SU1616908A1 - Method of producing dialkylsulfides - Google Patents

Abstract

The invention relates to disulfides, in particular to the preparation of dialkyl sulfides. The goal is to expand the resource base, reduce the cost and simplify the process. The preparation is carried out from high-sulfur gas condensate, which is rectified into a broad fraction of light hydrocarbons and stable condensate, separated from the last fraction of hydrocarbons NK-128 ° C and / or NK-139 ° C and / or NK-200 ° C by distillation in distillation columns , process the fractions separated from the stable condensate with an aqueous solution of alkali. The resulting base-alkaline solution of mercaptides is treated with alkyl halide, preferably ethyl bromide in the presence of boron fluoride. The resulting mixture of dialkyl sulfides is separated from the aqueous-alkaline solution, and the target products are separated by distilling the mixture into fractions, ° C: NC — 62-93-125-143-150-165-187-208-232. 1 hp f-ly, 1 ill., 1 tab.

Description

The invention relates to the technology of processing sour gas condensates to obtain dialkyl sulfides and can be used in gas, chemical, oil refining and petrochemical industries.

The purpose of the invention is to expand the resource base, reduce the cost and simplify the process.

The goal is achieved in the method of producing dia, -1 alkyl sulphides from sour condensate by rectifying it into a wide fraction of light hydrocarbons and a stable condensate, separating from the last hydrocarbon fractions

NK-128 0, and / or PK-139 ° C, and / or NK-200 C, containing the target products, by distillation in distillation columns with subsequent processing of the fractions separated from the condensate with an aqueous alkali solution, the resulting alkaline aqueous solution of mercaptides is subjected to halide treatment by al-: kilo in the presence of bo-loride., pa, the resulting mixture of dialkyl sulfates is separated from the aqueous-alkaline solution, and the individual dialkyl sulfides are separated by re-blending

fraction NK-62 C - 93 ° C - 1

125 ° С - 43 ° С

 187 С - 208 ° С - 232 ° С.

150 C - I65 ° C 05

ABOUT)

with about

00

In this case, ethyl bromide is used as alkyl halide.

The drawing shows a schematic diagram of the implementation of the method for producing dialkyl sulfides from high-sulfur gas condensate.

The feedstock entering the plant via line 1 is subjected in block 2 to one hundred and five-fold to produce a wide range of light hydrocarbons and stable condensate discharged along lines 3 and 4 for further processing. From the stable condensate supplied via line 4 to block 5, the separation from the NK-128 C fraction, and / or NK is 13.9 ° C, and / or the NK-200 ° C fraction, the mercaptans of the composition C, C, respectively. ,, -6C-Cg, this fraction is sent via line 6 to block 7, where it is purified from mercaptans by extraction with an aqueous solution of alkali. The remaining stable condensate is sent from block 5 through line 13 for further processing. The NK-I28 ° C fraction purified from mercaptans, NK-139 ° C to / or, and / or NK-200 ° C are fed by lipni 8 for further; processing and the resulting water-1 whole o-paci BOp of a mixture of mercaptidosis is directed along line 9 to block 10, where it is treated with ethyl bromide in the presence of boron fluoride. The mixture of dialkyl sulfides obtained in block 10 is separated from the aqueous-alkaline solution by known methods and is directed along the line 11 in. block rz J, where it is separated by one of the well-known methods of the KK-62 C fraction - - 125 C - - - 187 C - 20 & C - 232 C, detached 1) 1e along lines 14 and containing the corresponding methyl etchsulg id, diethyl sulphide ethyl opropyl sulphide, ethyl propyl sulphide 5 ethyl butyut .: sulphide, e-hilisopent shsulfide, egylpentyl sulphide, ethylhexyl sulphide 5 ethylheptyl with ulfid S etiloctyl, ulfid.

Example 1. The experiment was carried out at an industrial plant for the production of a mixture of natural mercaptides .. (orang SPM) of the Orenburg gas processing plant to an on-site installation for the preparation of dialkmsulide. 18 kg of a high sulfur sjdensat of the Orenburg gas condensate deposit 5, containing 0.83% mercaptan sulfur, were separated in the stabilizer 5, which is a glass coloccc / height

450 mm, diameter 30 mm at a pressure of 1 atm and temperatures of the stabilizer top 65 ° С, low 215 ° С for a wide fraction of light hydrocarbons

(4 kg) and stable condensate (14 kg). A stable condensate in a glass column 350 mm long, 30 ppm in diameter with a nichrome spade nozzle, at a pressure of 1 atm and a column top temperature of 40 ° C and a low 350 ° C fraction of the stable condensate NK-200 ° C were added 9 kg. The isolated fraction of NK-200 C, stably, of its condensate, was fed to the block of dipkylsulfides. Moreover, it was analyzed three times for mercaptans according to GOST 17323-71.

3 separatory funnels were charged with 400 ml of the HK-ZOO C fraction condenser of stable condensate and 100 ml of a 30% aqueous solution of caustic soda, i.e. in volume ratio condensate-extractant 4: 1. At room temperature and atmospheric pressure, the mixture was vigorously stirred for 10 minutes and settled. At the end of the extraction, condensate and spent mercaptide

the alkaline solution was analyzed for the content of mercaptan sulfur. At the same time, a purified condensate containing 0.27 wt.% Mercaptan sulfurum and a spent mercaptide alkaline solution containing

5.6 wt.% Mercaptide sulfur.

The floor; a water-alkaline solution of a mixture of merhaptids (jOO ml) was loaded into the reactor, which is a 250 ml co-flask flask equipped with a reflux condenser, a dropping funnel, and a stirrer. To the aqueous-alkaline solution of the mercapine mixture was added 0.05 g of boron fluoride to the dropwise with constant interleaving;: 75% were added to the cooling to 10-5 ° C: - l bromine; 100% ethyl, t . regenerate solution 8; io. At the end of the addition, the mixture was vigorously stirred for about 5 hours, the organic layer of the dialkyl sulfide mixture was separated from the water-alkaline solution in a separatory funnel and washed with water. The resulting mixture of dialkylsulfide by distillation at atmospheric pressure in a laboratory setup, consisting of a round bottom flask. , Liebig's thermometer and refrigerator,

divided into fractions NK-62 С - 93 - 125 ° С - 143 С - - - - 208 "С -.

When separating the mixture of dialkylsul feeds into fry ctions, the following were obtained: individual dialkyl sulfides, rel.

Methylethyl Sulfide

Diethyl sulfide 8.9

Ethyl isopropyl sulfide 50, 5

Ethylpropylsulfd12, 9

Ethyl butyl sulfide 15, 4

Ethyl isopentyl sulfide 3, 2

Ethylpentyl sulfide2,4

Ethylhexyl sulfide 1.9

Etsh1heptylsulfid 1,6

Ethylactyl sulfide 0.7

PRI mme R 2. Illustrate the implementation of the method in the industrial version.

High-sulfur gas condensate in the amount of 58. entered the stabilizer, where at.-pressure of 60 atm. and the top temperature of the stabilizer is 65 ° C and the bottom 215 ° C is divided into a wide fraction of light hydrocarbons and a stable condensate. A wide fraction of light hydrocarbons is sent for further processing. From a stable condensate in a packed column at a pressure of 6 atm and a top temperature of 40 ° C, the bottom 305 ° C, the NK-200 ° C fraction is released. The fraction of stable condensate NK-200 ° C in the amount of 48. served in the lower part of the extractor with a content of 2.667% by weight of mercaptan sulfur. 15m / h of a 20% aqueous solution of caustic soda is fed to the top of the extractor, i.e. in a volume ratio of 3: 1. In the extractor, the mercaptan is extracted with an alkali solution at a pressure of 3 atm.

Cleared of condensate mercaptans from the top of the extractor were sent for storage to a warehouse of stable condensate.

As a result of the extraction, a purified condensate was obtained containing 0.25 wt.% Mercaptan sulfur and a spent aqueous alkaline solution of a mixture of mercaptids containing 5.7 wt.% Mercaptan sulfur.

169086

The spent aqueous-alkaline solution of a mixture of mercaptides in the amount of 15 m / h was removed from the bottom of the reactor. j on the level of the section and filed in the short part of the reactor. In the upper part of the reactor, 4.5 m / h of ethyl bromide and 4.5 kg of fluoride boron were fed. The cubic part of the reactor was cooled to 10–10–15 ° C in an upstream heat exchanger, and the mixture was stirred with a mechanical stirrer for 0.5 h. In the reactor operating under a pressure of 0.2–0.3 atm, 15 methyl ethyl bromide was reacted with merpaptide ffl mixtures. Formed with a mixture of dialkyl sulfides from the top of the reactor is sent to a separation tank, where additional separation of dialkyl sulfides and water occurs. The resulting 1.6 dialkyl sulfides were taken out of the tank and sent to the warehouse of dialkyl sulfates.

The spent alkaline solution in an amount of 15 with a content of 0.3% by weight of mercaptan sulfur from the bottom of the reactor and separation tank is fed to the extractor for reuse as an extragent.

10 kg were taken from the resulting mixture of dialkylsulphides and further processed in a laboratory setup identical to Example 1. 35 The table shows the results of the separation into fractions of a mixture of dialkylsulphides indicating the quantitative yields of the target products.

A positive effect in comparison with the prototype is achieved due to the fact that in order to obtain dialkyl sulfides in the proposed method, a natural high-sulfur 45 gas condensate is used as the sulfur-containing compound. The use of high-sulfur gas condensate, in addition to expanding the raw material base of the method, eliminates the need for preliminary synthesis of sulfur-containing compounds, their cleavage, purification and involvement in further interactions. This simplifies the process, reduces the number of its stages and reduces the consumption of materials.

The proposed method, in addition to using natural gas condensate as a raw material, involves carrying out a technological process for obtaining dialkyl sulfides on the process equipment used in the processing of natural high-sulfur gas condensate, which reduces capital costs for the implementation of the method and considerably reduces the cost of it.

Claims (1)

1. A method of producing dialkylsulfide by reacting a sulfur-containing I o compound with an alkyl halide in the presence of a base and a catalyst. The process is characterized by the fact that the high-utilization of sulfur is used as a sulfur containing compound | gas condensate, which is rectified, and a broad fraction of light carbohydrate and stable condensate is separated from the last fraction of hydrocarbons NK-128 C and / or NK-139 ° C and / or NK-200 C by distillation into distillation columns, handle vyd lennye stable condensate fraction of aqueous alkali, the resulting aqueous alkaline solution is subjected merkapti- rows halide by alkyl in the presence of boron fluoride, the resulting mixture of dialkyl sulfides is separated from the aqueous-alkaline solution, and the target products are isolated by distillation of the mixture into NK-62 C fractions at 93 ° C-125 ° C - - - - 187 ° C - - 232 C. 2, Method pop. 1, differing from one and the other with the fact that methyl bromide is used as alkyl halide. ethyl. K-139 ° С K-200 ° С 62 С 93 C 1 125 C 143 ° C 87 C 208 ° C 232 ° C. Discontinuance 61, 92, 109 Methylethyl Sulfide Diethyl sulfide Ethyl isopropyl sulfide Ethylpropyl sulfide Ethylbutyl sulfide Ethyl is optionally sulfide; Ethyl Pentyl Sulfide 165 Ethylhexyl sulfide 186 Ethylheptyl sulfide 208 Ethyl octyl sulfide 124 0.12 0.89 5.05 1.29 1.62 8.9 50.5 12.9 0.13 . 1,3 / J five JL fO 7 / f2 W N V /four