Petroleum sulfide oxidation process

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: oxidation is performed at 20-60°C with hydrogen peroxide aqueous solution in presence of molybdenum-containing catalyst, in particular molybdenum bis-alkylsulfoxide peroxo complexes.

EFFECT: increased yield of sulfoxides, oxidation selectivity, and oxidation rate.

2 tbl, 6 ex

 

The invention relates to improvements in the method of oxidation of sulfides oil and can be used in the refining and petrochemical industries.

Currently sulfides oil mainly oxidize aqueous solution of hydrogen peroxide in the presence of various catalysts.

There is a method of oxidation of sulfides oil with an aqueous solution of hydrogen peroxide in the presence of a catalyst of sulfuric acid (USSR author's certificate No. 206579. BI No. 1, 1968). The disadvantages of this method are the high corrosivity of sulfuric acid and low depth conversion of sulphides in the sulfoxidov (65-68%).

It is known that as a catalyst for oxidation of sulfides oil use carbonyl compounds (USSR author's certificate No. 774173. BI No. 20, 1989). The disadvantages of this method are the high consumption of catalyst (1-5% for raw materials), low selectivity (70-72%) and low oxidation rate.

There is also known a method of oxidation of sulfides oil in the presence of a catalyst compounds of molybdenum and calcium (USSR author's certificate No. 524799. BI No. 30, 1976). A significant disadvantage of this method is the large loss of catalyst dissolving it in the organic phase and the low oxidation rate.

The closest in technical essence and the achieved result is a method (prototype), where chislenie sulfides oil and hydrogen peroxide is carried out in the presence of paracomplex molybdenum (RF patent No. 2238935. BI No. 30, 2004).

Oxidation of sulfides oil in the presence of paracomplex molybdenum is carried out at 60°C. the duration of the oxidation 20-40 minutes. Depth conversion of sulphides in the sulfoxidov 87-92%. The flow of catalyst 0,003-0,005% of the mass. for raw materials.

The aim of the invention is to increase the degree of transformation of sulphides in the sulfoxidov, reducing the duration of oxidation and consumption of catalyst.

This goal is achieved by oxidation of sulfides with hydrogen peroxide in the presence of bis-alkylsulfonic of paracomplex molybdenum.

The method is as follows. Dissolve 15 g of Moo3(or 18.0 g H2MoO4) in 1 liter of 10%aqueous hydrogen peroxide solution at a temperature of 60-70°C. When hydrogen peroxide reacts with molybdenum oxide and formed paracomplex molybdenum. Then the resulting reaction mass is then cooled to 25-30°and under intensive stirring and cooling poured in 400-500 ml of dimethyl sulfoxide or other sulfoxidov (cannot pour on the contrary - in the solution proximaldistal acid sulfoxidov. In this case, a possible release of the reaction mass). The reaction mass is poured with a rate that the temperature did not exceed 30°C. For a sharp reduction in temperature it is necessary to provide for the supply of cold water to cool the reactor. When is aimogasta proximaldistal acid with alkylsulfonyl formed bis-alkylsulfonate paracomplex molybdenum, containing in the inner sphere sulfoxidov as ligands. Being in the inner sphere of the complex, sulfoxidov significantly enhance the catalytic activity of the latter in the reactions of oxidation of sulphides. The yield of bis-alkylsulfonic of paracomplex molybdenum formula MoO(O2)2LL', where L and L' are the same or different sulfoxidov, depending on the nature of sulfoxidov from 70 to 80% mole. The obtained product was analyzed by spectrophotometric methods. In the infrared region of the spectrum observed intense absorption band at 810, 1090,2350 cm-1characteristic of sulfoxidov (Shigeru UAE. The chemistry of organic sulfur compounds. M.: Chemistry, 1975. - 401 C.) and for paracomplex groups (in cm-1):

(Volnov I.I. Paracomplex chromium, molybdenum, tungsten. M.: Nauka, 1989. 104 C.) on the Basis of experimental data and literature sources it is assumed that the obtained bis-alkylsulfonate paracomplex molybdenum have the following structural formula:

where R and R' is an alkyl radical C-C8normal structure or ISO-structure.

As ligands LL'can be sulfoxidov having a cyclic structure

3-C12) mainly saturated character. Good results concentrate sulfoxidov obtained from crude oil and having a structure as described above. It should also be noted that the catalyst can be obtained by using any molybdenum-containing compounds: Moo3N2MoO4, molybdate ammonium stearate, molybdenum, molybdenum naphthenate, acetylacetonate molybdenite, phosphorus molybdenum acid and other Oxidation is carried out in chetyrehkolkoy flask (reactor)equipped with a mechanical stirrer, thermometer, reflux condenser and addition funnel. In the flask is charged with raw material and heated to a predetermined temperature. In the heated raw material under stirring enter all of the hydrogen peroxide and catalyst and maintained at a given temperature. The start of the response counts with time added to the reaction cooled mass of the calculated amount of hydrogen peroxide and catalyst. Upon completion of the reaction the contents of the reactor are cooled and separated the organic layer (oxidate) from water. In oxidate determine the content sulfoxide sulfur non-aqueous potentiometric titration (Wimer D.C. Titration of sulfoxide in Acetic Anhydride. Anal. Chem. 1958. V.30. no.1. P.2060).

As raw materials use diesel and oil fractions of high-sulphur oil and concentrate self the Dov. The sulphide concentrate is produced by extraction of 86%sulfuric acid (Chertkov AB, Spirkin VG, Demichev NR. The use of sulphuric acid for the extraction of organic sulfur compounds from petroleum fractions. - Petrochemicals, 1965, volume 5, No. 5, s). The content of sulfide sulfur in the raw materials is determined by the potentiometric method of iodometry (Halpern GD, Girin, G.P., Lucanica VG Methods of analysis of organic compounds of oil, mixtures thereof and derivatives.- M.: Nauka, 1969, 95 S.)

The invention is illustrated by the following examples.

Example 1. To 100 g of the fraction of diesel fuel Arlan oil boiling within 190-360°containing 0.9% of the mass. sulfide sulfur is added at 60°With one dose of 3.3 ml of a 27%aqueous hydrogen peroxide solution and 0.001 g of bis-alkylsulfonic of paracomplex of molybdenum derived from ammonium molybdate and dimethyl sulfoxide with the aforementioned method. After 10 minutes of mixing in the reactor with stirrer get 100,2 g oxidate content sulfoxide sulfur 0,88% of the mass. The depth of oxidation of sulphides in the sulfoxidov or 97.7%.

Example 2. To 100 g diesel fraction Chekmagushsk oil boiling within 190-280°and containing 1% sulfide sulfur is added at 40°With one dose of 3.1 ml of 30%aqueous hydrogen peroxide solution and 0.0015 g of bis-alkylsulfonic of paracomplex molybdenum, obtained from OK the si molybdenum and diethylsulfoxide with the aforementioned method. After 7 minutes of mixing in the reactor with stirrer get 100 g of oxalate content sulfoxide sulfur 0,98% of the mass. Depth conversion of sulphides in the sulfoxidov 98,0%.

Example 3. To 100 g of low-viscosity distillate oil fraction with temperature limits boiling 300-400°containing 0,77% of the mass. sulfide sulfur is added at 60°With one dose of 3.1 ml of 30%aqueous hydrogen peroxide solution. At the same time in the reaction mass contribute 0.0008 grams bis-alkylsulfonic of paracomplex of molybdenum derived from molybdenum acid and dibutylsebacate with the aforementioned method. After 10 minutes of mixing in the reactor with stirrer get 100,2 g oxidate content sulfoxide sulfur 0,75% of the mass. The depth of oxidation of sulphides in the sulfoxidov of 97.8%.

Example 4. To 100 g of distillate sreznevskii oil fraction with temperature limits boiling 350-420°and containing 0,87% of the mass. sulfide sulfur is added at 20°With one dose of 3.6 ml of 25%aqueous solution of hydrogen peroxide. Simultaneously in the reaction mixture contribute 0.002 g of the catalyst complex MoO(O2)2LL', where L and L' - sulfoxidov hexylthiophene. After 10 minutes of mixing in the reactor with a mechanical stirrer get oxidat content sulfoxide sulfur 0,86% of the mass. The depth of oxidation of sulphides in the sulfoxidov is 98,7%.

Example 5. To 95,5 g to the of centrata sulphide content of sulfide sulfur to 8.5 wt. -%, selected from the diesel fraction Arlan oil boiling within 260-360°C, add at room temperature (+25° (C) 0,0095 g (0.001% of the mass.) catalyst complex obtained from molybdenum acid and oil sulfoxidov. Then added dropwise 32,0 ml of 25%aqueous solution of hydrogen peroxide. The reaction mixture under stirring samorazogreva and oxidation ends 10 minutes Content sulfoxide sulfur in oxidized product of 8.3% of the mass. The depth of oxidation of sulphides in the sulfoxidov is 98.8%.

Example 6. To 87,7 g asphalt-free oil residual oil fraction containing 1,04% of the mass. sulfide sulfur, at 25°add one dose of 3.6 ml of 25%aqueous solution of hydrogen peroxide. Simultaneously in the reaction mixture contribute 0.0008 g (0,0001% of the mass.) catalyst complex obtained from oxide of molybdenum MoO3and sulfoxide of tiiana according to the method described above. After 12 minutes, stirring receive oxidat content sulfoxide sulfur 1,02% of the mass. The depth of oxidation of sulphides in the sulfoxidov is 98,1%.

For comparison conducted experiments on the oxidation of diesel fraction Arlan oil containing 2.1% of the mass. General and 0.9% of the mass. sulfide sulfur, and hydrogen peroxide in the presence of paracomplex derived from various compounds of molybdenum. The results of the experiments are shown in the table is 1. Table 2 presents data on the oxidation of this substrate in the same conditions in the presence of bis-alkylsulfonic of paracomplex molybdenum. As can be seen from the tables, when using bis-alkylsulfonic of paracomplex molybdenum as a catalyst for the depth conversion of the sulfides in the sulfoxidov increases by 5-8%, duration of oxidation decreases to 3-5 times the amount of catalyst in 3 times, also increases the selectivity of the reaction (decreases formation of acidic products and sulfones).

Table 1

Oxidation of sulfides oil distillate in the presence of paracomplex molybdenum

In table. 1 and 2 the temperature 60°With the amount of hydrogen peroxide to 1.2 mol per 1 g-atom of sulfide sulfur.
Paracomplex molybdenum obtained by dissolving the peroxideThe number of paracomplex molybdenum, % mass. from raw materialsThe duration of oxidation, minutesContent sulfoxide sulfur oxidate, % of the mass.The content of sulfones in oxidate, % of the mass.The acidity of oxidate, g KOH/lDepth conversion of sulphides in the sulfoxidov, %
Acetylacetonate, molybdenum0,0050400,79 0,10,387,7
Of ammonium molybdate0,0035400,830,20,492,2
Molybdenum acid0,0025200,840,20,193,3
The molybdenum naphthenate0,0030200,82UTS.0,1to 91.1
Oxide of molybdenum0,0030300,83UTS.0,292,2
Stearate molybdenum0,0035400,78UTS.0,286,6

Table 2

Oxidation of sulfides oil distillate in the presence of bis-alkylsulfonic of paracomplex molybdenum
Bis-alkylsulfonate paracomplex molybdenum obtained by dissolving the peroxideLisandvaartuse componentThe number of desulfated of paracomplex molybdenum, % mass. from raw materialsThe duration of oxidation, minContent sulfoxide sulfur oxidate, wt.%The contents of the su is Ivanov in oxidate, wt. -%The acidity of oxidate, g KOH/lDepth conversion of sulphides in the sulfoxidov, %
Acetylacetonate molybdeniteteofan sulfoxide0,001150,87UTS.0,296,7
Of ammonium molybdatethe sulfoxide0,001100,880,050,197,7
Molybdenum aciddibutylated0,0008150,89UTS.0,198,8
The molybdenum naphthenateoil sulfoxidov0,000770,88UTS.0,198,7
Oxide of molybdenumdiethylsulfoxide0,0008100,870,050,196,7
Stearate molybdenumoil sulfoxidov0,00170,860,050,295,5

The method of oxidation of sulfides oil and hydrogen peroxide in the presence of a molybdenum-containing catalyst, characterized in that as to what telesfora use bis-alkylsulfonate paracomplex molybdenum and the reaction is carried out at 20-60° C.



 

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17 cl, 2 tbl, 2 ex

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3 cl, 15 ex

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2 cl, 2 tbl, 18 ex

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