The purification method of crude oil, gas condensate and oil products from the hydrogen sulfide and/or low molecular weight mercaptans

 

(57) Abstract:

The invention relates to petrochemistry, in particular to methods of refining oil, gas condensate and oil products, and oil-water emulsions from hydrogen sulfide and/or low molecular weight mercaptans, and can be used in oil, gas, refining, petrochemical and other industries. Cleaning of oil, gas condensate and oil products from the hydrogen sulfide and/or low molecular weight mercaptans carry out the processing of raw materials by aminotranferase (ATP), General formula

< / BR>
where R is alkyl or oxyalkyl, taken in an amount of 0.5 to 2 mol per 1 mol of hydrogen sulfide and/or mercaptans FROM1-C4. When ATP is used in the form of an aqueous solution previously obtained by the interaction of the primary alkylamine or alkanolamine with about 37% aqueous formaldehyde solution (formalin), taken in a molar ratio of primary amine: formaldehyde = 1:(2,5-3,5), preferably 1:3. In addition, processing of the feedstock is carried out at 15-85oC. the Method can significantly improve the degree of purification of raw materials in comparison with known methods. 3 C.p. f-crystals.

The invention relates to petrochemistry, in particular if low molecular weight mercaptans, and can be used in oil, gas, refining, petrochemical and other industries.

Known methods of purification of oil and oil products from the hydrogen sulfide by treating them with oxygen and/sludge nitrogen-containing organic reagents-converters, in particular anhydrides, haloganated, inorganic salts of carboxylic acids, peroxide, isocyanates, diisocyanates, diisopropylcarbodiimide, diethylazodicarboxylate, fumaronitrile, maleic anhydride, diaminoethane, Minami, aminocarbonyl, polyamidine, triallylisocyanurate etc. /Pat. The UK 2185994, 2185995, 2186590; U.S. Pat. USA 4909925, 5074991, 5169411, 5190640, 5223127, 5266185, 5284576, 5354453 and others/.

There is also known a method of cleaning gas from mercaptans by processing its sodium salt arylsulfonic acid taken in the quantity 6,24-10 wt. % (based on the feedstock, at room temperature for 1-2 hours /auth. mon. 1810377, C 10 G 29/20, 1993/.

A disadvantage of the known methods that prevent their wider application in industry is the scarcity and high cost of the reagents-neutralizers. In addition, the known methods in most Westen purification method of crude oil and petroleum products from the hydrogen sulfide and/or mercaptans by processing the feedstock effective amount of the nitrogen - and oxygen-containing dipolar organic reagent, which ion of the Quaternary ammonium salts and received by epoxydecane tertiary organic amine oxide alkylene, preferably ethylene or propylene. While processing the raw materials an effective amount of the reagent of the Converter is directly proportional to the concentration of hydrogen sulfide and mercaptans, preferably carried out at a temperature of 100-400oF /Pat. USA 5344555, C 10 G 29/20, 1994 /.

The disadvantages of this method are the scarcity and high cost of used reagent-catalyst, not a high degree of purification of the raw materials from mercaptans and significant energy consumption due to the necessity of carrying out the process at elevated temperatures, in addition, the reagent does not have the selectivity to hydrogen sulphide and light mercaptans /simultaneously reacts with contained in the raw material oil acids, water, etc./, which leads to increased his consumption and cost of the cleanup process as a whole.

Closest to the proposed invention is a method of purification of sulfur crude oil and petroleum products from the hydrogen sulfide and/or mercaptans by processing raw material an effective amount of hexamethylenetetramine /it has been/ at a temperature of 100-350o

The disadvantages of this method are not sufficiently high degree of purification of raw materials from hydrogen sulfide and mercaptans, as well as significant energy consumption due to the need for the cleaning process at elevated temperature 38-177oWith/, which is associated with low reactivity it has been in relation to hydrogen sulfide and mercaptans at ordinary temperatures.

The objective of the invention is to increase the degree of purification of oil, gas condensate and oil products from the hydrogen sulfide and low molecular weight mercaptans, as well as expansion of the range of the applied reagents-converters and reducing energy consumption for the process.

According to the invention, the mentioned technical result is achieved by the described method for purification of oil, gas condensate and oil products from the hydrogen sulfide and/or low molecular weight mercaptans by processing the feedstock with an organic reagent, in which the organic real notrivial preferably take in the amount of 0.5-2 mol per 1 mol of hydrogen sulfide and/or mercaptans C1-C4. In addition, aminocarbonyl used in the form of an aqueous solution previously obtained by the interaction of the primary alkylamine or alkanolamine with about a 37% aqueous solution of formaldehyde /formalin/ taken in a molar ratio of primary amine formaldehyde 1:(2,5-3,5), preferably 1:3.

In addition, processing of raw materials is preferably carried out at a temperature 15-85oC.

Distinctive features of the proposed method are the use of the above aminotranferase /next ATP/ found in the optimal molar ratio in aqueous solution, obtained by the interaction of the primary alkylamine or alkanolamine with an aqueous solution of formaldehyde /formalin/ as reagent-catalyst of hydrogen sulfide and low molecular weight mercaptans, as well as the preferred carrying out of the process when the found optimal temperature range /15-85oS/.

These distinctive features of the proposed technical solutions determine its novelty and inventive step in comparison with the prior art, since the use of ATP in the found optimal molar ratios as reagents-neutralizirati not documented and can improve the degree of purification of raw materials, as well as to reduce the temperature of the process and, therefore, reduce the degree of hydrogen sulfide corrosion of the equipment and reduce the pollution emissions of highly toxic sulfur compounds, as well as to reduce the energy consumption for the process.

It should be stated that obtaining alkylaminocarbonyl, i.e. perhydro(1,3,5-dioxazine-5-yl)alkanes interaction of the primary alkylamine with 30% aqueous formaldehyde solution are described in the literature (see J. Walker. The formaldehyde. M: Goskomizdat, 1957, S. 316/. However, not described in literature and their use as reagents catalysts for the purification of crude oil, condensates, refined petroleum products from hydrogen sulfide and mercaptans.

We offer the molar ratio of the applied aminotranferase /0,5-2:1/ is connected with the stoichiometry of the flowing neutralization reactions of hydrogen sulfide and low molecular weight mercaptans to form a liquid non-volatile, non-corrosive, soluble in petroleum and petroleum products nitrogen - and sulfur-containing organic compounds - amidosulfuron and is optimal, because when the molar ratios less than 0.5:1 significantly reduced the degree of purification of the raw material from which hydrogen sulfide, low molecular weight mercaptans and not to what innosti. The increase in molar ratio of more than 2:1 already does not lead to further increase the degree of purification of raw materials and, therefore, uneconomical.

The feasibility of using ATP in aqueous solution. obtained by the interaction of the primary alkylamine or alkanolamine with an aqueous solution of formaldehyde /formalin/, due to their relatively low thermal stability and decomposition by heating and distillation. In the proposed method, in principle, can be used and anhydrous ATP extracted from aqueous solution by vacuum distillation at low temperatures, however, it is not economically feasible because of the significant inputs for production of anhydrous product. Should indicate that the proposed method is most appropriate to use aqueous solutions of ethylaminoethanol and/or ethanolamines obtained by the interaction of monoethylamine and/or monoethanolamine with a 37% solution of formaldehyde (formalin), because of the number of primary amines exactly ethylamine and ethanolamine are the most technologically advanced available and relatively inexpensive source products to get used ATF.

Preferred conducting procsize 15oC significantly reduced the rate of the reaction of ATP with low molecular weight mercaptans /reaction with hydrogen sulfide occurs with sufficient speed and at lower temperatures, therefore, increases the processing time of the raw material. The temperature rise above 85oSince it is not economically feasible due to the increasing energy consumption for performing the cleaning process. Most preferably the process at 20-50oWith, because raw streams usually have a temperature in this range, which eliminates the need for pre-heating of raw materials. Moreover, the cleaning process may be carried out in periodic mode, for example, using apparatus with stirrer and/or a circulating pump, and in continuous mode continuous dosage of the applied solution of ATP in the flow of raw material using known mixing devices flow type: PWG, GARTH, diaphragm or valve mixers and centrifugal pumps. This purification process can be carried out both at atmospheric and elevated pressures.

The proposed method has been tested in laboratory conditions and is illustrated by the following specific but not ogran is. % of hydrogen sulfide /0,0013 mol/ and 0,158 wt.% mercaptan sulfur, including a 0.035 wt.% low molecular weight mercaptans C1-C4/0,00093 mol, placed in a temperature-controlled reaction flask equipped with a mechanical stirrer. Then, into the flask under stirring injected with 0.9 g of 35% aqueous solution of ethylaminoethanol previously obtained by the interaction of a 50% aqueous solution of monoethylamine on THE 6-02-794 with a 37% aqueous solution of formaldehyde /formalin according to GOST 1625-89/ taken in a molar ratio ethylamine: formaldehyde in solution of 1:3 at room temperature and atmospheric pressure. The molar ratio of hydrogen sulfide and mercaptans FROM1-C4: ethylaminoethanol in the reaction mixture is 1:1,2. Then the flask contents are stirred at 40oAnd atmospheric pressure. After stirring for 1 h conduct a quantitative analysis of the purified oil content of hydrogen sulfide and mercaptan sulfur by potentiometric titration and simultaneously determine the intensity of the smell of purified oil organoleptic method.

The degree of purification of oil from the hydrogen sulfide is 100% and mercaptans - -30%; purified oil content of hydrogen sulfide and light methyl-, ethylmercury export". The project, revision 1, , Ufa, IPTER, 1995 odor of hydrogen sulfide and light mercaptans in the purified oil is out of line is not detected, i.e., oil destoryed and decrease its toxicity and corrosional for subsequent storage, transportation and processing.

Example 2. Deodorizing cleaning emulsion sulfur oil containing 10 wt. % emulsion of water and 0.02 wt.% of hydrogen sulfide, carried out analogously to example 1, using as reagent-catalyst efficiency of 43.5% aqueous solution of ethanolamines, i.e., 1-hydroxy-2-(perhydro-1,3,5-dioxazine)-5-yl-ethane, previously obtained by the interaction of monoethanolamine on THE 6-02-915-84 with a 37% solution of formaldehyde in a molar ratio of 1: 3 at room temperature /22oWith/ I atmospheric pressure. The molar ratio of hydrogen: ATP in the reaction mixture is 1:0,59. The mixture is intensively stirred at room temperature and atmospheric pressure. After stirring for 3 h conduct a quantitative analysis of the purified oil and separated water emulsion on the content of hydrogen sulfide. The degree of purification of oil and water from the hydrogen sulfide is 100%. The rear of hydrogen sulfide is not detected, i.e., netremotetod and 0,253 wt.% mercaptan sulfur, including to 0.17 wt.% mercaptans WITH1-C4, carried out analogously to example 1 using 35% aqueous solution of ethylaminoethanol in example 1. The molar ratio of hydrogen sulfide and mercaptans FROM1-C4: ATP in the reaction mixture is 1:2. The mixture is intensively stirred at 35oAnd atmospheric pressure. After stirring for 2 h perform quantitative analysis of the purified condensate on the content of hydrogen sulfide and mercaptan sulfur. Purity gas from which hydrogen sulfide is 100% and mercaptans - 74%. The smell of hydrogen sulfide and light mercaptans is not detected, i.e., the condensate destoryed.

Example 4. Cleaning straight-run petroleum fractions N. K. - 300oWith, used as a solvent of paraffin in oil and containing 0.01 wt.% of hydrogen sulfide and of € 0.195 wt.% mercaptan sulfur, including 0.07 wt.% mercaptans WITH1-C4, carried out analogously to example 1 using 54,5% aqueous solution of ethanolamines previously obtained by the interaction of monoethanolamine with a 37% solution of formaldehyde in mühlen ratio of 1: 2,5 at room temperature. The molar ratio of hydrogen sulfide and mercaptans FROM1- C4: At the Le stirring for 3 h perform quantitative analysis of the purified oil to hydrogen sulfide, mercaptan sulfur and determine the corrosivity test on a copper plate. The degree of purification of the raw material from which hydrogen sulfide is 100% and mercaptans - 42%. The cleaned product test copper plate stand, the back of sulfide and light mercaptans is not detected, i.e., reduced its corrosional and toxicity for use as a solvent of paraffin.

Example 5. Purification of sulphur fuel oil, used as boiler fuel, and containing 0.025 wt.% of hydrogen sulfide, carried out analogously to example 1 using 40% aqueous solution of ethanolamines previously obtained by the interaction of monoethanolamine with a 37% solution of formaldehyde in a molar ratio of 1:3.5 at room temperature. The molar ratio of hydrogen: ATP in the reaction mixture is 1:1. The mixture is intensively stirred at 50oC for 1 h, the Degree of purification of the raw material from which hydrogen sulfide is 100%, i.e., the purified oil content of hydrogen sulfide meets the requirements of GOST 10585.

Comparative experiment proved that when cleaning high-carbon oil containing 0,049 wt.% hydrogen sulfide and 0,158 wt.% mercaptan sulfur, izvestnee 48% and from mercaptans - 13%. The purified oil has a specific smell of servodata and light mercaptans, i.e., the desired deodorization of oil is not achieved.

The data presented in examples 1-5 show that the purification of oil, gas condensate and oil products proposed method can significantly improve the degree of purification of raw materials from hydrogen sulfide /100% and 48% respectively/ and mercaptans /30-74% and 13%, respectively, and thereby reduce the degree of hydrogen sulfide corrosion of equipment, and also to reduce the pollution emissions of toxic hydrogen sulfide and low molecular weight mercaptans, in addition, the proposed method in contrast to the known provides a high degree of purification of the raw material at normal temperature /15-35oTo/ that allows you to reduce the energy consumption of the process in comparison with the known.

1. The purification method of crude oil, gas condensate and oil products from the hydrogen sulfide and/or low molecular weight mercaptans by processing the feedstock with an organic reagent, characterized in that the organic reagent used aminocarbonyl General formula

< / BR>
where R is alkyl or oxyalkyl.

2. The method according to p. 1, wherein there that Aminat is. the manual on PP. 1 and 2, characterized in that aminocarbonyl used in the form of an aqueous solution previously obtained by the interaction of the primary alkylamine or alkanolamine with about 37% aqueous formaldehyde solution (formalin), taken in a molar ratio of primary amine: formaldehyde = 1: (2,5-3,5), preferably 1: 3.

4. The method according to p. 1, characterized in that the treatment is carried out at a temperature of 15-85oC.

 

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EFFECT: reduced consumption of reagents at high degree of purification of raw material.

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