Method for isolation of aromatic c6-c9-hydrocarbons and reformed gasoline component from gasoline fraction reformat

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: method consists in liquid-phase multistage countercurrent extraction of aromatic hydrocarbons from gasoline fraction reformat with sulfolane containing 0.2-2% water at sulfolane/feed volume ratio (1.6-2.0):1 and temperature 30-50°C, followed by removal of nonaromatic hydrocarbons remaining in extracted phase via extractive-azeotropic rectification with sulfolane and high-octane lower aliphatic alcohols at ratios (0.55-0.70):1 and (0.05-0.08):1 by weight, respectively.

EFFECT: enabled production of benzene, toluene, xylenes, and sum of C9-arenes and reformed gasoline component meeting environmental requirements.

1 dwg, 5 tbl, 2 ex

 

The invention relates to the refining industry and can be used for separation of aromatic hydrocarbons From6-C9from reformate gasoline fraction with simultaneous achievement reformulating environmentally friendly component of gasoline.

In accordance with European specifications for motor gasoline Euro-3, in force since 2001, the total content of aromatic hydrocarbons in gasoline should not exceed 42% (vol.), including benzene is not more than 1% (by vol.). The program Euro-4, which should be introduced in 2005, provides for further reduction of the amount of arenes in gasoline to 30% (vol.) [1].

At the same time, the main component of the Russian automotive gasoline is reforming catalysate with a concentration of arenes to 65-68% (vol.), including benzene, up to 8% (vol.).

Benzene and toluene are extracted mainly from reformate fraction 62-105°and total xylenes, and part of the toluene from reformate fraction 105-140° [2, 3]. The disadvantage used in industry methods of production of benzene and its homologues, the necessity of the preliminary distillation separation of raw materials to usagepage gasoline fraction with subsequent separately administered by the catalytic reforming process and extraction or extractive distillation leads the increase in required capital investment and energy consumption.

Arena C8there is also from the xylene fraction catalyzate reforming method simple distillation [4]. In this case, loss of xylenes in an industrial setting because of their contact with the distillate composition azeotropes with saturated hydrocarbons with a boiling point 132-152°and with kubovy the remainder of the column selection total xylenes reach 38%.

Reduce capital and energy costs may result in extraction of the allocation of arenes With6-C9from reformate broad gasoline fraction NK - 180°followed by purification from impurities saturated hydrocarbon extractive-azeotropic rectification.

Closest to the technical essence and the achieved effect of the present invention, the method of selection arenes from hydrocarbon fractions by extraction with sulfolane followed by extractive distillation (Pot-05862, the Netherlands, 1982; S.A., v.97, 130410). The disadvantage of this method, adopted as a prototype, as most industrial processes solvent extraction of aromatic hydrocarbons, is a large flow of recirculating flow (risaykl) - up to 100% wt. and above raw materials, Athanasios their extract phase, in which the concentrated admixture of saturated hydrocarbons along with a significant number of the most volatile arena - benzene. Risaykl return the extraction column, resulting in the most difficult to remove saturated hydrocarbons not removed from the cycle, decreases the performance of the extractor, decreasing the concentration of the extractant in the system and, as a consequence, the selectivity of the separation of hydrocarbons.

One of the purposes of the present invention is the complete exclusion of recycled hydrocarbon streams. This goal is achieved when you remove saturated hydrocarbons remaining in the extract phase, using extractive-azeotropic distillation with the same selective solvent and the extraction step - by sulfolane, and with high-octane aliphatic alcohol as azeotroping component, not in need of regeneration. The distillate of the column extractive-azeotropic distillation is combined with sugar, obtained in the extraction step, and the combined product is environmentally friendly reformulating component of gasoline.

The raw material used stable katapusan reforming faction 62-180°With the following composition, % wt.: benzene - 6.9, toluene - 22.5, arena C8- 17,2, arena With9- 9.0, saturated hydrocarbons - 44.4.

Conditions multistage countercurrent extraction arenes from reformate gasoline fraction is presented in table 1 and the results obtained in table 2. The raffinate, udovletvor what would be modern and future environmental requirements on the content as benzene, and the amount of arenes obtained under conditions of both experiments, however, the yield of raffinate in experiment No. 1 is low, as in the extract remains a lot of saturated hydrocarbons.

Therefore, subsequent experiments extractive-azeotropic distillation was performed using the extract phase obtained in experiment No. 2. The process conditions of the extractive-azeotropic rectification is presented in table 3 and the results in table 4.

Example 1.

In the lower part of the extraction column efficiency 5 theoretical stages serves reforming catalysate FR. 62-180°With (1000 g/h), containing 55.6% wt. arenes, the composition of which is given above. In the upper part of the extraction column at the same temperature with a speed of 2000 g/h serves sulfolane containing 0.2% wt. water.

In the multistage countercurrent extraction after stable mode selected raffinate and extract phases, the composition of which is analyzed by gas chromatography. According to the analysis calculated the yield and composition of the raffinate, extract and the degree of extraction of arenes. The results of the experiment are given in table 2, the experience No. 1.

Example 2.

In the lower part of the extractor efficiency 7 theoretical stages serves reforming catalysate FR. 62-180°With the same composition with a speed of 1000 g/h at a temperature of 30°C. In the upper part of the extractor is served with soon the TEW 1600 g/h at a temperature of 50° With sulfolane containing 2% wt. water.

In the countercurrent extraction after stable mode is selected raffinata phase, which is washed with water from the impurities of the extractant. The carrying amount of the extract phase is sent to the extractive column-azeotropic rectification efficiency 15 theoretical plates. The column is irrigated from above sulfolane (280 g/h), and is supplied from the bottom azeotropically component - ethanol (32 g/h). The distillate of the column extractive-azeotropic distillation is combined without regeneration azeotroping component from the raffinate of the extraction column and analyzed. From VAT residue column extractive-azeotropic distillation using a sharp water vapor is distilled over aromatic hydrocarbons, which are secondary rectification separated into benzene, toluene, arena C8and C9.

The material balance of the combined allocation process arenes With6-C9from reformate gasoline fraction in example 2 are presented in table 5. The combined stream of the raffinate and the distillate of the column extractive-azeotropic distillation may be used as reformulating environmentally friendly component of gasoline. The basic substance content in the product aromatic hydrocarbons amounted, % wt.: benzene - 99.9, toluene - 9.95, arena C8- 99.5.

Schematic diagram of the combined allocation process arenes from reformate gasoline fraction is represented in the drawing. In the lower part of the extractor (1) is served raw, in the upper - sulfolan. From rafinate phase in the extractor (2) restrained water sulfolan. In a distillation column (3) of aqueous solution of sulfolane Argonauts water is returned to the extractor (2).

From the extract phase in the extractive column-azeotropic rectification (4), in the lower part of which is ethanol, and the top - sulfolan, Argonauts azeotrope of ethanol saturated with the hydrocarbon extract phase. The distillate of the column (4) is combined with the raffinate and is used as a component of gasoline without regeneration of ethanol. From VAT residue column (4) in a distillation column (5) using a sharp water vapor uparivaetsya extract. Sulfolan after cooling in the heat exchanger partially served on irrigation columns (4)and a large part is returned to the extractor (1). From the extract in distillation columns (6), (7) and (8) respectively emit benzene, toluene and total xylenes.

Table 1

Conditions of experiments multistage countercurrent extraction arenes from reformate gasoline fraction sulfolane
Parameters the market process No. of experiments
12
The number of theoretical stages57
Temperature, °:  
the top of the extractor5050
the bottom of the extractor5030
The mass ratio of sulfolane:raw materials2:11.6:1
The water content in sulfolane, % wt.0.22.0

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Table 3

Conditions of experiments extractive-azeotropic distillation with removal of saturated hydrocarbons from the extract phase of experience No. 2
The process parametersNo. of experiments
2and2in
Mass to extractant ratio:  
sulfolan0.55:10.7:1
ethanol0.05:10.08:1
The mass ratio in the calculation of the reformate:  
sulfolan0.22:10.28:1
ethanol0.02:10.032:1
The final temperature of the cubic residue, °180180

Table 4
Cleaning results arenes extractive-azeotropic rectification
The process parametersNo. of experiments
2I2s
The output of the hydrocarbon portion of the distillate to reformat, % wt.4.85.5
The content of arenes, % wt.:  
the hydrocarbon portion of the reformate19.812.0
VAT residue98.499.7
The degree of extraction, % wt.:  
the amount arenes99.099.1
including: benzene94.294.0
toluene99.899.9
arena C8+100100
The degree of extraction in the combined process, % wt.:  
the amount of arena the 67.367.4
including: benzene89.589.3
toluene76.876.9
arena C869.069.0
arena924.024.0

Table 5

The material balance of the combined allocation process arenes With6-C9+from catalyzate reforming of gasoline fractions
WardConsumption
Componentwt.%.Componentwt.%.
Reformate100Component of gasoline65.4
including: benzene6.9Benzene6.17
toluene22.5Toluene17.3
arena C817.2Arena C811.87
arena9+9.0Arena9+2.16
saturated hydrocarbons44.4  
Ethanol3.2  
Sulfolan with 2% masodi188  

Sources of information

1. Kaminsky ET, Khavkin VA Deep oil processing: technological and economic aspects. - M.: Publishing house "Technika". LLC "TOMOGRAPH", 2001, 384 S.

2. The economy of the production of aromatic hydrocarbons / Angelidou, Vilimek, Mladenov and others - M.: Tsniiteneftehim, 1978, 68 S.

3. Gail A.A., Som V.E., Warsaw O.M. Aromatic hydrocarbons: Selection, application, market. The Handbook. - SPb: Hemostat, 2000, 544 S.

The method of separation of aromatic hydrocarbons From6-C9from reformate gasoline fractions by extraction with sulfolane containing 0.2-2.0 wt.% water, characterized in that the extract phase is subjected to extractive-azeotropic distillation in the presence of sulfolane and high-octane aliphatic alcohol, preferably ethanol, and the top product of the column extractive-azeotropic rectification without regeneration azeotroping component is used as a component reformed gasoline.



 

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