The method of purification of hydrocarbons from mercaptans

 

(57) Abstract:

The invention relates to the field of purification of hydrocarbons or trademarks of hydrocarbon fractions from mercaptans, in particular high-boiling tertiary mercaptans, and can be used in gas, oil and petrochemical industries. The method of purification of hydrocarbons from mercaptans are by oxidation of mercaptans oxygen-containing gas in an alkaline medium in the presence of phthalocyaninato catalyst, ethanolamine and promoting supplements - complexes of copper with the disodium salt of ethylenediaminetetraacetic acid (Trilon B), used in the amount of 50-90% by weight of the catalyst. The method allows to achieve and maintain a high degree of purification after prolonged use promoting additives. 1 C.p. f-crystals, 2 PL.

The present invention relates to the field of purification of hydrocarbons from mercaptans and can be used in gas, oil and petrochemical industry.

A known method of purification of hydrocarbons from mercaptans, where the alkaline solution phthalocyaninato catalyst is added as a promoter sodium phosphate or phosphates of other alkaline metal which changes due to the low degree of purification.

Also known catalyst for the oxidation of mercaptans, where the alkaline solution phthalocyaninato catalyst is added to the promoter of ammonium molybdate [2]. This catalyst does not provide a high rate of oxidation of the mercaptans, in particular high-boiling.

Interest method of sweetening kerosene, which for oxidation of difficultly oxidizable high-boiling tertiary mercaptans are offered as promoting additives mercury ions and thiosulfate ions, or ions cyanide [3]. Despite the relatively high degree of purification draws attention to the high toxicity of the components of the proposed promoter.

Closest to the proposed method to the technical essence and the achieved result is a method of purification of hydrocarbons from mercaptans, in particular high-boiling tertiary mercaptans. In this way in an alkaline solution phthalocyaninato catalyst is proposed to use the promoting additive - bromides of metals of variable valence I, VI, VII groups of the Periodic system or their complexes with ethanolamines [4]. Bromides of metals used in the amount of 10-100% by weight phthalocyaninato catalyst.

The main gas use promoting additives in alkaline solution phthalocyaninato catalyst.

The present invention is to achieve and maintain the high degree of purification of hydrocarbons from high-boiling mercaptans with long-term use promoting additives.

According to the invention this object is achieved by purification of hydrocarbons from mercaptans by oxidation of mercaptans oxygen-containing gas in an alkaline medium in the presence of phthalocyaninato catalyst and promoting additives. As the promoting additive is proposed to use a complex salt of copper with the disodium salt of ethylenediaminetetraacetic acid (EDTA or Trilon B) in an amount of 50-90% by weight phthalocyaninato catalyst.

Distinctive features of the proposed method is used as the promoting additive complex salt of copper with Trilon B in the amount of 50-90% by weight phthalocyaninato catalyst.

These distinctive features of the proposed method to determine the novelty and inventive step in comparison with the prior art. Use as promoting additive complex of copper with Trilon B allows you to achieve and maintain a high degree of purification from high-boiling tertiary mercaptans p is outstay information about promoting additive - the complex salt of copper with Trilon B.

Proposed for use in the invention is water-soluble phthalocyanine catalysts, such as desulphitation cobalt (GSFC), tetrasulfonated cobalt (TSFC), dichlorobicyclo-phthalocyanine cobalt (DHTODFG) or YWCAS and others, belong to the group known highly active catalysts for the oxidation of mercaptans oxygen in alkaline solution and provide a sufficiently high rate of oxidation of the mercaptans.

The proposed use of the alkaline solution is an aqueous solution of caustic soda or sodium hydroxide with a concentration of 10-15 wt.% and ethanolamines with a concentration of 3-8 wt.%.%. Alkali and ethanolamines are known to the group bases and are designed for ionization of mercaptans, which precedes the stage of oxidation of mercaptans.

The proposed method has been tested in laboratory conditions on the example of the purification of a model mixture of n-dodecane and tert-dodecylmercaptan and kerosene fractions Samara refineries.

Preparation of the initial solution of the catalyst complex

The solution of the catalyst complex (50 ml) consists of three parts. Each of the three solutions is prepared on the m while mixing, slowly add 0.0025 g of the trylon B.

Solution 2. In 10 ml of water is dissolved initially, 0.01 g sodium hydroxide. Then dissolve 0.005 g phthalocyaninato of coalisator YWCAS.

Solution 3. In 25 ml of water was dissolved 5 g of sodium hydroxide. Then 1.5 monoethanolamine.

After obtaining the solution 2 is added to solution 1. Solution 3 is added to the mixture of solutions 1 and 2. The result is a 50 ml solution of the catalyst complex containing 0,0073 wt.% complex of copper with Trilon B, 0.01 wt.% the catalyst YWCAS, 3 wt.% of monoethanolamine and 10 wt.% caustic soda.

Example 1. In a reactor with a stirrer download 100 ml of dodecane containing 0.2 wt.% tert-dodecylmercaptan in terms of sulphur, and 50 ml of the catalyst complex. The composition and the procedure for obtaining the catalyst complex described earlier.

The oxidation is carried out at atmospheric pressure, at a temperature of 50°C when the air flow through the bubbler at a rate of 0.2 l/min for 30 minutes. While the mercaptans into disulfides. After decanting cialisstory complex is separated from the hydrocarbons and used again in subsequent cycles to clear new portions of hydrocarbons.

The results of experiments on the purification of dodecane from mercaptans during the first six cycles of treatment with the use of the Eden data cleaning dodecane from mercaptan in the same conditions when using as promoting additives of copper bromide.

From the above table.1 experimental data shows that when cleaning a model mixture of n-dodecane from tert-dodecylmercaptan use in alkaline solution phthalocyaninato catalyst promoting additives in the form of a complex salt of copper and trylon B can achieve a fairly high degree of purification (lowering the content of mercaptan sulfur from 0.2 to 0.008 wt.%). In addition, the presence of this promoter allows you to save a achieved a high degree of purification with long-term use of the promoter (cycles I-IV) in alkaline solution phthalocyaninato catalyst in comparison with the well-known promoter (CuBr), when the degree of purification gradually decreases (the residual content of mercaptan sulfur from 0.008 wt.% grew up 0,0745 wt.%).

Example 2. In a reactor with a stirrer download 100 ml kerosene fraction Samara refineries, containing 0,0326 wt.% mercaptan sulfur and 50 ml of the catalyst complex, the composition and obtaining the catalyst complex described earlier. Conditions for clearing kerosene fractions are the same as in example 1.

The results of the experiments on cleaning oil fraction from mercaptans during the first six cycles of purification when used as an item is data cleaning oil fraction from mercaptans in the same conditions when using as promoting additives previously known copper bromide.

From the above table.2 experimental data shows that when cleaning oil fraction Samara refineries from mercaptans use in alkaline solution phthalocyaninato catalyst promoting additive complex salt of copper and trylon B can achieve a fairly high degree of purification (reduction of the content of mercaptan sulfur 0,0326 wt.% 0.0018 wt.%). In addition, the use of this promoter allows you to save a achieved a high degree of purification with long-term use of the promoter (cycles I-VI) in alkaline solution phthalocyaninato catalyst, compared with the use of known promoter (CuBr), when the degree of purification gradually decreases(the residual content of mercaptan sulfur from 0,0020 wt.% grew up 0,0220 wt.%).

Sources of information

1. U.S. patent No. 2999806, 12.09.61. Cleanup of hydrocarbon distillates from mercaptans”. Company Universal Oil Products”. R. J. Chemistry, VII, No. 19, 1962, 19 M 201.

2. Patent GDR, CL 01 J 31/22, No. 134195, Appl. 23.09.77, No. 201185, publ. 14.02.79. “The catalyst and its application”. R. J. Chemistry, 21 L 205, 1979.

3. U.S. patent No. 3271294. “Oxidation of mercaptans”, R. J. Chemistry, St., P, No. 5, 1968.

4. Auth. certificate No. 513069, Appl. 22.05.74. “The way PTS is 9.

1. The method of purification of hydrocarbons from mercaptans by oxidation of oxygen-containing gas in an alkaline medium in the presence of phthalocyaninato catalyst, ethanolamine with promoting additive, characterized in that as the promoting additives using the complexes of copper with the disodium salt of ethylenediaminetetraacetic acid (Trilon B).

2. The method according to p. 1, characterized in that the promoting additive is used in an amount of 50-90% by weight phthalocyaninato catalyst.



 

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EFFECT: the invention ensures increased efficiency of separation, decreased corrosive attack of the reaction medium, simplification of the method.

6 cl, 8 ex

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