Method of petroleum refining from hydrogen sulfide

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

 

The invention relates to petrochemistry, in particular to methods of refining oil, gas condensate and its fractions, as well as oil-water emulsions (oil) from the hydrogen sulfide with the use of chemical reagents, neutralizers, and can be used in oil and gas, refining and petrochemical industries.

Known methods for removal of sulfur crude oil and petroleum products from the hydrogen sulfide by treatment of the feedstock with oxygen and/or nitrogen-containing organic reagents - anhydrides, haloganated, inorganic salts of carboxylic acids, peroxide, isocyanates, azodicarboxylate, condensation products of polyamines with aldehydes, Quaternary ammonium compounds, triallylisocyanurate, isoxazolidine and others (U.S. Pat. USA№№4909925, 5223127, 5266185, 5284576, 5344555, 5354453, 6117310 and others).

The main disadvantages of known methods of preventing their wide application in industry, are the scarcity, high cost and high consumption of organic reagents used-neutralizers of hydrogen sulfide.

Known purification method of crude oil and petroleum products from the hydrogen sulfide by treatment of the feedstock with hexamethylenetetramine (it has been)taken up to 100 thousand ppm at a temperature of 100-350°F (37,8-176,6°). While it has been used in the form of ~ 40%aqueous solution, pre is varicella obtained by the interaction of ~ 37%aqueous solution of formaldehyde (formalin) with ammonia (U.S. Pat. U.S. No. 5213680, C 10 G 29/20, 1993).

In the specified method is available and relatively inexpensive reagent neutralizer sulfide. However, the method does not provide the desired degree of purification of the raw material from which hydrogen sulfide due to the low rate of interaction with it has been, especially when carrying out the process at temperatures below 82-100°C. carrying out the process at temperatures above 100°leads to significant energy consumption for heating of the feedstock. Another disadvantage of this method is excessively high consumption of reagent used (up to 10 thousand ppm).

A known method of cleaning oil from sulfur compounds, including hydrogen sulfide, by processing of raw materials inorganic reagent: a mixture of 50-100%nitric acid with iron, taken in an amount of 0.1-1%, at a temperature of 30-100° (U.S. Pat. Of the Russian Federation No. 2134285, C 10 G 17/02, 1999).

The main disadvantage of this method is the significant corrosion of equipment and pipelines for carrying out the process in an acidic medium, high corrosiveness of the chemical reagent. In addition, handling of the oil with a mixture of nitric acid with iron leads to contamination of the purified oil iron, a significant increase in acid number of the oil (up to 20 mg KOH/100 ml of oil), and resinification of oil due to partial oxidation of the hydrocarbon components of the oil mixture AZ is based acid with iron, especially when carrying out the process at elevated temperatures (60-100°). The increase in acidity 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. Abstract of Diss. for obtaining the academic degree of Cand. technology. Sciences., M, Gubkin Russian state University named after I.M. Gubkin, 1999. -25 C.).

There is also known a method of cleaning oil from the hydrogen sulfide by processing raw materials 20-50%aqueous solution of hydrogen peroxide at a temperature of 0-60°and a pressure of 0.5 to 2 MPa. When this aqueous solution of hydrogen peroxide charge at the rate of not less than 20 ml (based on a 35%solution of N2About2) per 1 g of hydrogen sulfide, which corresponds to a molar ratio of N2O2: H2's at least 8 : 1 (U.S. Pat. Germany No. 3151133, C 10 G 27/12, 1983, R.J. “Chemistry”, PP, 1984).

The disadvantages of this method are not sufficiently high degree of purification of oil from the hydrogen sulfide due to the low rate of oxidation in the environment of oil, especially at low temperatures of the process (0-25° (C), and high consumption and high cost of the used reagent. In addition, hydrogen peroxide is metastability product spontaneously decompose to water and oxygen when the protractor is the training and storage, therefore the need for transportation and storage of hydrogen peroxide in special (aluminum) clean container at a temperature not exceeding 30°With; it is not allowed to use the equipment and pipelines of unalloyed and low-alloyed steels, cast iron and other structural materials, which are catalysts for the decomposition of hydrogen peroxide (see GOST 177-88. Of hydrogen peroxide. M., Publishing house of standards, 1988, p.3, p and p.12, paragraph 4.2).

Closest to the proposed invention is a method of purification of water-cut oil (oil-water emulsion) from hydrogen sulfide by treatment with inorganic sulfur-containing reagent is a liquid or gaseous sulfur dioxide, taken in an amount of 1-10 mol per 1 mol of hydrogen sulfide, when the pH of the aqueous phase is less than 6, preferably at a pH of less than 4, then add in the peeled raw alkaline reagent to a pH of more than 6 to neutralize the excess of sulfur dioxide and sulfur formed and positionby acids. At the same time as the alkaline reagent mostly use a hydroxide, a carbonate of an alkali metal, ammonia or organic amines (U.S. Pat. U.S. No. 5346614, C 10 G 17/08, 1994).

The main disadvantages of this method are the complexity of the process because of its mnogostadiinost (acidification to a pH below 4, the treatment with sulfur dioxide, the processing of the alkaline reagent is m by checking the pH of the aqueous phase), not a high degree of purification of anhydrous (dehydrated) oil because of the low rate of oxidation of hydrogen sulfide in anhydrous oil contamination of the purified oil produced elemental sulfur, significant corrosion of equipment and pipelines for carrying out the process in an acidic environment, the corrosivity of the applicable sulfur dioxide and sulfur formed and positionby acids, as well as high consumption of alkali to neutralize the excess of sulfur dioxide and the resulting acids. In addition, the reagent sulfur dioxide is volatile and toxic, so transporting and applying it to fields requires compliance with strict safety measures. These deficiencies significantly reduce the effectiveness of the whole process and prevent a wide practical implementation of this method for field cleaning of large amounts of hydrogen sulfide-containing oils.

The objective of the invention is to increase the efficiency of the process by simplifying the way (excluding mnogostadiinost its implementation), increasing the degree of purification of anhydrous (dehydrated) oil from hydrogen sulfide, prevent contamination of the pure raw elemental sulfur and reduce corrosional reaction medium, peeled raw materials and, consequently, the degree of corrosion of equipment and pipelines. The task of izaberete the Oia is also expanding the range available, non-toxic, less corrosive and more efficient inorganic chemicals-catalysts, suitable for commercial cleaning waterless and watered hydrogen sulfide-containing oils.

According to the invention the mentioned technical result is achieved by the described method of cleaning oil from the hydrogen sulfide by processing the feedstock sulfur-containing inorganic reagent-catalyst, in which the sulfur-containing inorganic reagent is used an aqueous solution of pyrosulfite or hydrosulfite alkali metal, preferably sodium, or hydrosulfite ammonium and the process is carried out in the presence of an aqueous solution of hydroxide, carbonate, orthophosphate and/or sulfite of an alkali metal, preferably sodium or ammonia.

When this aqueous solution of sodium pyrosulfite (Na2S2O5or hydrosulfite (bisulphite) sodium (NaHSO3), or hydrosulfite (bisulphite) ammonium (NH4S3take the rate of not less than 1 mol pyrosulfite or 2 mol of hydrosulfite on 1 mol of hydrogen sulfide, preferably 1.1 to 2.0 mol/mol or 2.1 to 4.0 mol/mol, respectively. Preferably use 10-40%aqueous solution of pyrosulfite or hydrosulfite. An aqueous solution of hydroxide, carbonate, orthophosphate, alkali metal sulfite, preferably sodium or ammonia be the ut at a rate of not less than 0.5 mol, preferably 1-2 mol, hydroxide, carbonate, orthophosphate, sodium sulfite or ammonia per 1 mol of hydrogen sulfide. Preferably use 10-45%aqueous solution of the hydroxide or 10-25%aqueous solution of carbonate, orthophosphate or sulfite of an alkali metal, preferably sodium, or ~25%aqueous ammonia solution (ammonia water technical GOST standard 9-92). When this aqueous solution of hydroxide, carbonate, orthophosphate or sulfite of an alkali metal, preferably sodium or ammonia is injected into the feedstock in the form of a separate stream or in conjunction with the applied aqueous solution of pyrosulfite or hydrosulfite in the form of a previously prepared solution of reagent-catalyst. To reduce reagent consumption and waste water generation part of the waste water of a reagent solution after separation from the pure raw returns to the process in the application of the reagents in the surplus from the stoichiometry of the reactions occurring neutralization of hydrogen sulfide). The oil treatment is carried out at a temperature of 10-80°C, preferably at 20-40°C, at atmospheric or elevated pressures. As used in the proposed method, the reagent-neutralizer sulfide is an aqueous solution, and practically insoluble in petroleum and petroleum products, to improve its dispersion in the cleaned si is d, it is advisable to measure the catalytic Converter in the flow of oil before the centrifugal pump, which is the effective mixing device, or to enter into the pipe with turbulent motion through effective spray device. To improve the dispersion of the catalyst in raw materials and accelerate the neutralization reactions of hydrogen sulfide in the composition can be additionally introduced an effective amount up to 0.1%) of the known water-soluble emulsifier (surfactant) type sulfonic acid, naphthenate, OP-10, etc. and to prevent scaling in the process equipment is known of the scale inhibitor type trylon B (EDTA), NTA, NTF, eddc, etc. (0.1-0.2%).

Distinctive features of the proposed method are the use of an aqueous solution of pyrosulfite or hydrosulfite alkali metal, preferably sodium, or hydrosulfite ammonium found in the optimal molar ratio as inorganic reagent-catalyst of hydrogen sulfide in crude oil and petroleum products, the process in the presence of an aqueous solution of the above alkaline reagents found in optimal quantities and in the specified temperature range (10-80°).

These distinguishing features of the proposed technical solutions determined by its novelty and inventive step in comparison with the prior art in this field as carrying out the cleaning process is not the tee and petroleum products from sulfide materials processing aqueous solutions of pyrosulfite or hydrosulfite in the presence of the above-mentioned alkaline reagents, taken to find the optimal molar ratios, are not described in literature and can improve the efficiency of the process by simplifying the way (the process in one stage, without control and regulation of the pH of the medium, essentially one neutralizer - aqueous-alkaline solution of the pyrosulfite or hydrosulfite), increasing the degree of purification of anhydrous (dehydrated) oil hydrogen sulfide from the exceptions of education and contamination of the purified oil (including water-free oil) corrosive elemental sulfur, reducing corrosional reaction medium and purified oil and, therefore, corrosion of equipment and pipelines, as well as by expanding the range of non-volatile, low-toxic, non-corrosive and available reagents converters suitable for treatment of both dry and flooded hydrogen sulfide-containing oil in the field.

The necessity and feasibility of the process in the presence of aqueous solutions of the above alkaline reagents, taken in the found optimal molar ratio, due to the fact that in this case pyrosulfite and hydrosulfite selectively react with the hydrogen sulfide with the formation of the neutral compound is sodium thiosulfate (or ammonium), which is then separated together with the “produced” water for subsequent assertion of Oceanography the crude product storage tanks, the result can be no contamination of the purified oil corrosive elemental sulfur and achieved some reduction in the total sulfur content in the treated oil. In the proposed method, as the alkaline reagent may be any of inorganic and organic bases which are able to interact with the hydrogen sulfide with the formation of hydrogen sulphide, which is then selectively reacts with the applicable pyrosulfite or hydrosulfite with the formation of thiosulfate, for example, sodium:

Thus, in this case cleaning the oil from the hydrogen sulfide is due to the total flow of the reaction:

When used as reagents aqueous solutions of hydrosulfite ammonium and ammonia to clean the oil from the hydrogen sulfide is due to the total flow of the reaction leading to the formation of ammonium thiosulfate:

As shown by tests, effective cleanup of oil from the hydrogen sulfide is also achieved during the process and in the absence of an alkaline reagent, but in this case, the hydrogen sulfide reacts with the applicable sulfites with education, mainly elemental sulfur and polythionates, resulting not excluded Zagra the imposition of the purified hydrogen sulfide from the oil corrosive elemental sulfur, i.e. not achieve one of its goals - reducing corrosional purified oil (for the achievement of other named technical results). The expediency of application as a reagent-Converter it pyrosulfite or hydrosulfite sodium, and as the alkaline reagent of the above mentioned inorganic bases due to their availability and relatively low cost (issued by the industry in large scale), which is very important taking into account the need for cleaning of large amounts of hydrogen sulfide-containing oils. It should be noted that the water Hydrosulphite solution (bisulphite) ammonium is also cheap product previously manufactured by OST 6-08-84-78 (currently, however, its production is discontinued and therefore it cannot be recommended to be widely used in the proposed method).

We offer the molar ratio of Na2S2O5: H2S or NaHSO3: H2S associated with the stoichiometry of the flowing neutralization reactions of hydrogen sulfide (4 or 5) and is optimal, because at a molar ratio less than 1 : 1 or 2 : 1 is not achieved the required degree of purification of oil and do not exclude the possibility of formation of side reaction products, and the increase in the ratio over 2 : 1 or 4 : 1 is not economically feasible. And h is th the molar ratio of the alkaline reagent : hydrogen sulfide is associated with stoichiometry flowing reactions (4 and 5). As studies have shown, when carrying out the process in a molar ratio of alkaline reagent : hydrogen sulfide is less than 1 : 1 is achieved the required degree of purification of oil from hydrogen sulfide, however, in this case, part of the hydrogen sulfide is neutralized with the formation of undesirable elemental sulfur and polythionates and therefore is not precluded by the oil pollution corrosive elemental sulfur. Considering the fact that crude oil and petroleum products, as a rule, contain corrosive oil (naphthenic acids and, from the point of view of reducing corrosional purified hydrogen sulfide from the oil, the desired simultaneous neutralization of their alkali, in the proposed method, it is advisable to introduce in the oil of an alkaline reagent in a surplus from the stoichiometry of reactions 4 and 5, i.e. the process in a molar ratio of NaOH : H2's more than 1:1, preferably in the ratio from 1.2 : 1 to 2 : 1 (or more - depending on the content of naphthenic acids in processed raw materials). It should be noted that the neutralization of petroleum acids and effective reduction in corrosional oil while processing its aqueous solutions of alkali (NaOH, KOH, NH3and the like) at temperatures of 20-50°and the above-described and experimentally confirmed in U.S. Pat. U.S. No. 2302281,4199440, 6258258.

The proposed concentration pyrosulfite, hydrosulfite sodium solution (10-40%) one is camping optimal because the use of a more dilute solution (less than 10%) leads to an increase in water content in the purified crude product, and the increase in the concentration of sulfite more than 40% is impractical because of precipitation (crystallization) when using the reagent in the winter. The same applies to the concentration of the alkaline reagent in the solution. As studies have shown, the technical result is achieved by the simultaneous introduction of the found optimal quantities of alkali and pyrosulfite or hydrosulfite sodium in the flow of the oil being processed in separate threads or a single thread in the form of a previously prepared aqueous-alkaline solution of the pyrosulfite or hydrosulfite sodium. From the point of view of simplification of the process in field conditions most appropriate joint introduction of the reagents in the form of pre-cooked (commodity) Converter using a single metering pump.

The proposed method can be carried out at ordinary or elevated temperatures (10-80° (C) and pressures (0.1 to 1.0 MPa). Thus preferably carrying out the process at temperatures of 20-40°because at temperatures below 10-20°increases the viscosity of heavy oil, deteriorating the dispersion solution of the neutralizer in the oil and reduces the degree of its purification from hydrogen sulfide, as the temperature increases above 80°not economically feasible due to the increase of energy consumption for heating oil. Treatment plants sulfur crudes after step thermochemical dehydration oil flows typically have a temperature in the range of 30-60°therefore, additional heating of the oil being processed in the implementation of the proposed method is not required. The process pressure has no significant impact on the velocity of the flowing reaction of neutralization and purification of the oil from the hydrogen sulfide.

The return process separated from the purified oil extract of an aqueous solution of the reagents and use it for making a new portion of the catalyst by dissolving solid commodity sodium pyrosulfite (according to GOST 11683) and caustic soda (according to GOST 2263) or sodium carbonate (according to GOST 5100) allows to reduce the consumption of the reagents in the process of refining oil and reduce wastewater generation, especially in the case of the process with excess reagents from the stoichiometry of reactions 4 and 5.

The proposed method has been tested in laboratory conditions and is illustrated by the following specific but not limiting examples.

Example 1. 100 ml of dehydrated sour crudes containing 0.025 wt.% hydrogen sulfide (0,00067 mol) and 0.2 wt.% emulsion of water, placed in the given out the bathroom reaction flask, equipped with a mechanical stirrer. Then, into the flask under stirring enter 0,17 ml of 20%aqueous sodium hydroxide solution and 0.80 ml of 20%aqueous solution of sodium pyrosulfite, previously prepared by dissolving solid commodity sodium pyrosulfite technical GOST 11683 in the water. The molar ratio of hydrogen : sodium hydroxide : sodium pyrosulphite in the reaction mixture is 1 : 1,5 : 1,5. The reaction mixture is intensively stirred at room temperature (23° (C) within 3 hours and perform quantitative analysis of the purified oil to the content of residual hydrogen sulfide by potentiometric titration according to GOST 17323. The degree of purification of oil from the hydrogen sulfide is 100%, i.e. the purified oil content of hydrogen sulfide with the requirements of GOST R 51858-2002 on marketable oil.

Example 2. Purification of sour crude oil containing 0.025 wt.% hydrogen sulfide and 0.2 wt.% water, spend the same conditions of example 1, but using as the alkaline reagent 20%aqueous sodium carbonate solution, and as the inorganic reagent 39%commodity water Hydrosulphite solution of sodium (sodium bisulfite according to GOST 902). The molar ratio of hydrogen : sodium carbonate : hydrosulfite sodium in the reaction mixture is 1 : 1,5 : 3. The degree of purification of oil from the hydrogen sulfide is 100%.

When is EP 3. Clean water-cut oil containing 0,019 wt.% hydrogen sulfide and 10 wt.% water is performed similarly, and in the conditions of example 1, but using as the alkaline reagent 10%aqueous solution of sodium phosphate (trisodium phosphate), and as the inorganic reagent 30%-aqueous solution of sodium pyrosulfite. The molar ratio of hydrogen : trisodium phosphate : sodium pyrosulphite in the reaction mixture is 1 : 0,5 : 2. The degree of purification of oil from the hydrogen sulfide is 100%.

Example 4. Cleaning oil containing 0.025 wt.% hydrogen sulfide and 0.2 wt.% water is performed similarly, and in the conditions of example 1, but using as the alkaline reagent 20%aqueous solution of sodium sulfite (Na2SO3), and as the inorganic reagent 40%aqueous solution of sodium pyrosulfite. The molar ratio of hydrogen : sodium sulfite : sodium pyrosulphite is 1:1:1. The degree of purification of oil from the hydrogen sulfide is 100%.

Example 5. Cleaning oil containing 0.025 wt.% hydrogen sulfide and 0.2 wt.% water is performed similarly, and in the conditions of example 1, but using as reagent-neutralizer 20%aqueous-alkaline solution of sodium pyrosulfite, previously prepared by dissolving solid commodity sodium pyrosulfite (according to GOST 11683) and caustic soda (according to GOST 2263) in water in a molar ratio of Na2S2O 5: NaOH=1:1, taken at the rate of 1.5 mol pyrosulfite and 1.5 mol of sodium hydroxide to 1 mol of hydrogen sulfide. That is, the molar ratio of hydrogen : sodium hydroxide : sodium pyrosulphite in the reaction mixture in terms of the initial reactants is 1 : 1,5 : 1,5. The degree of purification of oil from the hydrogen sulfide is 100%, i.e. the effective cleanup of oil from the hydrogen sulfide is achieved in the case of processing previously received an alkaline solution of sodium pyrosulfite.

Example 6. Cleaning of the fuel oil containing 0,009 wt.% of hydrogen sulfide, spend the same conditions of example 1, but using as reagent-neutralizer caustic solution of sodium pyrosulfite composition of example 5. The molar ratio of hydrogen : sodium hydroxide : sodium pyrosulphite is 1 : 1,5 : 1,5. The degree of purification of oil from the hydrogen sulfide is 100%.

Example 7. Cleaning oil containing 0.025 wt.% hydrogen sulfide and 0.2 wt.% water is performed similarly, and in the conditions of example 1, but using as the alkaline reagent 25%aqueous ammonia solution (according to GOST 9), and as the inorganic reagent 40%aqueous Hydrosulphite solution of ammonia (NH4SO3), previously obtained by the interaction of sulfur dioxide with an aqueous solution of ammonia. The molar ratio of hydrogen : ammonia : hydrosulfite ammonium in actionnow mixture is 1 : 1,5 : 3. The degree of purification of oil from the hydrogen sulfide is 100%.

Example 8. Cleaning straight-run petroleum fractions NK 300°used as a solvent of paraffin in oil and containing 0,009 wt.% hydrogen sulfide having a pH of 9.9 mg KOH/100 ml, spend the same conditions of example 1 using as the alkaline reagent 20%aqueous sodium hydroxide solution, and as the inorganic sulfur-containing reactant 20%aqueous solution of sodium pyrosulfite. The molar ratio of hydrogen : sodium hydroxide : sodium pyrosulphite in the reaction mixture is 1 : 2 : 1,5. The degree of purification of the raw material from which hydrogen sulfide is 100% and the acidity of 1.8 mg KOH/100 ml While the purified raw material withstands the test on a copper plate, i.e. during the process of the proposed method decreases the acidity, precluded the formation and contamination of the processed raw material is elemental sulfur, which results in reduction of corrosional and toxicity of raw materials for use as a solvent paraffin oil production.

Comparative experiment showed that when cleaning anhydrous (dehydrated) oil containing 0.025 wt.% hydrogen sulfide and 0.2 wt.% water, in a known manner (prototype) the degree of purification of the raw material from which hydrogen sulfide is 80%, i.e. the purified oil does not meet the standards GOST R 51858.

Data PR the examples 1-7 show the process proposed method can improve the degree of purification of the raw materials from hydrogen sulfide (100 and 80%, respectively) without the use of volatile, toxic and corrosive chemical reagent is sulfur dioxide and to produce oil, the appropriate content of hydrogen sulfide standards GOST R 51858. The data of example 8 show that the process proposed method provides simultaneous reduction of acidity and corrosional purified raw materials by neutralizing contained oil acid alkali agent exception of education and contamination of the processed raw material is elemental sulfur. In addition, in contrast to the known method in the proposed method, the process of cleaning the raw material from which hydrogen sulfide is carried out in one stage (without prior acidification of raw materials, control of pH and subsequent processing of peeled raw alkaline reagent) using a single, pre-prepared reagent-catalyst (examples 5 and 6), it is suitable for cleaning waterless and watered hydrogen sulfide-containing oils in field conditions. These advantages of the proposed method allows to increase the efficiency of the process as a whole in comparison with the known method.

1. The method of cleaning oil from the hydrogen sulfide by processing the feedstock sulfur-containing Neorganicheskie the reagent-Converter characterized in that as the latter is used an aqueous solution of pyrosulfite or hydrosulfite alkali metal or hydrosulfite ammonium and the process is carried out in the presence of an aqueous solution of hydroxide, carbonate, orthophosphate and/or sulfite of an alkali metal or ammonia.

2. The method according to claim 1, characterized in that the aqueous solution of the pyrosulfite or hydrosulfite alkali metal, preferably sodium, or hydrosulfite ammonium take rate of not less than 1 mol pyrosulfite or 2 mol of hydrosulfite on 1 mol of hydrogen sulfide, and use 10-40%aqueous solution of pyrosulfite or hydrosulfite.

3. The method according to claim 1, characterized in that the aqueous solution of hydroxide, carbonate, orthophosphate and/or sulfite of an alkali metal, preferably sodium or ammonia charge at the rate of not less than 0.5 mol, preferably 1-2 mol, hydroxide, carbonate, orthophosphate and/or sodium sulfite, or ammonia on 1 mol of hydrogen sulfide, and use 10-45%aqueous solution of the hydroxide or 10-25%aqueous solution of carbonate, orthophosphate or sodium sulfite, or ammonia.

4. The method according to claim 3, characterized in that the aqueous solution of hydroxide, carbonate, orthophosphate and/or sodium sulfite, or ammonia is injected into the feedstock in the form of a separate stream or in conjunction with the applied aqueous solution of pyrosulfite or hydrosulfite as pre-prepared solution of reagent-Converter.

5. The method according to claim 1, characterized in that the treatment is carried out at a temperature of 10-80°C.

6. The method according to any one of claims 1 to 5, characterized in that a portion of the spent water of a reagent solution after separation from the pure raw return in the process.



 

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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: 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

FIELD: chemistry.

SUBSTANCE: The invention relates to raw hydrocarbons processing plants and can be used in oil industry when hydrogen sulphide and low-molecular mercaptans are removed from sulphurous oil. The invention relates to purifier which removes hydrogen sulphide and low-molecular mercaptans from oil. The purifier comprises a sulphurous oil feeding pipe, a oil separator connected in series with the gas pipeline by pipes, an oil pump, a mixing unit, an oxidation reactor, a high pressure separator with gas pipe and purified oil storage tanks, a tank for preparation and storage of the catalyst alkaline solution fitted with dosage pumps where their outlet is connected with the inlet of the oil pump, an air compressor with its outlet connected to the inlet of the mixing unit, and a flare line. The device is also fitted with a water pipe feeding fresh washwater. The water pipe is connected to the pipeline between the high-pressure and the low-pressure separators, furthermore, the gas feeding pipes of oil separator and low pressure separator are connected by a drain gas pipe; the gas pipe of the high pressure separator is connected with the flare line. It is also connected with the purified oil storage tanks through the shunt pipe with a pressure regulator.

EFFECT: increase of stock oil quality in order to conform with the GOST R 51858-2002 standard.

1 dwg

FIELD: chemistry.

SUBSTANCE: in one version of the invention, in order to remove residual sulphur-containing compounds, a stream of alkaline material containing sulphur-containing compounds, which is first oxidised and separated, is fed into a post-treatment apparatus. The sulphur-containing compounds are in amount of 500 ppm by weight in form of sulphur. The stream of alkaline material is then brought into contact with a layer of solid adsorbent in the post-treatment apparatus and disulphides, which are fed into the post-treatment apparatus as part of the sulphur-containing compounds in the stream of alkaline material, are adsorbed on the layer of adsorbent. An alkaline stream containing less than 20 ppm by weight (in form of sulphur) sulphur-containing compounds is then output from the post-treatment apparatus. In another version, oxidation and adsorption are combined in order to remove residual sulphur compounds from a concentrated alkaline stream in the presence of a phthalocyanine metal deposited on the solid adsorbent. This method is particularly suitable as post-treatment step in a flow scheme for regenerating alkali.

EFFECT: cheap production of depleted alkali with low content of sulphur impurities.

16 cl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalytic composition containing disulphonic acid of cobalt phthalocyanine or chloro- and oxy-substituted derivative thereof, an alkaline agent, a synergetic additive and water, wherein the alkaline agent used is alkanolamine of formula (CH3)n-N-(CH2-CH2-OH)3-n where n=0-2, and the synergetic additive used is a linear (polyethylene glycol) or cyclic (crown ether) polyether, with the following ratio of components in wt %: disulphonic acid of cobalt phthalocyanine or chloro-and oxy-substituted derivative thereof 15-25, alkanolamine 7-25, polyethylene glycol or crown ether 0.5-4, water - up to 100.

EFFECT: high specific catalytic activity in demercaptanisation processes.

7 ex, 1 tbl

FIELD: oil-and-gas industry.

SUBSTANCE: invention relates to preparation of hydrogen-sulphide-bearing oil and comprises cleaning oil of hydrogen sulphide at feed of 40-60% go total weight of oil being cleaned, 1st flow for separation with subsequent oxidation of hydrogen sulphide by air oxygen. After oxidation, oil flow is fed to high-pressure separator. Extra desorption cleaning assembly is mounted whereto 40-60% of total weight of cleaned oil is fed, 2nd flow. For blowing hydrogen sulphide off from oil into extra desorption cleaning assembly from high-pressure separator. After cleaning, oil flows are mixed and directed to low-pressure separator. Mix of gases from low-pressure separator and desorption cleaning assembly is used for oil heating.

EFFECT: higher quality of commercial oil owing to decrease in concentration of chlorides to first group of GOST R 51858-2002, decreased consumption of process solutions.

1 dwg, 1 tbl, 9 ex

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