Composition for neutralizing hydrogen sulfide and light mercaptans in oil environments
The invention relates to chemical compositions, in particular to the means for neutralization of hydrogen sulfide and light methyl-, ethyl mercaptan in petroleum environments, and can be used in the oil and petrochemical industry. Composition for neutralizing hydrogen sulfide and light mercaptans contains 16-35% of the nitrite of an alkali metal, 3-30% of nitrogen-containing primary and/or alkaline reagent and 100% water. As the nitrite of an alkali metal it mainly contains sodium nitrite, as nitrogen-containing basic and alkaline reagents - alkanolamine (mono-, triethanolamine, methyldiethanolamine), and/or ammonia and/or sodium hydroxide, and potassium. The technical result is to increase the efficiency of neutralization of hydrogen sulfide and simultaneously lung methyl-, ethyl mercaptan in petroleum and petroleum products, reducing acidity and corrosional purified raw materials, as well as expansion of the range available, cheap and high-tech (non-corrosive and stable during transportation and storage of chemicals-converters for commercial purification of hydrogen sulfide - and mercaptoundecanoic oils. 3 C. p. F.-ly.
The invention of ethylmercaptan in oil environments and can be used in oil production and refining industries.
Known composition to neutralize the hydrogen sulfide in the production of oil wells, including polyglyceryl - products of waste glycerol and aqueous solution of sodium chloride in the following ratio of components, about. %: polyglyceryl 60-90 and an aqueous solution of sodium chloride 10-40 (U.S. Pat. Of the Russian Federation No. 2136864, E 21 In 43/22, 37/06, 1999).
The disadvantage of this structure is not sufficiently high neutralizing capacity against hydrogen sulfide (3.7 volume of hydrogen sulfide on 1 volume of neutralizer) and light mercaptans, which then requires the use of large amounts of catalyst, which increases material costs and reduced efficiency of the whole process.
Known application of 40% aqueous solution of hexamethylenetetramine (it has been), previously obtained by the interaction of ~37% aqueous solution of formaldehyde (formalin) with ammonia for neutralization of hydrogen sulfide and mercaptans in petroleum and petroleum products (U.S. Pat. U.S. No. 5213680, C 10 G 29/20, 1993).
However, this structure does not provide an effective neutralization of hydrogen sulfide and especially light mercapto the mercaptans at ordinary temperatures, which then requires carrying out the process at elevated temperatures (above 82-100°C) and high consumption of the used catalysts (up to 100 thousand ppm). This leads to increased energy consumption for heating of raw materials and reduce the efficiency of the process as a whole.
Known to use a mixture of 50-100% nitric acid with iron, taken in an amount of 0.1-1.0% for the oxidative purification of oil and gas condensate from sulfur compounds, including hydrogen sulfide and light mercaptans (U.S. Pat. Of the Russian Federation No. 2134285, C 10 G 17/02, 1999).
The main disadvantage of this oxidation mixture is its high corrosivity with respect to conventional structural materials. In addition, the application of a mixture of 50-100% nitric acid with iron for neutralization of hydrogen sulfide and mercaptans leads to contamination of the purified oil iron and increase its acid number. Increasing acidity (up to 20 mg KOH/100 ml of oil) and, therefore, corrosional oil requires subsequent leaching of treated oil with an aqueous solution of alkali, which leads to more complicated and expensive purification process in General (Sapeva A. M. Liquid-phase demercaptanization of oils and gas condensates. Avtoreferat the oxidative purification of oil from sulfur compounds, including 50-96% aqueous solution of formic acid and 30-90% aqueous solution of hydrogen peroxide, taken in a molar ratio of HCOOH: H2O2in the range from 1:4 to 4:1, preferably 1:1 (U.S. Pat. U.S. No. 5310479, C 10 G 19/02, 1994). The composition has a high oxidative capacity compared to sulphur compounds, including hydrogen sulphide and light mercaptans. However, as the mixture of nitric acid with iron, it has extremely high corrosion aggressivity, and low chemical stability during storage (due to rapid spontaneous decomposition of hydrogen peroxide and contained naturalyou acid).
As the prototype was taken neutralizer sulfide consisting of hydrogen peroxide and water. In an advantageous version of the application it represents 20-50% aqueous solution of hydrogen peroxide, which are taken at a rate of not less than 20 ml (based on a 35% solution of N2ABOUT2) 1 g neutralizing of hydrogen sulfide (U.S. Pat. Germany No. 3151133, C 10 G 27/12, 1983; RJ "Chemistry", PP, 1984).
The main disadvantage of this Converter is not sufficiently high efficiency, especially in relation to light mercaptans, which does not allow to obtain goods the temporary requirements in accordance with GOST R 51858-2002 on the prepared oil. In addition, hydrogen peroxide is metastability product spontaneously decompose to water and oxygen during transportation and storage, and therefore the need for transportation and storing it in a special, pre-passivated aluminum tanks at a temperature not exceeding 30°C and not below minus 30°C; it is not allowed to use the equipment and pipelines of unalloyed and low-alloyed steel, cast iron and other structural materials, which are catalysts for the decomposition of hydrogen peroxide (see GOST 177-88. Of hydrogen peroxide. M.: Izd-vo standards. 1988. S. 2, 3, 5 and 12). These shortcomings, as well as a relatively large flow rate and high cost of hydrogen peroxide, the contamination of the purified oil produced corrosive elemental sulfur, hinder the practical application of aqueous solutions of hydrogen peroxide as a neutralizer for deodorizing purification of hydrogen sulfide-containing oil in the field.
The present invention is the task of creating a composition for neutralizing hydrogen sulfide and light mercaptans in oil environments, with high efficiency in relation to hydrogen sulfide and simultaneously to the lower flow rate, as well as adaptability to practical field application. The invention simultaneously solves the problem of reducing the acidity and corrosional purified raw materials due to the application of the composition with a neutralizing ability against are contained in the raw material oil (naphthenic) acids.
The problem is solved in that the composition for neutralizing hydrogen sulfide and light mercaptans in oil environments, including oxidizing agent and water as the oxidant contains a nitrite of an alkali metal, and optionally contains a nitrogen-containing basic and/or alkaline reagent in the following ratio, wt.%:
Nitrite of an alkali metal 16-35
Nitrogen-containing basic and/or alkaline reagent 3-30
Water To 100
As the nitrite of an alkali metal proposed composition mainly contains sodium nitrite, as nitrogen-containing basic and alkaline reagents - alkanolamine, and/or ammonia, and/or a hydroxide of alkaline metal (sodium and/or potassium). As alkanolamine composition mainly contains mono-, triethanolamine, methyldiethanolamine or mixtures thereof.
The inventive catalyst of hydrogen sulfide and light color it with a pour point of not higher than minus 20°C density in the range of 1.13-1.35 g/cm3(depending on the ratio of components) and the value of pH from 11 to 14. As a source of raw materials for the preparation of the proposed composition predominantly use sodium nitrite technical GOST 19906 or sodium atomistically in solution on THE 38-1021278-90 (produced in large scale for use as inhibitors of atmospheric corrosion and for other purposes), and as a nitrogen-containing basic chemicals mainly used monoethanolamine technical on THE 6-02-918-84 or triethanolamine technical on THE 6-02-916-79, and as the alkaline reagent is sodium hydroxide according to GOST 2263 or GOST 11078, or potassium GOST 9285. These raw materials are produced by the domestic industry in large scale and are accessible, affordable products, i.e. from the point of view of availability of raw material, the composition is industrially applicable.
Technology of preparation of the composition is simple and dissolving the resulting optimum amounts of the starting components (nitrite of an alkali metal and an alkaline reagent) in fresh or demineralized water or steam condensate at a normal temperature is the technology of applying the proposed composition is continuous dosage found the optimal number of Converter preferably based 4-9 g per 1 g neutralizing of hydrogen sulfide and light methyl-, ethyl mercaptan, a sulfur stream of oil with temperature in the range of 20 to 100°C, preferably 30 to 70°C, at atmospheric or increased pressure (the pressure has no effect on the rate of oxidation reactions and the degree of neutralization of hydrogen sulfide and light mercaptans). Treatment plants sulfur crudes after step thermochemical dehydration oil flows typically have a temperature in the range of 40 to 70°With no further heating the cleaned oil when applying the proposed Converter is not required. Since the proposed Converter is a water-salt solution and practically insoluble in petroleum and petroleum products, to improve its dispersion in the cleaned raw material, it is advisable to measure the catalytic Converter in the flow of oil before centrifugal pump pump, which is the effective mixing device, or to enter into the pipeline in the oil flow with turbulence through effective spray device. You should indicate that to improve the dispersion of the catalyst in the oil and accelerate oxidation reactions in the composition of the catalyst can be dopolnitelnye, OP-10, or water-soluble phase transfer catalyst type Quaternary ammonium salt, etc.,
The need and feasibility of additional introduction in the composition of the catalyst containing primary and/or alkaline reagent due to the fact that in acidic and neutral environments, i.e. in the environment of oil and oil products nitrites oxidize hydrogen sulfide and light mercaptans, low speed and allocation of undesirable oxides of nitrogen (NO and NO2), and in the presence of optimal amounts of alkaline agent with sufficient speed and with the formation of ammonia, which then interacts with contained in crude oil (carboxylic) acids, thereby, achieved by reducing the acidity of the treated oil. Should indicate that the effective reduction in the acidity and corrosional crude oil in the processing of its gaseous or liquid ammonia at temperatures of 20 to 50°C and above is described in U.S. Pat. U.S. No. 6258258, C 10 G 17/00, 2001, When applying the proposed composition of the ammonia formed as a result of reactions of hydrogen sulfide oxidation by nitrite directly in oil and then consumed for neutralization of petroleum acids and other acidic impurities (carbon dioxide, phenols, etc.,), d is corrosional. Additional introduction of nitrogen-containing basic reagent is also due to the fact that nitrite selectively oxidize hydrogen sulfide to elemental sulfur, which in the presence of an amine as a catalyst for further interacts with contained in the oil mercaptans, including easy methyl-, mercaptan, resulting in preventing the pollution of treated oil corrosive elemental sulfur. Hydroxides, carbonates, phosphates of alkali metals do not possess catalytic activity in the reaction of elemental sulfur with mercaptans, so it is appropriate to introduce them into the composition together with the amine (to reduce consumption alkanolamine). The proposed concentration of amine and/or alkali (3-30%) is optimal, because reducing it to less than 3% leads to a decrease in the rate of oxidation reactions, and the increase above 30% decrease in the solubility of nitrite and crystallization in the application of the neutralizer in the winter. The proposed concentration of nitrite (16-35%) is also optimal, because the use of more dilute composition (less than 16%) leads to an increase in the cost of transportation and storage of large amounts of catalyst and increase the water content in the treated oil, and the increase in concentration above 35% necelesobrazno search of known technical solutions showed in science and technology there is no object, similar to the claimed combination of features and properties, which allows to make a conclusion on compliance with its criteria of "novelty" and "inventive step".
To prove the conformity of the object to the criterion of "industrial applicability" below are specific examples of the preparation of catalysts (studies 1-3) and test it on the efficiency of neutralization of hydrogen sulfide and light mercaptans in petroleum and petroleum fractions (examples 4-7).
Example 1. In capacity, equipped with a mechanical stirrer, a load of 75 g of sodium azotistogo in solution on THE 38.1021278-90 grade B with a mass concentration of nitrite 295 g/DM3and under stirring portions add 25 g of monoethanolamine (MEA) technical beyond 6-02-915-84, and the resulting aqueous-alkaline solution of sodium nitrite stirred for 0.5 h at room temperature to obtain a homogeneous product. The resulting composition composition, wt.%: sodium nitrite - 18,5, IEA -25 and water - the rest with a pH of 11.7 and a density of 1.15 g/cm3used for neutralization of hydrogen sulfide and light mercaptans in oil (example 4) and the oil fraction (example 7).
Example 2. In the capacity of example 1 load 52 g of the obtained solution was added with stirring 5 g of sodium hydroxide according to GOST 2263, and then 8 g of monoethanolamine. The resulting solution was stirred for 0.5 h to obtain a homogeneous product. The resulting composition composition, wt.%: sodium nitrite - 35, sodium hydroxide and 5 IEA -8 and water -52 with a density of 1.31 g/cm3used for neutralization of hydrogen sulfide and light mercaptans in oil (example 5).
Example 3. In the capacity of example 1 load 50 g of water, 30 g of sodium nitrite technical and 5 g of sodium hydroxide. After complete dissolution of nitrite and sodium hydroxide in the resulting solution was added with stirring 15 g of technical triethanolamine (tea) TU 6-02-916-79 and stirred for 0.5 h to obtain a homogeneous product.
The resulting composition composition, wt.%: sodium nitrite - 30, sodium hydroxide and 5, the tea - 15 and water - 50 with a density of 1.31 g/cm3used for neutralization of hydrogen sulfide and light mercaptans in oil (example 6).
Example 4. The test composition on the efficiency of neutralization of hydrogen sulfide and light methyl-, ethyl mercaptan in petroleum. In the temperature-controlled reaction flask with stirrer enter of 0.26 ml (0.3 g) of the catalyst of example 1, and then load 100 ml (92 g) high-carbon oil containing 0.2 wt.% emulsion of water, of 0.025 wt.% (250 ppm) does neutralizer: hydrogen sulfide + methyl-, ethyl-mercaptan in the reaction mixture is 9:1, i.e., the specific consumption of the Converter (the expense ratio) amounts to 9 g/g, the Reaction mixture was intensively stirred at a temperature of 50°C for 3 h and conduct quantitative analysis of the purified oil to the content of residual hydrogen sulfide and light mercaptans, and calculate the degree of purification of oil. The degree of purification of oil from the hydrogen sulfide is 100% and from the lungs methyl-, mercaptan - 87%, i.e., the proposed Converter in example 1 when the feed ratio of 9 g/g provides effective neutralization of hydrogen sulfide and light methyl-, ethyl mercaptan and allows you to get the commodity oil, corresponding to the standards GOST R 51858-2002 content of hydrogen sulfide and methyl-, ethyl mercaptan.
Example 5. Test Converter according to example 2 on the efficiency of neutralization of hydrogen sulfide and light methyl-, ethyl mercaptan in petroleum spend the same conditions of example 4, but at specific discharge (supply factor) Converter 4.5 g/, the Degree of purification of oil from the hydrogen sulfide is 100% and from the lungs methyl-, mercaptan - 89%, i.e., the neutralizer according to the example 2, when the feed ratio of 4.5 g/g provides effective neutralization of grey is 6. Test Converter according to example 3 on the efficiency of neutralization of hydrogen sulfide and methyl-, ethyl mercaptan in petroleum spend the same conditions of example 4, but at specific discharge neutralizer 7 g/, the Degree of purification of oil from the hydrogen sulfide is 100% and from light mercaptans - 98%, i.e., the catalyst from example 3 when the feed ratio of 7 g/g provides effective neutralization of hydrogen sulfide and light mercaptans, and allows to obtain marketable oil GOST R 51858.
Example 7. In the reaction flask according to example 4 is injected to 0.12 ml of neutralizer in example 1, then load 100 ml of distilled oil fractions N. K. - 300°used as a solvent of paraffin in oil and containing 0.01 wt.% of hydrogen sulfide, 0.01 wt.% lung methyl-, ethyl mercaptan, having a pH of 9.9 mg KOH/100 ml Mass ratio of catalyst: hydrogen sulfide + methyl-mercaptan in the reaction mixture is 9:1, i.e., the expenditure ratio is 9 g/g, the Reaction mass is stirred at 50°C for 3 h, and then conduct a quantitative analysis of the purified fractions the content of residual hydrogen sulfide and light mercaptans, determine its acidity according to GOST 5985 and corrosivity test copper PLA is g KOH/100 ml The purified fraction test copper plate stand, i.e., reduced acidity and toxicity of the product for use as a solvent paraffin oil production.
Comparative experiment showed that the application of a known Converter - 30% aqueous hydrogen peroxide solution (prototype), the degree of purification of high-carbon oil from the hydrogen sulfide is 90%, from light mercaptans - 35%, i.e. well-known Converter does not provide an effective neutralization of hydrogen sulfide and light mercaptans, and allows you to get marketable oil GOST R 51858. Comparative experiment on cleaning of straight-run petroleum fractions N. K. -300°C showed that the purified raw material contains elemental sulfur, and test copper plate does not stand up, i.e., the known Converter does not provide the reduction of acidity and corrosional pure product.
The data presented in examples 4-6 show that the composition has high efficiency of neutralization of hydrogen sulfide and simultaneously lung methyl-, ethyl mercaptan in petroleum environments and provides commercial oil that meets modern design requirements of example 7 show the proposed Converter provides reduced acidity and corrosional purified raw materials. In addition, the proposed Converter, in contrast to the known, is non-corrosive and stable during transportation and storage of the product, which allows its use for commercial cleaning sulfide and mercaptoundecanoic oils.
1. Composition for neutralizing hydrogen sulfide and light mercaptans in oil environments, including oxidizing agent and water, characterized in that as the oxidant contains a nitrite of an alkali metal, and optionally contains a nitrogen-containing basic and/or alkaline reagent in the following ratio, wt.%:
Nitrite of an alkali metal 16-35
Nitrogen-containing primary and/or
alkaline reagent 3-30
Water To 100
2. Composition under item 1, characterized in that as the nitrite of an alkali metal it contains sodium nitrite.
3. The composition according to PP.1 and 2, characterized in that as the nitrogen-containing basic chemicals it contains alkanolamine and/or ammonia, and as the alkaline reagent is sodium hydroxide and/or potassium.
4. The composition according to p. 3, characterized in that as alkanolamine about
FIELD: oil-refining industry; methods of oil refining.
SUBSTANCE: the invention is pertaining to the field of oil refining, in particular to a method of refining of petroleum, gas condensate and their factions and also oil emulsions from hydrogen sulfide. Refining is carried out by treatment of raw material by 10-45 % water solution of pyrosulfite or hydrosulfite of alkali metal or ammonium hydrosulfite in quantity of no less than 1 gramme-molecule of pyrosulfite or no less than 2 gramme-molecule of hydrosulfite per 1 gramme-molecule of hydrogen sulfide. The process is carried out at the temperature of 10-80°C at the presence of 10-45 % water solutions of hydroxide water solution , or 10-25 % of a water solution of carbonate, orthophosphate and-or sodium or ammonia sulfite at the ratio of 0.5-2 gramme-molecule of the given reagent per 1 gramme-molecule of carbon sulfide. At that the indicated solution is introduced in the feed stock in the form of a separate stream or together with the water solution of pyrosulfite or sodium hydrosulfite in the form of a previously prepared water solution of the reagent - neutralizer. Part of a spent water solution of reagents after separation from the rectified raw material is preferably returned in the process. Technical effect - increase of separation efficiency at simplification of the method and decrease of corrosive attack of the reactivity medium.
EFFECT: the invention ensures increased efficiency of separation, decreased corrosive attack of the reaction medium, simplification of the method.
6 cl, 8 ex
FIELD: crude oil treatment.
SUBSTANCE: invention relates to freeing crude oil, gas condensates, and fractions thereof from hydrogen sulfide using neutralization reagents. Cruse oil is purified by treating starting material with 10-45% aqueous solution of alkali metal pyrosulfite or hydrosulfite, or nitrite, or ammonium hydrosulfite taken on the basis of at least 1 mole pyrosulfite or 2 mole hydrosulfite, o5 1 mole nitrite per 1 mole hydrogen sulfide. Process is conducted in presence of alkaline caprolactam production effluent taken in amounts 3 to 15 g per 1 g hydrogen sulfide at 10 to 80°C.
EFFECT: enhanced process efficiency and extended application area for alkaline caprolactam production effluent.
5 cl, 9 ex
FIELD: crude oil treatment.
SUBSTANCE: process of removing hydrogen sulfide and mercaptans from crude oil is characterized by that, after purge of oil with hydrocarbon-containing gas to remove hydrogen sulfide, the rest of hydrogen sulfide is removed by oxidation with air oxygen in presence of water-alkali and ammonia solutions of phthalocyanine catalysts under pressure up to 2.5 MPa followed by separation of exhausted air by reducing pressure to 0.15-0.30 MPa. Exhausted air containing 40-75% hydrocarbons is used at the same pressure is used as hydrocarbon-containing purge gas.
EFFECT: reduced loss of hydrocarbons with exhausted air and reduced consumption of air and reagents in oxidative purification stage.
4 cl, 1 dwg, 1 tbl
FIELD: oil-producing industry; petrochemical industry; other industries; equipment for purification of the petroleum from hydrogen sulfide and mercaptans.
SUBSTANCE: the invention may be used for the field purification of the sulfur-bearing oils from hydrogen sulfide and the light methyl mercaptans and ethyl mercaptans. The prepared petroleum through the pipeline (1) is fed into the upper part of the blowing column (3) (Fig.1), and the hydrocarbon gas through the pipeline (2) is fed into the lower part of the blowing column. The partially purified petroleum from the vat of the column (3)is fed into the separator (4), which through the by-pass pipelines is connected to inlet pipelines of the sulfur-bearing oil and the hydrocarbon gas. Further the petroleum from the vat of the separator (4) and the reactant-neutralizing agent from the vat of the tank (5) by means of the mixer (10), in the capacity of which predominantly use the centrifugal pump, is fed into the tubular reactor (11), which is supplied with the quiescent mixer of the reaction mixture. The reaction mixture from the tubular reactor (11) comes in the buffering tank (13). In other version of the installation (Fig.2) the prepared petroleum goes through the pipeline (1) into the nozzle of the liquid-gas ejector (14), which gaseous fitting pipe is connected to the feeding pipeline (2), and the liquid fitting pipe is connected to the sulfur-bearing petroleum feeding pipeline. The gas-petroleum mixture from the liquid-gas ejector (14) comes into the separator (15), which upper part is connected to the suction fitting pipe of the liquid-gas ejector (16) of the pump -ejector installation. The invention allows to reduce the share of the total sulfur, the water, the light mercaptans and the products of the hydrogen sulfide neutralization by the reactant in the separator oil, to reduce the material inputs at operation of the installation.
EFFECT: the invention allows to reduce the share of the total sulfur, the water, the light mercaptans and the products of the hydrogen sulfide neutralization by the reactant in the separator oil, to reduce the material inputs at operation of the installation.
8 cl, 2 dwg
FIELD: petroleum and gas processing.
SUBSTANCE: invention relates to the area of neutralization of hydrogen sulfide in oil-field media by neutralizing reagents and can be used to neutralize hydrogen sulfide in crude oil, water-oil emulsion, associated oil and natural gas (in produce of oil and gas wells), formation and waste waters, water-based process fluids (well killing fluids, displacement fluids, washing fluid, etc.). Hydrogen sulfide neutralizer is 3-36% aqueous solution of alkali metal pyrosulfite, in particular sodium pyrosulfite. To reduce corrosive activity of neutralizer and also to reduce contamination of purified crude material with thus formed elementary sulfur, neutralizer is supplemented by 1-15% of alkali and/or nitrogen-containing reagent, in particular sodium hydroxide, carbonate, phosphate, and/or sulfite as alkali reagent and aqueous ammonia and/or water-soluble organic amine as nitrogen-containing reagent. A process of purification of oil-field media using above-defined neutralizer is also described.
EFFECT: enhanced hydrogen sulfide neutralization efficiency and enlarged assortment of accessible, nontoxic, stable, and effective neutralizers.
6 cl, 16 ex
FIELD: oil and gas production.
SUBSTANCE: hydrogen sulphide containing oil (see Fig.1) is supplied in a charge separator 2 equipped with a gas bubbler flask 4 where due to pressure reduction and hydrocarbon gas blowing and/or exhaust air, desorption removal of a portion of hydrogen sulphide is observed. Partially refined oil with the introduced oxidation catalyst (see positions 5-10) is supplied by a pump 12 to a reactor 15 where it is additionally purified from hydrogen sulphide and light mercaptan due to their oxidation by introduced air. The reaction mixture is supplied in the high pressure separator 16 ensuring partial separation of exhaust air due to pressure reduction to 0.2 MPa which from the top of the separator is supplied through the gas bubbler flask 4 in the charge separator 2 for blowing hydrogen sulphide from oil. Further it is supplied in the low pressure separator 22 wherefrom the refined and degassed oil is supplied in the first buffer reservoir 25. After filling, oil from the separator is supplied to parallel second reservoir 26, and the filled reservoir 25 is settled for at least 3 hours for water sediment containing water-soluble products of hydrogen sulphide oxidation. In the other version of installation (see Fig.2) the oil refined from hydrogen sulphide, with the pump 27 is supplied in electrodehydrator 30 for separation of emulsion water and salts.
EFFECT: invention allows reducing the concentration of total sulphur, water, salts and products of hydrogen sulphide oxidation in commodity oil and reducing expenses for installation operation.
15 cl, 2 dwg