The catalyst containing phosphorus, and a method of hydrotreating of crude oil using this catalyst

 

(57) Abstract:

The invention relates to a catalyst based on aluminum, which contains, calculated on the weight content of the oxide 2-10 wt.% of cobalt oxide COO, 10-30 wt.% molybdenum oxide of Moo3and 4-10 wt.% oxide of phosphorus P2ABOUT5with a surface area by BET method in the range of 100 - 300 m2/g crushing strength CSH more than 1.4 MPa and an average diameter of pores in the range of 8-11 nm, the volume of pores of diameter greater than 14 nm is less than 0.08 ml/g, volume of pores with a diameter of less than 8 nm is not more than 0.05 ml/g and a volume of pores with a diameter of 8 to 14 nm in the range 0,20 - 0,80 ml/year Present invention also relates to a method of Hydrotreating, in particular hydrosulfurous, using the inventive catalyst. The technical result is an increase in the activity of the catalyst. 2 S. and 6 C.p. f-crystals, 1 Il., table 4.

The invention relates to a catalyst for Hydrotreating a hydrocarbon oil feedstock, which contains cobalt, molybdenum and phosphorus.

Hydrotreating of petroleum fractions is becoming increasingly important in the processing of oil along with the growth of the necessity of making very heavy fractions and the tightening of the specifications of the final products.

Such Panetti always with a high content of heavy fractions, which have a relative deficiency of hydrogen in the heavy fractions or more light produced from these fractions and contain a large number of heteroatoms, such as sulfur and nitrogen.

Generally, the Hydrotreating refers to the cleaning of hydrocarbon oil fractions without substantially changing the basic structure defined by the carbon atoms. It involves the removal of heteroatoms, such as sulfur and nitrogen, the removal of metals and partial or complete hydrogenation. When it is necessary, the oil fraction hydronaut, and then released from the formed product, which means that the purified oil fraction can be selected.

"Stiffness" of the Hydrotreating is directly related to working conditions. The term "working conditions" covers the nature of the raw material, the total pressure in the reaction zone, the partial pressure of the various compounds, the reaction temperature, time volumetric flow and flow rate of hydrogen. In General, the heavier raw materials and/or the more difficult it is amenable to transformation, especially the hard working conditions are necessary, i.e. the higher the pressure, temperature, flow rate of hydrogen and lower hourly volume flow.

When exploring a variety of media is it in terms of weight content of the oxide 2-10 wt.% of cobalt oxide COO, 10-30 wt.% molybdenum oxide of Moo3and 4-10 wt.% oxide of phosphorus P2O5and which preferably has a distinctive physico-chemical characteristics, has activity in Hydrotreating, far greater than the activity of the compositions of the prior art.

Used matrix is prepared on the basis of aluminum oxide (at least 50 wt.% aluminium oxide) and preferably essentially consists of aluminum oxide.

The catalyst is characterized by the fact that the phosphorus content, expressed in weight percent of phosphorous pentoxide P2O5based on the final catalyst is in the range from 4.0 to 10.0%, preferably from 4.5 to 8.0%, and more preferably from 5.6 to 8.0% or from 5.6 to 6.5%. The catalyst is also characterized in that the content of cobalt, expressed in weight percent of cobalt oxide COO based on the final catalyst is in the range from 2.0 to 10.0%, preferably from 3.5 to 7.0% and more preferably from 3.5 to 5.5%. The catalyst is also characterized in that the molybdenum content, expressed in weight percent molybdenum oxide, Moo3based on the final catalyst is in the range from 10 to 30%, mainly from 10 to 18.9%, preferred is result:

Surface area by BET method: surface Area by BET method, measured on the final catalyst is in the range from 100 to 300 m2/g, preferably from 120 to 250 m2/g and more preferably from 130 to 240 m2/,

CSH: Resistance to crushing by the method of the shell, denoted by the "CSH" and measured on the final catalyst is more than 1.4 MPa, and more preferably 1.6 MPa.

The average diameter of pores of an Average diameter of pores is determined by the profile of pore distribution obtained using mercury porometry. According to the distribution curve can be calculated curve derivative. The curve of the derivative passes through one or more of the highs, the abscissa of which determines the diameter of the pores. For the inventive catalyst obtained the maximum or maxima correspond to the diameter of pores in the range from 80 to ( nm), preferably from before and more preferably from to

The volume of pores with a diameter less than the Volume of pores with a diameter less than is at most 0.05 ml/g, preferably at most a 0.035 ml/g and more preferably at most of 0.025 ml/year

The volume of pores with a diameter greater than the Volume of pores with a diameter greater than is less than 0.08 ml/g, preferably less than 0.06 ml/g or more predostavljaet less than 10% of the total pore volume or more preferably, less than 8%.

The volume of pores with a diameter in the range from to

The volume of pores with a diameter from before is in the range from 0.20 to 0.80 ml/g, preferably from 0.30 to 0.70 ml/g, and 20-60% of the total pore volume comprises pores with a diameter

The catalyst of the present invention can be obtained using any method known to a skilled in this area specialists.

Hydrogenating element introduced during the mixing or after molding (as is preferable).

For molding followed by calcination, and hydrogenating element being before or after calcination. The preparation of the catalyst in all cases complete calcination at a temperature of from 250 to 600oC.

One of the preferred methods include mixing of the wet gel of aluminum oxide within a few tens of minutes, and then passing the resulting paste through a die of the extruder to form extrudates with a diameter preferably in the range from 0.4 to 4 mm

The catalyst also contains a hydrogenating function. Hydrogenating function provide a molybdenum or cobalt. It can be introduced into the catalyst at various stages and early as the carrier, and hydrogenating the remaining element(s) is introduced after mixing or, in most cases, after calcinations.

It is preferable in any way to obtain molybdenum is introduced simultaneously with cobalt or after him.

Preferably hydrogenating element is injected at one or more ion exchange operations on the calcined carrier with the use of solutions containing metal salts as precursors.

It can be entered on one or more of the operations of impregnation molded and calcined carrier with a solution of one or more precursors of cobalt oxide, whereas the precursor(s) of molybdenum oxide is injected in advance in the process of mixing media.

When the elements are introduced at several stages of impregnation corresponding salts, precursors, it is necessary to conduct the intermediate calcination of the catalyst at a temperature in the range from 250oWith up to 600oC.

Phosphorus is injected at any stage of the preparation of the catalyst. It can be entered separately or in a mixture with cobalt and/or molybdenum. For example, you can enter it before patsatsia of aluminum oxide. Also, for example, it can be entered in the extrudate oxide and the with cobalt or molybdenum in the oxide of aluminum, in the form of an extrudate with an intermediate annealing or without him. It is also possible partial or full introduction of phosphorus together with cobalt or molybdenum to aluminum oxide in the form of extrudate with intermediate annealing or without him. Phosphorus can also be entered at the end and separately. It should be noted that this list of routes of administration are given only for explanation, and we can offer even more options.

As the metal elements can be added in the form of oxides, with the aim to activate they should be prosulfuron. It should be noted that any suitable method of in situ or ex situ sulfurylase.

The present invention also relates to a method of Hydrotreating using the proposed catalyst.

Processing may be any raw material from benzilnikotinova fraction (initial boiling point 80o(C) vacuum distillate or vacuum residues.

The total pressure is in the range from 0.5 to 20 MPa, the temperature is in the range from 200oWith up to 480oWith, preferably in the range from 260oWith up to 450oSince that time the volume flow ranges from 20 to 0.05 h-1and the consumption of hydrogen is as much as, and is 0.5 to 6 MPa, preferably 0.5 to 5 MPa. Examples of the two boundary cases are hydrodesulfurization benzilnikotinova faction, which is performed at a pressure of 1.5 MPa, a temperature of 300oWith, the hourly volumetric flow rate 10 h-1and the consumption of hydrogen of 100 l/l of raw materials, and hydrodesulfurization deasphalting vacuum residue, which is carried out at a pressure of 20 MPa, a temperature of 390oWith, the hourly volumetric flow rate of 0.5 h-1and the flow of hydrogen to 1500 l/l raw materials.

The following examples illustrate the present invention and in no way limit it.

Prepared a large number of media on the basis of aluminum oxide. This purpose was used a commercially available gel SB3 sold by Condea. The gel is mixed with water and nitric acid and then stirred for 15 minutes. After stirring the resulting paste is passed through the cylindrical head of the extruder, get extrudates with a diameter of 1.2 mm, Then the extrudates are dried overnight at a temperature of 120oC and then calcined at a temperature of 550oC for 2 hours in moist air containing 7.5% is about. water.

EXAMPLE 1: the Catalyst C1 (this is not the catalyst of the present invention).

To the dry impregnation of the carrier. As cobalt salts using cobalt nitrate Co(NO3)26N2Acting as a salt of molybdenum use heptamolybdate ammonium. Mo7O24(NH4)64H2O and phosphorus is injected in the form of H3RHO4. After dry impregnation, the extrudates are dried overnight at a temperature of 120oC and then calcined at a temperature of 550oC for 2 hours in moist air containing 7.5% is about. water. Below is the final content of the metal oxide and the main physico-chemical characteristics:

Moo3- 18.2 wt.%

Soo - 4.1 wt.%

P2O5to 1.9 wt.%

SBET- 205 m2/g

CSH - 1.3 MPa

EXAMPLE 2: the Catalyst C2 (the catalyst of the present invention).

To extruded media type cobalt, molybdenum and phosphorus. Salt three elements injected simultaneously by dry impregnation of the carrier. As cobalt salts using cobalt nitrate Co(NO3)26N2O. as a salt of molybdenum use heptamolybdate ammonium. Mo7O24(NH4)64H2O and phosphorus is injected in the form of H3RHO4. After dry impregnation, the extrudates are dried overnight at a temperature of 120oC and then annealed at t is the actual content of the metal oxide and the main physico-chemical characteristics:

Moo3- 18.2 wt.%

Soo - 4.1 wt.%

P2O5- 5.7 wt.%

SBET- 170 m2/g

CSH - 1.8 MPa

EXAMPLE 3: the Catalyst C3 (not a catalyst of the present invention, the catalyst for comparison)

To extruded media add cobalt and molybdenum. Salts of these elements can be added simultaneously by dry impregnation of the carrier. As cobalt salts using cobalt nitrate Co(BUT3)26N2O, as a salt of molybdenum use heptamolybdate ammonium. Mo7O24(NH4)64H2O. After dry impregnation, the extrudates are dried overnight at a temperature of 120oC and then calcined at a temperature of 550oC for 2 hours in moist air containing 7.5% is about. water. Below is the final content of the metal oxide and the main physico-chemical characteristics:

Moo3- 18.2 wt.%

Soo - 4.1 wt.%

P2ABOUT5- About the weight.%

SBET- 235 m2/g

CSH - 1.2 MPa

EXAMPLE 4: Comparative test: the hydrogenation of toluene

Activity three of the above catalysts is compared with the hydrogenation of toluene. Before using catalysts sulfureous in situ. The reaction is carried out at a pressure which Yunosti are given in table. 1. Catalyst C3, not containing phosphorus, is the catalyst for comparison.

You may notice that two catalyst containing phosphorus, more active than a catalyst that does not contain phosphorus. In addition, our data show that the catalyst contains phosphorus in a larger proportion is significantly more active than the catalyst, which contains small amounts of phosphorus.

EXAMPLE 5: Comparative test: hydrodesulfurised straight-run gas oil.

Three of the above-described catalyst is compared when using the actual raw materials. Before applying catalysts sulfureous in situ. Activity when Desulfovibrio evaluated on a straight-run gasoil, the basic properties of which are given in table.2.

Simulated distillation: initial point - 153oC; 5% - 222oC; 50% - 315oWITH; 95% OF 415oC; endpoint - 448oC.

Hydrodesulfurization carried out under the following operating conditions: total pressure of 3 MPa; the hourly volumetric flow rate of 2 h-1; temperature - 310oWITH, 340oWith 360oWith; the flow rate of the hydrogen - 250 l/l raw materials.

The catalytic properties of the three catalysts at three temperatures the reaction of p which contains phosphorus.

It is obvious that the catalyst C2 of the present invention are significantly more active. Thus, this catalyst is particularly suitable for carrying out hydrodesulfurization.

For example.

Special physico-chemical characteristics of the catalyst are determined by the carrier. In the patent FR 2556611 emphasizes that a significant result is the medium that provides the maximum correlation between macropores and mesopores (see paragraph 6). In this application, the carrier is a Condea Gel SB3 (page 5) with a pore distribution as shown in Fig.1.

While in the claimed catalyst, the percentage of macropores more 250A is less than 10% and less than 0.08 ml/g pore over 140A, while 70 to 90% of the total pore volume of the catalyst according to the patent FR 2556611 ranges from 90 to 300A.

The applicant also cites a comparative analysis of catalysts C and D according to the patent FR 2556611 and the claimed catalyst. the average diameter of pores: C - 154 A; D - 145 A; the invention 80-110 A, i.e. C and D lie beyond the stated limits. When the pore distribution shown in table.4.

From table. 4 it is clear that C lies beyond the stated limits as 0.4 cm3/g>0,08 cm3/g, D lies in o, the most minor changes can lead to substantial changes in properties and in this case, these differences in physico-chemical properties caused by various media.

The scope of various catalysts, since the catalyst indicated in French patent applied for Hydrotreating heavy fractions, while the claimed catalyst used for Hydrotreating petroleum fractions.

1. A catalyst for Hydrotreating petroleum fractions, on the basis of aluminum oxide containing 2-10 weight. % of cobalt oxide COO, 10-30 weight. % of molybdenum oxide, Moo3and 4-10 weight. % of phosphorus oxide P2ABOUT5with a surface area by BET method in the range of 100 - 300 m2/g, the resistance to crushing SH more than 1.4 MPa and an average diameter of pores in the range of 8-11 nm, and the volume of pores of diameter greater than 14 nm is less than 0.08 ml/g, volume of pores with a diameter less than 8 nm is not more than 0.05 ml/g, and pore volume with a diameter of 8 to 14 nm is in the range 0,20 - 0,80 ml/year

2. The catalyst according to any one of the preceding paragraphs, in which the content of P2ABOUT5is 4.5 to 8.0%.

3. The catalyst according to any one of the preceding paragraphs, in which the content of P2ABOUT5with the 3.5 to 7.0% and the content of Moo3is 10.0% to 18.9%.

5. The catalyst according to any one of the preceding paragraphs, obtained by impregnation of a calcined carrier based on alumina with a solution of(s) cobalt, molybdenum and phosphoric acid, followed by drying and calcining in moist air.

6. The method of Hydrotreating of petroleum fractions using a catalyst according to any one of paragraphs. 1-5, which is carried out at 200-480oC, at a pressure of 0.5 to 20 MPa, the hourly volumetric flow rate of 0.05-20 h-4and the consumption of hydrogen 100-3000 l/l raw materials.

7. The method according to p. 6, which is carried out at a pressure of between 0.5 and 6 MPa.

8. The method according to any of the p. 6 or 7, in which the hydrotreatment is hydrodesulfurization.

 

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