RU2619930C1 - Method of cleaning hydrocarbonic media from hydrocarbon and mercaptanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of cleaning hydrocarbon media from H₂S and/or mercaptans, in which the hydrocarbon feed is treated with a cleaning composition containing an aqueous solution of an alkali metal nitrite, a water soluble amine and/or ammonia or a mixture of a water soluble amine and/or ammonia and a strong inorganic base in the presence of variable valence metals, in the absence of oxygen, and metals of variable valency are used in a high degree of oxidation.

EFFECT: elimination of the problem of entrainment of fumes of light fractions and environmental problems of utilization of exhaust air during the purification of oil or oil fractions.

14 cl, 1 tbl, 16 ex

Description

The invention relates to methods for purifying a variety of hydrocarbon media, including liquid hydrocarbon feedstocks, gaseous mixtures of hydrocarbons, and the like. from hydrogen sulfide and mercaptans in the absence of an oxidizing agent - atmospheric oxygen, which consists in adding a cleaner composition containing an alkaline metal nitrite aqueous solution, a water-soluble amine and / or ammonia or a mixture of a water-soluble amine and / or ammonia and an inorganic base in the presence of a metal in high oxidation states, such as cobalt, copper, iron and molybdenum, or mixtures thereof. A highly oxidized metal is a catalyst, a water-soluble amine or ammonia, or a mixture of a water-soluble amine or ammonia and an inorganic base is a cocatalyst, an alkali metal nitrite is an oxidizing agent.

The objective of the invention is the ability to clean in conditions that exclude the additional involvement of oxygen in the air for oxidation reactions, which in turn eliminates the problems of entrainment of vapors of light fractions and environmental problems of utilization (burning) of exhaust air when cleaning oil or oil fractions using methods used in industrial practice. This also allows the use of a cleaner to clean gas streams when the use of oxygen is excluded due to the formation of dangerous gas mixtures with oxygen and the introduction of inert nitrogen into the gas. The invention also solves the problem of choosing a cleaning method that is highly efficient and eliminates contamination of process equipment of pipelines, storage tanks and oil fractionation columns with hard-to-remove compounds. An additional object of the invention is to improve the index of copper plate for oil distillates characterizing the general corrosion of the fuel according to ASTM D130-12 or GOST 6321-92 "Fuel for engines. Copper plate test method. "

Various catalysts for the oxidation of mercaptans and hydrogen sulfide based on complexes of metals of variable valency are well known and described in the prior art: first of all, these are various variants of the phthalocyanines Co, Cu, Ni, Cr, V, Mo, Fe or Mn (US 2853432 A, US 3978137 A , US 2882224; US 2988500; US 3108081; US 3230180, US 3148156), porphyrins (US 29664533, US 923645), complexes with amines (RU 2408426, EA 018297). In a process widely used in industry for the purification of oil and oil products from sulfur-containing compounds, a catalyst is used — a cobalt disulfophthalocyanine disodium salt in the form of a 0.5% solution, in the presence of which the mercaptans and hydrogen sulfide are oxidized in an aqueous alkali solution (2-20% NaOH) [Handbook of modern gas processing processes. // Oil, gas and petrochemicals abroad. 1986. No. 7. from. 102]. However, the use of atmospheric oxygen in these oxidation processes results in losses of light hydrocarbons removed from the feed together with the exhaust air.

Known and widely used in industrial applications in airless environments for cleaning hydrogen sulfide and mercaptans with formaldehyde-based neutralizers or derivatives thereof with alcohols and / or urea, ammonia or organic amines (RU 2522459, RU 2517709, RU 2510615, RU 2160761, RU 2348679, RU 2118649, US 20130126429 A1, RU 2107085, RU 2246342, RU 2318864, RU 2470988, etc.). A common drawback of such methods is the environmental and sanitary problems associated with the use of highly toxic formaldehyde, identified as a carcinogen, and the formation of foul-smelling products of thiol-type reactions (semi-mercaptals and thiomercaptals, methylene dithiol derivatives). Another significant drawback of such methods is the accumulation of reaction products of hydrogen sulfide with formaldehyde of hard-to-remove deposits in pipes and tanks, as well as the insufficient efficiency of purification from mercaptans.

Recently, methods of purification with reagents based on the polycondensation products of aldehydes and amines, triazines, have been widely used (RU 2459861, US 20080053920, US20110220551 A1, US20080056974 A1, US 4978512, US 7438877, US 8512449 B1, etc.). The disadvantage of these methods are the relatively high cost of reagents. In addition, the common drawback of all of the above reagents is the presence of poorly soluble reaction products (dithiazines, tritian, polythiomethylene), which form hard-to-remove deposits in pipelines and storage tanks, as well as insufficient efficiency with respect to mercaptans.

Known methods using other than formaldehyde aldehydes - acrolein (EP 2367611 A1, US 8354087) and glyoxal (US 20120241361 A1, US 20120329930, US 4680127, RU 2499031). Acrolein is more expensive than formaldehyde and extremely toxic. The use of glyoxal causes problems with corrosion. In addition, such reagents are effective against hydrogen sulfide, but ineffective against mercaptans.

Oxidation using aqueous solutions of hydrogen peroxide (RU 2177494, RU 2121491, RU 2146693) has significant disadvantages associated with the danger of decomposition of hydrogen peroxide in the presence of nitrogen-containing bases, which occurs with the release of oxygen in a hydrocarbon medium, as well as the technological inconvenience of storing and using concentrated hydrogen peroxide . Used in industry extraction water-alkaline methods with the catalytic regeneration of alkali with atmospheric oxygen (processes such as Merox, Mericat, DMD and VHI) have a common disadvantage associated with the formation of hard-separable water-oil emulsions, as well as difficulties in the disposal of effluents.

Known methods of purification based on choline or choline hydroxides (US 4594147, US 4867865, US 5183560). A common drawback of such methods is the formation of volatile sulfur-containing reaction products, and they are not widely used in industry.

A known method of purifying oil from hydrogen sulfide RU 2252949, in which the treatment is carried out with a sulfur-containing inorganic reagent-neutralizer, in which an aqueous solution of an alkali metal pyrosulfite or hydrosulfite, mainly sodium, or ammonium hydrosulfite is used as a sulfur-containing inorganic reagent, and the process is carried out in the presence of an aqueous solution of hydroxide, carbonate, orthophosphate and / or sulfite of an alkali metal, mainly sodium, or ammonia. The main disadvantage of this method is the unsatisfactory purification of raw materials from mercaptans, as well as the relatively high consumption of an aqueous solution, which leads to undesirable watering of the processed raw materials, especially for cases with a high content of hydrogen sulfide and, accordingly, the introduction of large amounts of an aqueous phase into the oil.

Other purification methods are also known: based on maleimides (US 4,569,766), azodicarboxylates (EP 2274400, US 20090255849), hydroquinones (US20110315921 A1), quaternary ammonium salts (RU 2499031, US 5840177, US20080230445 A1, US 5840177I), (RU 2349627). However, such reagents are quite expensive in production and are not widely used in industry.

A known method of purification of oil from hydrogen sulfide (RF No. 2230095), in which the removal of hydrogen sulfide is carried out with an aqueous-alkaline solution of a water-soluble salt of nitrous acid, mainly alkali metal or ammonium nitrite, with a pH of at least 10 and a nitrite concentration in the solution of 3-40%. The process is preferably carried out at temperatures of 30-80 ° C. The disadvantage of this method is the low reaction rate - in real conditions, the contact time of the chemical and the hydrocarbon medium is limited. To achieve the result, the consumption of alkali metal or ammonium nitrite in this method is quite high and is 0.5-5 mol, preferably 0.9-2 mol per 1 mol of hydrogen sulfide, which is a disadvantage of the method. This leads to an increased consumption of oxidizing agent, which is a significant drawback. In addition, since alkali metal or ammonium nitrite is used in the form of an aqueous solution, this leads to unwanted watering of the dehydrated crude oil. A significant drawback is that when processing in temperature ranges below + 20 ° C, the process practically does not go. Elevated temperatures of raw materials above + 30 ° C in real production conditions exist at limited intervals of the production line to remove water and dissolved gases from oil. To accelerate the process by this method, as well as to remove, in addition to hydrogen sulfide, also light mercaptans, it is provided that compressed air is added to the reaction mixture in an amount of 0.06-0.12 nm ³ per 1 mol of hydrogen sulfide and 2 mol of light methyl, ethyl mercaptans and water or an aqueous-alkaline solution of a salt or a metal complex of variable valency, preferably taken from the calculation of 0.1-1.5 g of metal ions per 1 ton of raw material. The process is carried out under a pressure of 0.2-1 MPa. The amount of compressed air corresponds to the stoichiometry of oxidation of mercaptans and hydrogen sulfide by atmospheric oxygen known from the prior art. An aqueous or aqueous-alkaline solution of a salt or a metal complex of variable valency is used as a catalyst for oxidation by atmospheric oxygen. The disadvantage of this method is the general disadvantage characteristic of all oxidative processes using air oxygen: these are losses of light hydrocarbons by blowing, technological safety problems associated with the formation of mixtures of hydrocarbon vapors with air, and environmental problems in the combustion of exhaust air. Another disadvantage of this method is the inapplicability to the processing of gas hydrocarbon media in which the supply of compressed air is not acceptable for technological reasons. It should also be noted that the use of ammonium nitrites in hydrocarbon media with elevated temperatures is unsafe. In the invention, the solution is taken from the calculation of the flow rate per 1 mol of hydrogen sulfide 0.9-5 mol of alkali metal nitrite, which in practice means a large consumption of the solution, as well as water flooding. In addition, the treatment is carried out at 20-100 ° C (preferably at 30-80 ° C), which excludes the introduction in cases where the processing must be carried out in tanks in cold climates.

A known composition for neutralizing hydrogen sulfide and light mercaptans in petroleum media, including an oxidizing agent and water, characterized in that it contains an alkali metal nitrite and additionally contains a nitrogen-containing basic and / or alkaline reagent in the following ratio of components, wt. %: alkali metal nitrite 16-35, nitrogen-containing basic and / or alkaline reagent 3-30, the rest is water (RF №2241018). The disadvantage of this converter is its low efficiency in the processing of oil with a high content of phenols and naphthenic acids. The main disadvantage of this composition is the insufficiently high rate of neutralization of mercaptans; the neutralization reaction proceeds too slowly, which is not enough to carry out the process in real industrial conditions, in which the processing time is usually very limited. When processing at low temperatures close to 0 ° C, the process practically does not proceed. This method has not found mass application in industry, in particular, due to the length of processing time. For the purification of gaseous media, this composition is not applicable due to the insufficient reaction rate during rapid contact of the gas and the aqueous phase.

Closest to the invention is a method for the purification of hydrocarbons in the absence of air access with a composition containing a quaternary ammonium alkoxide or hydroxide in the presence of a highly oxidized metal, which is used as cobalt, iron, chromium and / or nickel (EAPO 016758). The highly oxidized metal is used as a catalyst in the presence of quaternary ammonium ethoxide or hydroxide. Despite the relative improvement in the depth of purification from mercaptans due to purification in the presence of a metal with a high degree of oxidation compared to known purification methods using only quaternary ammonium hydroxides (US 5840177 and US 6013175), this method still does not eliminate the main disadvantages, which are inherent when using quaternary ammonium bases - high unit costs for an expensive reagent and insufficient rate of neutralization of mercaptans. Ethoxides and hydroxides of quaternary ammonium salts are quite expensive and are not produced by domestic industry. The consumption of such scavengers in terms of weight even in the case of reaction stoichiometry in practice means 10 ppm of scavenger and higher by 1 ppm of mercaptan sulfur, which makes this cleaning method too expensive.

Another disadvantage of this method is that at room temperature the process is too slow and a temperature above + 50 ° C is desirable to accelerate. At temperatures below + 15 ° C, the process practically does not go. This method is practically not applicable for cold climatic conditions.

The task of using cheap and effective reagents produced by domestic industry is still relevant.

The task was to develop such a method of purification from hydrogen sulfide and mercaptans, which would be free from such disadvantages.

This problem was solved by the invention.

In the method for purifying hydrocarbon media from H ₂ S and / or mercaptans according to the invention, the hydrocarbon feed is treated with a purification composition comprising an aqueous solution of an alkali metal nitrite, a water-soluble amine and / or ammonia or a mixture of a water-soluble amine and / or ammonia and a strong inorganic base in the presence of metals variable valency, while the method is carried out in the absence of oxygen, and metals of variable valency are used in a high degree of oxidation.

Mostly highly variable oxidation metals are selected from the group consisting of Co (3+), Cu (2+), Fe (3+) or Mo (+6) and combinations thereof.

Metals of variable valency can be used, in particular, in the form of water-soluble salts or complexes.

Alkanolamines are predominantly used as a water-soluble amine, and alkali metal hydroxide — sodium or potassium — as a strong inorganic base.

Moreover, primary, secondary or tertiary ethanolamines are used as alkanolamines.

The hydrocarbon medium may be selected from the group consisting of crude oil, water-in-oil emulsions, oil residues, straight-run fractions and secondary distillates, low molecular weight hydrocarbons, aromatic solvents, hydrocarbon gas mixtures.

The metal of variable valency is preferably used at the rate of 1 mol per 30-1000 moles of mercaptan or hydrogen sulfide, more preferably at the rate of 1 mol per 100-800 moles of mercaptan or hydrogen sulfide, even more preferably at the rate of 1 mol per 150-600 moles of mercaptan or hydrogen sulfide sulfur.

An aqueous solution of alkali metal nitrite is preferably used at the rate of 1 mol of alkali metal nitrite per 2-6 moles of mercaptan and / or hydrogen sulfide.

A water-soluble amine or ammonia is preferably used at a rate of 1 mol per 2-20 moles of mercaptan and / or hydrogen sulfide.

The inorganic base is preferably used at the rate of 1 mol per 2-20 moles of mercaptan and / or hydrogen sulfide.

The treatment is preferably carried out at a temperature of from -5 to + 80 ° C., Even more preferably at a temperature of from +5 to + 50 ° C.

Thus, the invention is based on the preparation of such a method of purification from hydrogen sulfide and mercaptans, which allows it to be used in the absence of air access, to drastically reduce the time of neutralization of mercaptans, to reduce the cost of the processing by using cheap reagents and to make it industrially acceptable even for cases of raw materials high in hydrogen sulfide and mercaptans. An important advantage of the invention is the ability to treat hydrocarbon media with a purifier even at low temperatures close to 0 ° C, which allows it to be used in cold climatic conditions when the raw materials are in storage tanks without the possibility of heating. The invention also solves the problem of creating a neutralizer composition having high efficiency and eliminating contamination of the process equipment of pipelines, storage tanks and oil fractionation columns with hard to remove compounds. The objective of the invention is the ability to use a neutralizer in conditions that exclude the additional involvement of oxygen in the air for oxidation reactions, which in turn eliminates the problems of entrainment of vapors of light fractions and utilization (burning) of exhaust air. An additional objective of the invention is to develop a composition of a purifier from hydrogen sulfide and mercaptans, which is made from available components mass produced by the domestic industry. Another object of the invention is to improve the index of a copper plate for oil distillates characterizing fuel corrosion according to ASTM D130-12 or GOST 6321-92 “Fuel for engines. Copper plate test method. "

The use of highly oxidized valence metals as metal catalysts from a series of cobalt, iron, copper and molybdenum Co (3+), Cu (2+), Fe (3+) or Mo (6+) together with aqueous solutions of alkali metal nitrite , a water-soluble amine and / or ammonia, or a mixture of this water-soluble amine and / or ammonia with an inorganic base when processed in a medium without access to atmospheric oxygen, allowed to get rid of the above-mentioned disadvantages of the prior art, in particular, allowed to carry out a high-speed cleaning process efficiency, without involving oxygen, with a reduced reagent consumption compared to the prior art. The exact mechanism of these reactions is unknown, and perhaps a highly oxidized metal is not a “catalyst” in the strict sense of this definition. Therefore, this purification method is not limited to any particular reaction mechanism. In this method, the cleaning of the hydrocarbon medium is carried out with aqueous solutions or suspensions of these metal compounds in aqueous solutions of alkali metal nitrites, a water-soluble amine and / or ammonia, or a mixture of this water-soluble amine and / or ammonia with an inorganic base. The term “highly oxidized” as used in this context means that the metal is characterized by such an initial valency that it can be reduced without forming the metal as a chemical element. The authors do not limit themselves to any theory under the assumption that these metals act as catalysts. Suitable highly oxidized metals exhibiting the desired effect include Co (+3), Fe (+3), Cu (+2), Mo (6+), and combinations thereof. Metals may be present in the form of water soluble salts and complexes. Some examples of such metal complexes (not limited to only) suitable for use in the compositions and method described in this context include cobalt phthalocyanine disodium dichlorodisulfonic acid, which is a well-known industrial catalyst for the oxidation of mercaptans by IVKAZ-T air oxygen (not limited to im) and cobalt phthalocyanine salts, known as Merox catalysts from UOP or ARI from Merichem. Other examples of such metal compounds are their complexes with ethylenediaminetetraacetic acid (EDTA), produced on an industrial scale, as well as complexes with amines and polyhydric alcohols, which are readily prepared by in situ methods known in the art and practice.

These metal compounds of variable valency are used in the form of an aqueous solution or suspension in an aqueous solution containing alkali metal nitrite, a water-soluble amine or ammonia, or a mixture of a water-soluble amine or ammonia and an inorganic base. The resulting purifier reagent in the form of the specified aqueous solution or suspension in an aqueous solution can be added to the hydrocarbon medium intended for purification by standard methods, such as injection or simple pouring, while the additive is distributed throughout the volume of the medium with stirring, or the purified hydrocarbon can be bubbled flow through a layer of a solution of the specified cleaner in the contact apparatus. Cleaning by this method is carried out until the neutralizing properties of the cleaner are lost.

In addition to the indicated advantage in cleaning hydrogen sulfide and mercaptans, the cleaning method described in the invention solves the problem of reducing the acidity and corrosion of the purified raw materials, including according to the indicator on a copper plate in accordance with ASTM D130-12 or GOST 6321-92 “Fuel for engines. Copper plate test method. "

This cleaning method can be used at normal atmospheric or elevated pressure, as well as at room temperature or at elevated temperatures up to 60-80 ° C. Bearing in mind that in the systems for the preparation of crude oil or gas or when supplying oil products from a plant after the refrigerator, the temperature limits of the processed raw materials are usually in the range of 30-60 ° C, the purifier can be used at the temperatures of the processed raw materials in the above ranges. This converter can also be used at lower temperatures - close to 0 ° C.

Aliphatic amines, in particular lower alkylamines, alkanolamines, and as an inorganic base, alkali metal hydroxide (sodium or potassium) can be used as a water-soluble amine in the composition of the catalyst. All of these components are manufactured by industry and are multi-tonnage products.

Without limiting the essence of the invention, various organic substances — solvating additives used to improve the contact of the polar and nonpolar phases known from the prior art — lower aliphatic alcohols, dialkyl sulfoxides, alkyl amides, glycols, sulfolane, etc., can also be introduced into the described catalyst. (RU 2358004, RU 2224006, US 3409543, US 6960291, etc.). Substances that improve the process of emulsification of the composition in a non-polar hydrocarbon medium can also be introduced into the composition — these can be any surfactants known from the prior art, phase transfer catalysts: phenolates, cresolates or naphthenates of alkali metals, sulfonol, quaternary ammonium bases, fatty acid amides , N-oxides of amines, etc. (EAPO 018297, US 8900446, US 6960291 B2, etc.). Organic nitrogen-containing substances — the oxidation promoters of mercaptans and hydrogen sulfide (US 4,753,722 A) —are also known from the state of the art.

The authors do not limit the scope of the invention to consideration of any specific options for additional organic substances - additives in the composition of the described catalyst, which, as mentioned above, are used as solvating components, phase transfer catalysts or promoters of oxidation of mercaptans and are known from the prior art. Such organic additives in aqueous alkaline solutions used for the purification of hydrocarbon materials from mercaptans and hydrogen sulfide are widely described in the patent literature. As mentioned above, such additives are well known in the art and can be used as an addition to the neutralizer composition described in the invention; they can be selected for each individual cleaning task and each individual case without limiting the generality of the invention. Without highlighting these additives as a separate subject of the invention, the authors give examples of the use of such additives only as an illustration, but without limiting the generality of the invention. Ultimately, the selection of such organic additives for each individual case greatly depends on the conditions of a particular task, the economy of the issue, the properties of the raw materials, etc.

The authors believe that compounds of metals of variable valency in a high degree of oxidation from the series Co (3+), Cu (2+), Fe (3+) or Mo (6+) in the composition described here play the role of catalysts for the oxidation of mercaptans and hydrogen sulfide, alkali metal nitrite acts as an oxidizing agent, and a water-soluble amine or ammonia, or a mixture of a water-soluble amine or ammonia and an inorganic base, is a cocatalyst. However, in the context of the invention, the authors do not limit themselves to any particular theory, but point to a practical result achieved by available means and which can be implemented in industry.

It has been established that the scavenger-neutralizers according to this purification method selectively interact with H ₂ S and low molecular weight mercaptans, while the reaction product does not contain extraneous odor by-products, which distinguishes this method from purification by formaldehyde and triazine scavengers widely used in industry. Thus, purifiers ensure the removal of the most volatile mercaptans and hydrogen sulfide, the presence of which in the medium is the main cause of unpleasant odor and corrosion in the absence of a purifier consumption for reactions with less volatile mercaptans. It was found that the use of these metals in a high degree of oxidation leads to a significant increase in the rate of purification of the medium from hydrogen sulfide and low molecular weight mercaptans, and also allows cleaning at low temperatures. These factors are crucial for the implementation of treatment in real-world fishing conditions.

The following examples are presented to illustrate some specific embodiments of the invention (but not limited to). Obviously, the description and examples are presented only to illustrate the invention and are included in the scope and essence of the invention, as defined in the claims. It is also obvious that the examples cannot, in particular, exhaust all water-soluble compounds of the above metals of variable valency known from the prior art, respectively, the examples given are only an illustration of examples of embodiment of the subject invention, but do not exhaust all possible implementations of it. Other options included in the scope of the claims are obvious to a person skilled in the art after reading the description of the invention or putting it into practice, as described in this context.

The invention can be demonstrated by some of the examples below, which, however, only illustrate but do not exhaust the subject of the invention.

In the above experiments, neutralizing absorbers are used in the form of aqueous solutions of these substances at the level of natural solubility under normal conditions and at room temperature. Solutions are obtained by simply dissolving the components. All experiments are carried out in an argon atmosphere: i.e. the flask in which the oil is treated with a neutralizer is purged with argon before treatment.

In examples 1-7, crude oil with a hydrogen sulfide content of 254 ppm is used as a feedstock for refining. The residual water content of 0.2%.

In examples 8-12, crude oil with a hydrogen sulfide content of 24 ppm and a methyl ethyl mercaptan content of 416 ppm (total for methyl and ethyl mercaptans) is used as a feedstock for refining. The residual water content is 1%.

In examples 13-14, the N.K. fraction is used as raw material for purification. - 300 ° С - paraffin solvent in oil production with 89 ppm hydrogen sulfide content, 67 ppm methyl ethyl ethyl mercaptans. Test on a copper plate - does not stand up, class 3A.

The determination of hydrogen sulfide, methyl and ethyl mercaptans is carried out according to the standard method according to GOST R 50802-95. Tests on a copper plate fraction N.K. - 300 ° C are carried out in accordance with GOST 6321-92.

Example 1. In the preparation of the neutralizer, dry reagents are added to the solution sequentially after dissolution of all previous additives. Liquid reagents are added after dissolving the dry reagents. Mixing is carried out until a homogeneous product. All preparations are carried out at room temperature.

66.03 g of distilled water is added to the flask, 0.67 g of Merox catalyst is charged into it, 23.6 g of sodium nitrite are added after dissolution, 5.27 g of sodium hydroxide are added after dissolution, 4.43 g of diethanolamine are added after dissolution and stirred to obtain a homogeneous product. The resulting composition A1 of the composition (wt.%): Merox catalyst 0.67, sodium nitrite 23.6%, sodium hydroxide 5.27, diethanolamine 4.43, water, the rest is used to neutralize 254 ppm hydrogen sulfide in oil.

96 g of crude oil is charged into a thermostatic flask equipped with a mechanical stirrer and jacket. Then, the calculated amount of reagent is introduced into the flask based on the dosage of 750 g / t, i.e. 0.072 g. The flask was purged with argon to completely remove air. The reaction mixture is stirred for a predetermined time at the indicated temperature. Measurement of the hydrogen sulfide content is carried out in this example after 2 hours (result of 7 ppm) and after 3 hours (result of 0.5 ppm). The oil temperature in this experiment is + 32 ° C.

The table below shows the dosages of the finished aqueous solution of the absorber, the percentage of the substance in the solution and the ratio of this substance to hydrogen sulfide (and mercaptans), expressed in the number of moles of hydrogen sulfide (and mercaptans) per 1 mol of this substance.

Example 2. As in example 1, dry reagents are added to the solution sequentially after dissolution of all previous additives. Liquid reagents are added after dissolving the dry reagents. Mixing is carried out until a homogeneous product. All preparations are carried out at room temperature.

65.7 g of distilled water is added to the flask, 0.67 g of CuEDTA (copper + 2 and EDTA complex) is charged into it, 20.0 g of sodium nitrite are added after dissolution, 13 g of diethanolamine are added after dissolution and stirred to obtain a homogeneous product. The resulting composition A2 composition (wt.%): CuEDTA - 1.3, sodium nitrite - 20.0, diethanolamine - 13, water - the rest is used to neutralize 254 ppm of hydrogen sulfide in oil. The tests of the catalyst are carried out similarly to the procedure of example 1: the amount of 96 g of crude oil is loaded into a thermostatic flask equipped with a mechanical stirrer and a jacket. Then, the calculated amount of reagent is introduced into the flask based on the dosage of 530 g / t, i.e. 0.051 g. The flask was purged with argon to completely remove air. The reaction mixture is stirred for a predetermined time at the indicated temperature. Measurement of the hydrogen sulfide content is carried out in this example after 2 hours (result of 9 ppm) and after 3 hours (result of 0.5 ppm). The oil temperature in this experiment is + 32 ° C.

Example 3. As in examples 1 and 2, dry reagents are added to the solution sequentially after dissolution of all previous additives. Liquid reagents are added after dissolving the dry reagents. Mixing is carried out until a homogeneous product. All preparations are carried out at room temperature. The resulting composition A3 composition (wt.%): FeEDTA (complex of iron +3 and EDTA) - 1.2, potassium nitrite - 24.0, ammonia - 3.8, sodium hydroxide - 4.6, water - the rest is used to neutralize 254 ppm of hydrogen sulfide in oil.

Tests of the neutralizer are carried out similarly to the procedure in examples 1 and 2. Dosage 700 g / t Measurements of the hydrogen sulfide content are carried out in this example after 2 hours (result of 15 ppm) and after 3 hours (result of 4 ppm). The oil temperature in this experiment is + 32 ° C.

Example 4. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-3. The resulting composition A4 composition (wt.%): Na ₂ MoO ₄ ⋅ 2H ₂ O (sodium molybdate) - 0.55, sodium nitrite - 24.46, triethanolamine - 11.8, ammonia - 1.34, sodium hydroxide - 4 , 2, water - the rest is used to neutralize 254 ppm of hydrogen sulfide in oil. The tests of the converter are carried out similarly to the procedure in examples 1-3. Dosage 500 g / t. Measurements of the hydrogen sulfide content are carried out in this example after 2 hours (result 12 ppm) and after 3 hours (result 2 ppm). The oil temperature in this experiment is + 32 ° C.

Example 5. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-4. The resulting composition A5 composition (wt.%): Merox catalyst - 0.67, potassium nitrite - 25.0, ammonia - 2, sodium hydroxide - 3.13, water - the rest is used to neutralize 254 ppm hydrogen sulfide in oil.

The tests of the neutralizer are carried out similarly to the procedure in examples 1-4. Dosage 670 g / t. Measurement of the hydrogen sulfide content is carried out in this example after 2 hours (result 21 ppm). The oil temperature in this experiment is + 32 ° C.

Example 5 *. The preparation of the catalyst is carried out in the sequence similar to the procedure in example 5 with the only difference being that an aqueous-alcohol solution of alkyldimethylbenzylammonium chloride is additionally added as a phase transfer catalyst to the resulting reagent solution. The resulting composition A5 * composition (wt.%): Merox catalyst - 0.67, potassium nitrite - 25.0, ammonia - 2, sodium hydroxide - 3.13, alkyldimethylbenzylammonium chloride - 1, ethanol - 2, water - the rest is used for neutralizing 254 ppm of hydrogen sulfide in oil. The tests of the converter are carried out similarly to the procedure in examples 1-6. Dosage 670 g / t. Measurement of the content of hydrogen sulfide is carried out in this example after 2 hours (result of 9 ppm). The oil temperature in this experiment is + 32 ° C.

Example 6. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-5. The resulting composition A6 composition (wt.%): Merox catalyst - 0.335, potassium nitrite - 25.0, ammonia - 2, sodium hydroxide - 3.13, water - the rest is used to neutralize 254 ppm hydrogen sulfide in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-5. Dosage 670 g / t. Measurement of the content of hydrogen sulfide is carried out in this example after 2 hours (result 191 ppm). The oil temperature in this experiment is + 32 ° C.

Example 7. Prepared from example 5, composition A5 composition (wt.%): Merox catalyst - 0.67, potassium nitrite - 25.0, ammonia - 2, sodium hydroxide - 3.13, water - the rest is used to neutralize 254 ppm hydrogen sulfide in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-6. Dosage 670 g / t. Tests of this converter are carried out for three different cases at different temperatures. Measurement of the hydrogen sulfide content is carried out in one experiment after 4 hours at an oil temperature of + 21 ° C (16 ppm result), in a second experiment after 16 hours at an oil temperature of + 5 ° C (8 ppm result), in a third experiment after 24 hours at a temperature oil -5 ° C (result 18 ppm).

Example 8. The preparation of the Converter is carried out in the sequence similar to the procedure in examples 1-6. The resulting composition A8 composition (wt.%): FeEDTA (complex of iron +3 and EDTA) - 1.13, sodium nitrite - 15.35, piperidine - 3.9, sodium hydroxide - 7.34, water - the rest is used to neutralize hydrogen sulfide 24 ppm, methyl - ethyl mercaptans 416 ppm (total for methyl and ethyl mercaptans) in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-7. Dosage 1500 g / t. The measurements are carried out in this example after 6 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 14 ppm). The oil temperature in this experiment is + 32 ° C.

Example 9. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-8. The resulting composition A8 composition (wt.%): FeEDTA (iron complex +3 and EDTA) - 1.13, sodium nitrite - 30.7, piperidine - 3.9, sodium hydroxide - 7.34, water - the rest is used to neutralize hydrogen sulfide 24 ppm, methyl - ethyl mercaptans 416 ppm (total for methyl and ethyl mercaptans) in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-7. Dosage 1500 g / t. The measurements are carried out in this example after 6 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 13 ppm). The oil temperature in this experiment is + 32 ° C.

Example 10. The preparation of the neutralizer is carried out in a sequence similar to the procedure in examples 1-9. The resulting composition A10 composition (wt.%): FeSO ₄ (iron sulfate +2) - 0.47, sodium nitrite - 15.35, piperidine - 3.9, sodium hydroxide - 7.34, water - the rest is used to neutralize hydrogen sulfide 24 ppm, methyl - ethyl mercaptans 416 ppm (total for methyl and ethyl mercaptans) in oil.

The tests of the neutralizer are carried out similarly to the procedure in examples 1-9. Dosage 1500 g / t. The measurements are carried out in this example after 6 hours (result: hydrogen sulfide less than 6 ppm, mercaptans 321 ppm). The oil temperature in this experiment is + 32 ° C.

Example 11. The preparation of the neutralizer is carried out in the sequence similar to the procedure in examples 1-9. The resulting composition A11 composition (wt.%): CuEDTA (copper complex +2 and EDTA) - 1.3, sodium nitrite - 20.0, diethanolamine - 10.5, sodium hydroxide - 12, water - the rest is used to neutralize hydrogen sulfide 24 ppm, methyl - ethyl mercaptans 416 ppm (total for methyl and ethyl mercaptans) in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-10. With this converter, two experiments are carried out at different temperatures. The dosage in both experiments is 920 g / t. Measurements in the first experiment are carried out after 3 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 21 ppm). The temperature of the oil in the first experiment + 32 ° C. Measurements in the second experiment are carried out after 8 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 11 ppm). The temperature in the second experiment + 16 ° C.

Example 12. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-11. The resulting composition A12 composition (wt.%): Na ₂ MoO ₄ ⋅ 2H ₂ O (sodium molybdate) - 0.74, sodium nitrite - 15.35, piperidine - 3.9, ammonia - 1.34, sodium hydroxide - 7 , 34, water - the rest is used to neutralize 24 ppm hydrogen sulfide, methyl - ethyl mercaptans 416 ppm (total for methyl and ethyl mercaptans) in oil.

The tests of the converter are carried out similarly to the procedure in examples 1-11. With this converter, two experiments are carried out at different temperatures. The dosage in both experiments is 1500 g / t. Measurements in the first experiment are carried out after 6 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 12 ppm). The temperature of the oil in the first experiment + 32 ° C. Measurements in the second experiment are carried out after 4 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 4 ppm). The temperature in the second experiment + 49 ° C.

Example 13. The preparation of the Converter is carried out in the sequence similar to the procedure in examples 1-12. The resulting composition A13 composition (wt.%): Merox catalyst - 0.78, sodium nitrite - 22.9, monoethanolamine 3.34, sodium hydroxide - 9.1, water - the rest is used to neutralize hydrogen sulfide 89 ppm, methyl ethyl mercaptans 67 ppm in the N.K. fraction - 300 ° С - paraffin solvent in oil production.

The tests of the converter are carried out similarly to the procedure in examples 1-12. Dosage 350 g / t. The measurements are carried out in this example after 6 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 2 ppm). Test on a copper plate - maintains, class 1A. The oil temperature in this experiment is + 32 ° C.

Example 14. The preparation of the Converter is carried out in a sequence similar to the procedure in examples 1-13. The resulting composition A14 composition (wt.%): FeEDTA (complex of iron +3 and EDTA) - 2.5, sodium nitrite - 22.9, monoethanolamine - 3.34, sodium hydroxide - 9.1, water - the rest is used to neutralize hydrogen sulfide 89 ppm, methyl - ethyl mercaptans 67 ppm in the N.K. fraction - 300 ° С - paraffin solvent in oil production.

The tests of the neutralizer are carried out similarly to the procedure in examples 1-13. Dosage 350 g / t. The measurements are carried out in this example after 7 hours (result: hydrogen sulfide less than 0.5 ppm, mercaptans 12 ppm). Test on a copper plate - maintains, class 1A. The oil temperature in this experiment is + 32 ° C.

Example 15. The use of the Converter according to example 4 for the purification of associated petroleum gas from hydrogen sulfide. 40 ml of A4 converter according to Example 4 are poured into a glass packed absorber filled with Rashig rings with a diameter of 20 mm and a height of 500 mm, as described in Example 4. Then, at room temperature and atmospheric pressure, associated gas containing 0.09 g / m ^{3 of} hydrogen sulfide and 0.025 is passed through the absorber g / m ³ methyl sulfur and ethyl mercaptans. The gas feed rate is 16 dm ³ / h. The gas supply is controlled by a gas drum counter (with a liquid shutter). The purified gas leaving the top of the absorber is passed through an absorption bottle with a solution of potassium hydroxide of 35 wt. %, for the absorption of residual hydrogen sulfide and mercaptans. At the end of the experiment, the absorption solution is analyzed for sulfide and mercaptide sulfur content by potentiometric titration according to GOST 22387.2-97 and the residual concentration of hydrogen sulfide in the purified gas and the degree of gas purification are calculated. The degree of gas purification from hydrogen sulfide is 99.99% and from mercaptans 99.9%. In this case, foaming of the catalyst and the formation of solid reaction products is not observed. T.O. The neutralizer is suitable for the purification of both liquid and gaseous hydrocarbons.

Example 5 * compared with example 5 demonstrates an improvement in the result due to additives in the composition of the neutralizer.

Example 6 in comparison with example 5 demonstrates how the deviation from the proportions of the metal content in the composition (the ratio of moles of metal to moles of hydrogen sulfide) established by the invention affects the quality of cleaning, which is reflected in the claims.

Examples 7 and 11 give an idea of the health of the cleaning process when the temperature of the medium is lowered. Example 12 gives an idea of the effect of a rise in temperature.

Examples 8 and 9 give the idea that increasing the alkali metal nitrite content above the limits specified in the claims does not improve the result.

Examples 8 and 10 give the idea that the use of a metal compound is not highly oxidized, as defined in the claims, does not lead to the desired result.

Examples 13 and 14 show an improvement in fuel performance on a copper plate.

The results of the described experiments are summarized in table. The table shows the dosages of the finished aqueous solution of the scavenger, the percentage (%) of the substance in the solution and the ratio of this substance to hydrogen sulfide (and mercaptans), expressed in the number of moles of sulfur sulfide (and mercaptans) per 1 mol of this substance.

Claims (14)

1. A method for purifying hydrocarbon media from H ₂ S and / or mercaptans, in which the hydrocarbon feed is treated with a purification composition containing an aqueous solution of an alkali metal nitrite, a water-soluble amine and / or ammonia, or a mixture of a water-soluble amine and / or ammonia and a strong inorganic base in the presence of metals of variable valency, the method is carried out in the absence of oxygen, and metals of variable valency are used in a high degree of oxidation. 2. The method according to p. 1, in which the metals of variable valency in a high degree of oxidation are selected from the group comprising Co (3+), Cu (2+), Fe (3+) or Mo (+6) and combinations thereof. 3. The method according to PP. 1 and 2, in which metals of variable valency are used in the form of water-soluble salts or complexes. 4. The method according to p. 1, in which alkanolamines are used as a water-soluble amine, and alkali metal hydroxide is sodium or potassium as a strong inorganic base. 5. The method according to PP. 1 and 4, in which primary, secondary or tertiary ethanolamines are used as alkanolamines. 6. The method according to p. 1, in which the hydrocarbon medium is selected from the group comprising crude oil, water-oil emulsions, oil residues, straight-run fractions and secondary distillates, low molecular weight hydrocarbons, aromatic solvents, hydrocarbon gas mixtures. 7. The method according to p. 1, 2, 4 or 6, in which the metal of variable valency is used at the rate of 1 mol per 30-1000 moles of mercaptan or hydrogen sulfide sulfur. 8. The method according to p. 1, 2, 4 or 6, in which the metal of variable valency is used at the rate of 1 mol per 100-800 moles of mercaptan or hydrogen sulfide sulfur. 9. The method according to p. 1, 2, 4 or 6, in which the metal of variable valency is used at the rate of 1 mol per 150-600 moles of mercaptan or hydrogen sulfide sulfur. 10. The method according to p. 1, 2, 4 or 6, in which an aqueous solution of alkali metal nitrite is used at the rate of 1 mol of alkali metal nitrite per 2-6 moles of mercaptan and / or hydrogen sulfide. 11. The method according to p. 1, 2, 4 or 6, in which a water-soluble amine or ammonia is used at the rate of 1 mol per 2-20 moles of mercaptan and / or hydrogen sulfide sulfur. 12. The method according to p. 1, 2, 4 or 6, in which the inorganic base is used at the rate of 1 mol per 2-20 moles of mercaptan and / or hydrogen sulfide. 13. The method according to p. 1, in which the processing is carried out at a temperature of from -5 to + 80 ° C 14. The method according to p. 13, in which the treatment is carried out at a temperature of from +5 to + 50 ° C.