Way thin catalytic purification of benzene fractions from sulfur and unsaturated compounds

 

(57) Abstract:

Usage: petrochemistry. The inventive method is carried out by contacting the feedstock and hydrogen with solifidianism before using the catalyst. The catalyst contains 8-20 wt.% trioxide of molybdenum, 2-6 wt. % of oxide of cobalt and/or Nickel, the rest is aluminum oxide. The process is carried out at a temperature of 230-280oC, pressure of 2.0-5.0 MPa, the space velocity of the feedstock 1-3-1, the ratio of hydrogen: the raw material is equal to 100-150 nm3/m3. Technical result: the involvement in the process of purification of the feedstock with higher contents of sulfur and unsaturated hydrocarbons. 1 C.p. f-crystals., table 1.

The technical field to which the invention relates

The invention relates to methods of producing aromatic hydrocarbons, in particular benzene from pyrolysis condensate fraction or crude coking benzene.

Art

The known method for the catalytic purification of aromatic hydrocarbons containing tifany using as a catalyst a mixture of oxides of cobalt and molybdenum (US 3642927, 1972).

The disadvantage of this method is the lack of efficiency of treatment.

Most BL is aliciously purification of benzene fractions from sulfur and unsaturated compounds, in which used catalyst containing 0,050,5 wt.% platinum or palladium, the rest is aluminum oxide (RU 2091439, 1997).

The disadvantage of this method is the use of expensive palladium and platinum, as well as the fact that the required quality of the product, i.e., sulfur content less than 1 ppm, bromine number 0,002 g Br2/100 g, is achieved only at low contents of sulfur and olefins in the feedstock (sulfur content does not exceed an 8.4 ppm, and bromine number - 0.03 g Br2/100 g).

The invention

The technical problem solved by the present invention, is involvement in the process of fine catalytic purification of raw materials with a higher content of sulfur and unsaturated hydrocarbons (high values of bromine number), as well as reducing the cost of the process due to the use of cheaper catalyst.

This technical problem is solved in the way thin catalytic purification of benzene fractions from sulfur and unsaturated compounds by contacting the feedstock and hydrogen at elevated temperature and pressure with a catalyst, solifidianism before use, and contains 820 wt. % of molybdenum trioxide and 26 wt.% hydroxy is 2,05,0 MPa, space velocity of the raw material from sulfur and unsaturated compounds 13 h-1, the ratio of hydrogen:feedstock 100150 nm3/m3.

The main distinctive feature of the invention is that when a thin catalytic aftertreatment of the benzene fractions containing moisture and tar, sulfur and unsaturated compounds by contacting the feedstock and hydrogen with a catalyst at elevated temperature and pressure using sulpicianus catalyst containing 820 wt.% trioxide of molybdenum and 26 wt.% oxides of cobalt and/or Nickel, the rest is aluminum oxide.

An additional distinguishing feature is that the process is carried out at a temperature 230280oWith the pressure 2,05,0 MPa, the space velocity of the raw material 13 h-1, the ratio of hydrogen:feedstock 100150 nm3/m3.

The present invention meets the condition of patentability "Inventive step" on the following basis. The prior art on the filing date for an invention it was not known that the set of features characterizing the present invention, leads to the solution of the aforementioned problem, namely, that in the process of fine catalytic aftertreatment can be used is xadow cobalt and/or Nickel. In result, it becomes possible not only to reduce the cost of the purification process, but also to make use of raw materials with a higher content of sulfur and unsaturated hydrocarbons.

Information confirming the possibility of carrying out the invention

The method according to the present invention is illustrated by the following examples.

Example 1.

Charged to the reactor 100 cm3catalyst containing 15 wt.% of molybdenum trioxide (Moo3) and 3.5 wt.% of cobalt oxide (COO), the remainder alumina. Top load sulfur in an amount of 5% by weight of the catalyst. Install the supply of hydrogen to 400 nm3/m3and begin heating the reactor up to 280oWith a gradually increasing pressure to 2.0 MPa. After exposure for 1 h under these conditions, reduce the temperature to 250oWith and at the same time raise the pressure up to 2.5 MPa. When reaching the preset parameters set the material with a bulk velocity 1 h-1and the ratio of N2: raw materials 150 nm3/m3. The raw material used benzene-toluene fraction of the following composition: benzene to 95.5 wt.%, toluene and 3.5 wt.%, xylenes 0.5 wt.%, ethylbenzene 0.5 wt.%, total sulfur 32 ppm, bromine number 0,08 Br2/100 g, moisture content 500 total sulfur content is of 0.6 ppm, bromine number - 0.02 g Br2/100 g, the amount of actual pitches of 5 mg/100 ml, the conversion of benzene to cyclohexane - 0,002%. The catalyst works 100 hours without a decrease in catalytic activity.

The table below shows other examples according to the method of example 1.

Examples 14 illustrate the operation of the method in terms of the present invention, examples 517 are shown for parameters outside the claimed conditions, example 18 method according closest analogue.

Example 5 shows that when using a catalyst with a lower content of Moo3in comparison with the present invention increase the content of total sulphur and bromine number in the hydrogenation product (compare with example 2). Example 6 shows that the use of a catalyst with a high content of Moo3in comparison with the present invention does not lead to further decrease in the content of total sulfur and reduce the bromine number in the hydrogenation product and therefore impractical (comparison example 3).

Example 7 shows that when using a catalyst with low content of oxides of cobalt and/or Nickel in comparison with the present invention increase the content of total sulphur and bromine number in the hydrogenation product (comparison with princely compared with the present invention does not lead to further decrease in the content of total sulfur and reduce the bromine number in the hydrogenation product and is therefore inadvisable.

Example 9 shows that the use of the catalyst containing the Moo3and Soo, without sulfatirovnie grey leads to a sharp increase in the conversion of benzene to cyclohexane (comparison example 4), which causes an undesirable loss of product.

Example 10 shows that the execution of the process at low temperature in comparison with the present invention leads to an increase in the content of total sulphur and bromine number in the hydrogenation product (comparison example 3). Example 11 shows that at higher temperatures compared to the claimed increases the conversion of benzene to cyclohexane (compare with example 2).

Example 12 it follows that the pressure in the process of purification compared with the present invention does not lead to further decrease in the content of total sulfur and bromine number in the hydrogenation product and because it is impractical (compare with example 2). Example 13 shows that carrying out the process under reduced pressure compared with the present invention leads to an increase in the hydrogenation product of total sulfur and bromine number (comparison example 3).

Example 14 shows that the reduction in flow rate in the process of purification compared to the real izobreteny 4). Example 15 shows that the increase in flow rate in the process of purification compared with the present invention leads to an increase in the content of total sulphur and bromine number in the hydrogenation product (comparison example 3).

From example 16, it follows that increasing the ratio of hydrogen:feedstock compared with the present invention does not lead to further decrease in the content of total sulfur and bromine number in the hydrogenation product and because it is impractical (comparison example 1). Example 17 shows that the decrease in the ratio of hydrogen:feedstock compared with the present invention is the cause of the increase in the content of total sulfur and bromine number in the hydrogenation product (comparison example 3).

Example 18 shows the implementation of the method the fine catalytic purification of benzene fractions from sulfur and unsaturated compounds according to the known method is the closest analogue. The content of total sulphur and bromine number in the hydrogenation product increase dramatically, which affects the quality of the benzene (comparison example 1).

Thus, the above examples show that the implementation of this method thin catalytic purification of benzene frac feedstock with a higher content of total sulfur and bromine number upon receipt of the product of the required quality (total sulfur content less than 1 ppm, the bromine number of not more than 0.002 g Br2/100 g, the conversion of benzene to cyclohexane, not more than 0,002%) and to reduce the cost of the process due to the use of cheaper catalyst.

The most successful present invention can be applied in the petrochemical industry for the extraction of aromatic hydrocarbons, in particular benzene from pyrolysis condensate fraction or crude coking benzene.

1. Way thin catalytic purification of benzene fractions from sulfur and unsaturated compounds by contacting the feedstock and hydrogen with a catalyst based on aluminum oxide at elevated temperature and pressure, wherein the used catalyst, sulpicianus before use, containing 8-20 wt.% trioxide of molybdenum, 2-6 wt.% oxide of cobalt and/or Nickel, the rest is aluminum oxide.

2. The method according to p. 1, wherein the process is carried out at a temperature of 230-280oC, pressure of 2.0-5.0 MPa, the space velocity of the feedstock 1-3-1, the ratio of hydrogen: the raw material is equal to 100-150 nm3/m3.

 

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