then calcined at a temperature of 450°C for 5 hours.

At the same time preparing an impregnating solution in a solvent is poured 400 DM3water, add 50 DM3orthophosphoric acid and load 160 kg of cobalt nitrate with continuous stirring at a temperature of 80°C. To the resulting solution with a concentration of 50 g/DM3COO at pH 2.0 load 110 kg paramolybdate ammonium to obtain a solution with a concentration of 190 g/DM3Moo3.

Then hold the carrier impregnated with the active compounds of components, which is as follows. In the capacity of the load estimated number obtained as described above medium, then from the dipstick add the estimated amount of the impregnating solution (80°C, pH 2.0)containing cobalt nitrate, paramolybdate of ammonia and phosphoric acid.

Saturated compounds active component carrier is dried at a temperature of 150°and calcined at a temperature of 450°C.

The finished catalyst contains the following ratio of components, wt.%:

Soo2,5
Moo38,0
Na2O0,01
La2the 31,5
P2About55,0
In2About30,5
Al2About3the rest of it.

The catalyst has an index of strength of 2.3 kg/mm diameter pellets. Test it with the Hydrotreating of diesel fuel at a temperature of 335°provides 93,0%depth of removal of sulfur compounds. Use it during hydrofining benzene-toluene-xylene fraction at 230°provides for reduction of sulfur compounds by 83% (mass.). This mainegenealogy period is 11 months, after 2 years of work required hydrogen treatment of the catalyst after 6 months.

The study proposed catalysts in Hydrotreating process provides obtaining the hydrogenated feed is cut with a low content of sulfur compounds. This will be achieved by improving the technical and economic indicators: saving energy and material resources.

A catalyst for Hydrotreating petroleum fractions, comprising the oxides of cobalt, molybdenum, sodium, lanthanum, phosphorus, boron, aluminum, characterized in that it has the following composition, wt.%:

Soo2,5-4,0
Moo38,0-12,0
Na2O0,01-0,08
La2About31,5-4,0
P2O52,0-5,0
In2About30,5-3,0
Al2O3Rest



 

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