Light petroleum product catalytic desulfurization process

FIELD: petroleum processing.

SUBSTANCE: catalytic removal of sulfur compounds, including mercaptans, hydrogen sulfide, sulfides, and the like, from light petroleum product, in particular gasolines, kerosene, diesels, and others, is accomplished by passing crude material at 20-30°C and volumetric flow rate 0.1 h-1 through catalytic system, said catalytic system being consisted of manganese and iron-containing cluster compound of general formula C18H15MnFeOCl2 deposited on anhydrous clinoptilolite at weight ratio 1:1.

EFFECT: enabled production of high-quality product from which up to 99 wt % sulfur is removed at ambient temperature.

5 tbl, 4 ex

 

The invention relates to the refining, in particular for cleaning light oil products, i.e. gasoline, kerosene, diesel fuel, etc. from sulfur compounds, including mercaptans, hydrogen sulfide, sulfides, etc. in the presence of catalysts.

The known method for the catalytic desulfurization of light oil in the presence of clinoptilolite containing the additive chromium oxide (SU 1305152, 23.04.1987, C10G 25/05).

However, the degree of desulfurization known way insufficient.

Closer to the claimed method according to essence and the achieved result is a method of purification of hydrocarbon mixtures from sulfur compounds by treatment with compounds of transition metals with subsequent separation of the purified mixtures and exhaust connections. As compounds of transition metals using metal-organic compounds, π-complexes or salts of these metals and the resulting reaction mixture is treated with chelating agents. An example of the used catalyst are cyclopentadienylmanganese Cr, Mo, W, Ni, Co, Mn, Fe or mixtures thereof. The process is conducted at 80-150°C. (SU 491683, 15.11.1975, 10G 29/06).

The disadvantage of this method is the necessity of heating the feedstock, i.e. excessive costs, and the possibility of cleaning materials only with a relatively low content of the source connected to the deposits of sulphur (total sulfur to 1.42%, mercaptane sulfur up to 0,09%).

The purpose of this invention is to simplify the process, its cheaper, as well as providing cleaning materials with high initial sulfur content.

This goal is achieved by a method of cleaning light oil from sulfur compounds sulfur by feeding the feedstock at a temperature of 20-30°With a bulk velocity of 0.1 h-1through a catalytic system consisting of manganese-iron cluster compounds of General formula C18H15MnFeOCl2printed on anhydrous clinoptilolite mass ratio of cluster connection: clinoptilolite, which is 1:1.

In the interaction of sulfur-containing compounds of different structure with a catalytic systems consisting of heterocyclic cluster centre activated by interaction with clinoptilolite acid-the main centres, there is a strong donor-acceptor interaction. As a result of this interaction the basic metal centers are restored, and the acid centers are oxidized.

Therefore, the sulfur compounds in these centers are restored to elemental sulfur, and, in turn, the acid sites (metals) restored the main centers of clinoptilolite.

The presence of clustered organic compound is one ligand and chlorine atoms play in oxidation-reduction process the role of stabilizer of the cluster, which prevents its collapse in such a complicated process.

As a result of regenerative processes, the formation of elemental sulfur with a purity of up to 0.01 wt.% of all sulfur compounds in General they are removed from the feedstock to 99 wt.% and initial content up to 5 wt.%

The method is carried out as follows.

As raw materials take a light oil, such as gasoline, diesel fuel, kerosene, and others), containing sulfur compounds (mercaptans, sulfides, hydrogen sulfide, etc.), and at a temperature of 20-30°served at atmospheric pressure with a bulk velocity of 0.1 h-1on the surface of the catalytic system consisting of 1 part of manganese-iron cluster compound and 1 part of anhydrous natural clinoptilolite. After the passage of the feedstock through the layer of the catalytic system at the end of the column is observed the formation of a yellow powder of elemental sulfur, which is washed with an alcohol solvent, for example ethanol. The result is a dry product is elemental sulfur.

The proposed method is illustrated by the following examples.

Example 1. The preparation of the catalytic system: manganese-iron containing the cluster compound of General formula C18H15MnFeOCl2- waterless natural clinoptilolite.

Take 200 g of the compounds of General formula C18 H15MnFeOCl2, dissolve it in 500 ml tetrahydrofurane solvent and slowly added to 200 g of dehydrated natural clinoptilolite. The mixture was kept during the day. The mixture is then heated to 65°With removal of the solvent. The result is a dry homogeneous catalytic mass of gray. The dry weight of 0.1 catalytic mass is 100 g with a particle size of 0.1 mm

Example 2.

Take 4 liters of gasoline containing 0,154 g/l of sulfur compounds, and at a temperature of 20-30°and atmospheric pressure with a bulk velocity of 0.1 h-1serves on the surface with a volume of 0.2 cm3catalytic system consisting of 1 part of manganese-iron cluster compound and 1 part of anhydrous natural clinoptilolite. After the passage of the feedstock through the layer of the catalytic system at the end of the column is observed the formation of a yellow powder of elemental sulfur, which is washed with 20 ml of 99%ethanol. The result 2,12 g of dry product is elemental sulfur (exit 95 wt.%).

Other examples of cleaning various grades of sulfur gasoline is given in table 1

Table 1 shows data on the effectiveness of the proposed catalytic system for the desulfurization of various grades of sulfur to elemental sulfur gasoline. These tables show that the proposed catalyti the mini system works well there where gasoline contains 0,126-0,964 g/l at the same time sulfur-containing compounds of different structure and hydrogen sulfide.

Example 3. The impact of the process on the efficiency of desulfurization of sulfur gasoline.

The main parameters of the process of desulfurization and the ratio of reactants is taken from example 2. Changing only the temperature of the process, which is 20°C. After completion of the process was obtained 206 g of elemental sulfur, which corresponds to a yield of 95 wt.%.

Other examples are shown in table 2.

Table 2 provides data showing the effects of process temperature on the cleaning efficiency of sulfur gasoline.

When it is detected that the temperature of the process seriously affects servicesalso the ability of the catalyst. The desulfurization process should be carried out in the temperature range 20-30°C.

Example 4. The influence of the feed rate of sulfur gasoline on the efficiency of desulfurization.

The main parameters of the process of desulfurization and the ratio of reactants is taken from example 2. Changing only the volumetric feed rate of sulfur gasoline, which is equal to 0.2 h-1.

The result is a dramatic reduction in the formation of elemental sulfur, a number which in this case is 1.07 g, which corresponds to 49% of its potential content.

The rest ol the measures presented in table 3.

Table 3 contains data showing the dependence of the rate of feed sulfur gasoline on the efficiency of the catalytic desulfurization. Data show that speed is of fundamental value, i.e. the lower the speed, the more effective cleaning.

Table 4 presents optimal conditions for catalytic sweetening to elemental sulfur of various grades of gasoline.

Table 5 presents the composition of the sulfur compounds in naphthalenide.

Results purification of other light oil similar results in clearing of gasoline.

The presented results for cleaning light oil, it follows that the claimed method allows to obtain high-quality refined products with a high degree of extraction of sulfur - up to 99 wt.% at room temperature.

Table 1
The efficiency of the catalytic purification systems of different brands of sulfur to elemental sulfur gasoline
No.Brand sulfur gasolineSulfur content, g/lThe catalyst Mn-Fe-containing clusterMn-Fe-containing clinoptiloliteClinoptiloliteThe volumetric feed rate, h-1 Process temperature, °The degree of obesserivaniya, %
1Naphtha gasoline with 54 PTS0,964+1:11:2+0,05

0,05

0,05

0,05
30

30

30

30
48

80

96

12
2Straight-run gasoline with 56 PTS0,672+1:11:2+0,05

0,05

0,05

0,05
30

30

30

30
59

68

95,8

17
3Naphtha gasoline with 52 PTS0,154+1:11:2+0,1

0,1

0,1

0,1

0,1
30

28

28

28

28
97

99

99

99

15
4The condensate with 60 PTS0,275+1:11,2+0,1

0,1

0,1

0,1

0,1
30

28

28

28
98

99

99

99

99
5Stable azobenzene with 62 PTS0,126+1:11,2+0,1

0,1

0,1

0,1
30

28

8

28
98

99

99

99

Table 2
The influence of the process temperature on the efficiency of the catalytic desulfurization of various grades of sulfur gasoline
No.Brand sulfur gasolineSulphur content, mg/lThe amount of catalyst, %The volumetric feed rate of raw materials, h-1Process temperature, °The degree of obesserivaniya, %
1Naphtha gasoline with 54 PTS0.964200,050

15

20

25

28

30

40
14

29

47

83

88

96

96
2Straight-run gasoline with 56 PTS0,672200,050

15

20

25

28

30

40
21

33

54

89

91

96

96
3Naphtha gasoline with 52 PTS0,154200,10

15

20

25

28

30

40
22

43

78

89

99

99

99
4The condensate with 60 PTS0,275200, 0

15

20

25

28

30

40
19

37

71

79

95

95

95
5Stable azobenzene with 62 PTS0,126200,10

15

20

25

28

30

40
34

67

83

89

99

99

99

Table 3
The dependence of the rate of feed sulfur gasoline on the efficiency of the catalytic desulfurization
No.Brand sulfur gasolineSulfur content, g/lThe ratio of the catalyst to sulfur gasolineThe volumetric feed rate, h-1Process temperature, °The degree of desulfurization, %
1Naphtha gasoline with 54 PTS0,9641287
0,12864
1:20,052896
1:10,012896
0,12896
2Straight-run gasoline with 56 PTS0,67212819
0,12878
1:20,052895,8
0,012896
1:10,52896
3Naphtha gasoline with 52 PTS0,15412834
0,12899
1:20,052899
1:10,012899
0,12899
4The condensate with 60 PTS0,27512824
0,12899
1:20,052899
0,012899
1:10,12899
5/td> Stable azobenzene with 62 PTS0,1261:212849
0,12899
1:10,052899
0,012899
0,12899

Table 4
Optimal conditions for catalytic purification to elemental sulphur various maarof gasoline
No.Mark sulfur gasolineThe actual octane number (mm)Sulfur content, g/lThe ratio of the catalyst to sulfur gasolineThe volumetric feed rate, h-1Process temperature, °The degree of desulfurization, %Process temperature, °The degree of desulfurization, %
1Naphtha gasoline with 54 PTS540,9641:20,0530960,0456
2Straight-run gasoline with 56 PTS0,6721:20,053095,80,04of 57.5
3Naphtha gasoline with 52 PTS520,1541:10,128990,0156
4Gasolines with 60 PTS600,2751:10,128980,0161,8
5Stable azobenzene with 62 PTS620,1261:1^0,128990,0164

Table 5
The composition of the sulfur naphtha gasoline sulfur
No.Brand sulfur gasolineThe density of the P20Fractional compositionGeneral. The bundle. sulfur, g/l

.
for H2Sfor CH3SHC2H5SHfor (C2H5)2SSum4H4S and C3 -C7With6H5SHFor (C6H4)2S
TNKTKKg%g%g%g%g%g%g%
lNaphtha gasoline with 54 PTS (MM) Kazakhstan0,713401800,9640,16318,030,27528,520,24925,320,14214,23to 0.0323,320,0616,320,0414,25
2Straight-run gasoline with 56 PTS (MM) Kazakhstan0,718421860,6720,07911,750,0558,180,09113,540,16928,130,096of 14.280,08712,950,07511,16
3Naphtha gasoline with 52 PTS (MM) Dagestan0,715381860,1540,01711,030,028/td> 18,180,03120,130,04327,930,0159,740,0127,790,0085,19
4Naphtha gasoline with 54 PTS (MM) Dagestan0,713401900,1780,01910,070,03016,350,03318,120,05631,160,02011,130,0158,120,009of 5.05
5Stable with 62 PTS (MM) Tyumen0,706321650,3760,07419,480,04913,030,10728,450,08622,470,0225,0450,0205,120,0286,40
6Stable with 60 PTS (MM)0,704381400,2750,04315,63being 0.036to 13.09of 0.08129,450,05821,090,025a 9.09-0,0207,280,0124,36
7Stabilin the th with 64 PTS (MM) Novosibirsk-Uzbekistan 0,698291420,1260,0129,520,2923,01in,02519,840,03729,890,0118,730,010to 7.930,0021,58

Way catalytic cleaning light oil from sulfur compounds by treatment on the catalytic system containing transition metal compounds, characterized in that the catalytic system used a system consisting of manganese-iron cluster compounds of General formula C18H15MnFeOCl2printed on anhydrous clinoptilolite mass ratio of cluster connection:clinoptilolite, which is 1:1, and the process is conducted at a temperature of 20-30°With a bulk velocity of the feedstock of 0.1 h-1.



 

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