RU2832622C1 - Method of removing sulphur-containing compounds from oil and gas condensate - Google Patents

Abstract

FIELD: oil, gas and coke-chemical industry.

SUBSTANCE: present invention relates to methods of cleaning oil, oil products and gas condensate from sulphur-containing compounds, including hydrogen sulphide and volatile methyl- and ethyl mercaptans, using acrylonitrile and compounds based thereon.

EFFECT: proposed method of removing sulphur compounds enables to efficiently purify oil, oil products and gas condensate using available reagents, which prevents corrosion of pipelines and equipment, increases purity of hydrocarbon products and reduces risk of personnel poisoning with sulphur-containing gases in production.

5 cl, 53 tbl

Description

Field of technology

The invention relates to the field of chemical technology for cleaning hydrocarbons, in particular to cleaning oil, petroleum products and gas condensate from sulfur-containing compounds. The invention can be used to ensure the purity of a hydrocarbon product, combat poisonous gases during the extraction, transportation and processing of hydrocarbons, as well as to protect pipelines and equipment from corrosion.

State of the art

Primary separation oil and gas condensate contain significant amounts of sulfur-containing compounds. The most undesirable are the presence of low-molecular H ₂ S, CH ₃ SH, C ₂ H ₅ SH, the content of which is standardized by GOST R 51858-2002.

These substances are toxic and undesirable in hydrocarbon products and also cause corrosion of pipelines and equipment. Thus, their removal is a pressing issue.

Chemical absorption methods are widely used to remove low-molecular sulfur-containing components. A wide range of compounds can be used as absorbers.

When alkali solutions are absorbed, mercapides and water are formed, which are capable of reverse hydrolysis, and alkaline effluents are also formed as waste.

H ₂ S + 2NaOH ↔ Na ₂ S + 2H ₂ O

R-SH + NaOH ↔ NaS-R + _H2O

Low-cost formaldehyde-based absorbers can be used. However, in the presence of water, a hydrolysis reaction of the absorption products with repeated formation of mercaptans is also possible. In addition, the polysulfides formed subsequently lead to deposits on hot surfaces of equipment and are the cause of coke formation and corrosion of the latter.

2OCH ₂ + 2 H ₂ S → HOCH ₂ SH

n HOCH ₂ SH → -(CH ₂ S)n- + n H ₂ O → coke

Alkanolamines can be used to absorb hydrogen sulfide. However, the process produces thermally unstable amine salts, which also easily release hydrogen sulfide when heated, leading to corrosion of equipment. Alkanolamines are ineffective for absorbing mercaptans.

The most effective absorbers of all lower sulfur-containing components are triazine compounds. However, their use is limited due to their high cost.

A method is known according to patent RU 2230095 C1 [1] “Method for cleaning oil from hydrogen sulfide”, in which cleaning oil from hydrogen sulfide is carried out by contact with an aqueous-alkaline solution of a water-soluble salt of nitrous acid.

The disadvantage of this method is the use of water-soluble forms of reagents and the need to heat the oil to a temperature of 30-80°C, since at temperatures below 30°C the viscosity of heavy oil increases, the dispersion of the aqueous alkaline solution of nitrite in oil deteriorates, the rate of oxidation reactions decreases and the required reaction time increases (more than 3 hours), as well as the need for increased pressure in the case of additional introduction of compressed air into the reaction mixture.

A method for purifying oil and gas condensate from hydrogen sulfide and mercaptans is known according to patent RU 2202595C2 [2] “Method for purifying oil and gas condensate from hydrogen sulfide and mercaptans” by oxidizing them with atmospheric oxygen in the presence of a catalyst in the form of a secondary or tertiary alkylamine, or tertiary alkanolamine, or a mixture thereof.

The disadvantage of this method is the need for a molar ratio of hydrogen sulfide/mercaptan sulfur = 1/1 in the feedstock oil, and in the case of a shortage of hydrogen sulfide, dissolved elemental sulfur must be dosed into the feedstock.

One of the promising directions of purification from sulfur compounds is the use of acrylonitrile and its compounds. Acrylonitrile mixed with substances possessing a mobile hydrogen atom enters into a cyanoethylation reaction, and mercaptans react especially easily:

R-SH + CH ₂ =CHCN → RS-CH ₂ -CH ₂ CN. In certain cases, the reaction may require the presence of a catalyst to reduce the reaction time. Alcohols, amines, water and hydrogen halides may also enter into the cyanoethylation reaction with acrylonitrile.

Thus, methods for removing sulfur are known according to patents US9896616B2 [3], "Acrylonitrile-based sulfur removers and methods for using them in oil field operations", CA2965625C [4] "Acrylonitrile-based sulfur removers for use in oil field operations", US11078403B2 [5] "Synergistic sulfide removers for use in oil field operations", CA2964076C [6] "Synergistic sulfide removers for use in oil field operations". In the above-mentioned patents [3], [4], [5], [6], a liquid with sulfur-containing compounds is treated with compositions containing acrylonitrile and acrylonitrile-based compounds.

Despite the broad wording in the formulas and descriptions of inventions, which cover all possible liquid media, in the presented examples of these inventions only aqueous solutions are considered.

The proposed methods in their presented form are applicable only for processing the aqueous phase or water-oil mixture and are not adapted for use in industrial cleaning of oil, oil products and gas condensate.

At the same time, the presence of water, in the case of processing oil and gas condensate, leads to a decrease in the efficiency of cleaning, since due to the stratification of fractions, the contact surface of substances is reduced, and acrylonitrile and its compounds dissolve in water, react with substances in water, so the reagent is wasted.

The essence of the invention

The aim of the present invention is to effectively remove sulfur compounds, including hydrogen sulfide and volatile methyl and ethyl mercaptans, from oil and gas condensate using available acrylonitrile and compounds based on it.

The proposed method for removing sulfur compounds allows for the effective purification of oil, petroleum products and gas condensate using available reagents, which prevents corrosion of pipelines and equipment, increases the purity of hydrocarbon products and reduces the risk of poisoning personnel with sulfur-containing gases in production.

The technical result of implementing the method is a reduction in the cost of cleaning oil, oil products and gas condensate from sulfur-containing compounds, an increase in the purity of raw materials for further processing, and ensuring environmental protection requirements and safe working conditions for workers.

The technical result is achieved in that the proposed method involves removing sulfur-containing compounds from oil, petroleum products, or gas condensate by introducing an additive containing acrylonitrile, or at least one compound based on acrylonitrile; introducing a synergistic additive containing at least one base, wherein the additive containing acrylonitrile or at least one acrylonitrile-based compound contains 25-100 wt.% acrylonitrile or an acrylonitrile-based compound and 0-75 wt.% of at least one hydrocarbon with a boiling point in the range of 30-380°C or a hydrocarbon fraction of various structures with a boiling point in the range of 30-380°C, including, as an option, a gasoline fraction of hydrocarbons with a final boiling point of 205-215°C, gas condensate, a diesel fraction with an initial boiling point of 170°C and a final boiling point of 360°C, liquid pyrolysis products containing benzene, toluene, xylenes in a total amount of up to 90 wt.%, as well as commercial products based on the said fractions: gasoline, diesel fuel and aromatic hydrocarbons, to obtain a synergistic additive, sodium hydroxide is dissolved in alcohol and an organic solvent, or only in an organic solvent, the acrylonitrile-based compound can be a compound with the general formula R-C=C-C≡N, where R is an alkyl, phenyl, naphthenic, or other radical, granulated or flaked alkali metal hydroxide can be used as a base, at least one organic amine can be used as a base, at least one amino alcohol can be used as a base, at least one alkali metal alkoxide can be used as a base, wherein the alkali metal alkoxide used can be crushed to a fraction of less than 2 mm (preferably less than 0.25 mm), at least one alkali metal can be used as a base, wherein the alkali metal can be crushed to a fraction of less than 2 mm (preferably less than 0.25 mm), at least one alkali metal oxide can be used as a base, wherein the alkali metal oxide used can be crushed to fractions less than 2 mm (preferably less than 0.25 mm), an alkali metal hydroxide crushed to a fraction of less than 2 mm (preferably less than 0.25 mm) can be used as a base, at least one ionic surfactant (hereinafter referred to as surfactant) can be used to stabilize the inorganic base, at least one non-ionic surfactant can be used to stabilize the inorganic base, at least one ionic surfactant can be used to stabilize the inorganic base, at least one non-ionic surfactant can be used to stabilize the inorganic base, the solution can be additionally heated to effectively dissolve the base, diesel fraction of hydrocarbons can be used as an organic solvent for the synergistic additive, isobutanol can be used as an alcohol for the synergistic additive, the alkali content in the synergistic additive may not exceed 19 wt.%, diesel fraction hydrocarbons can be used as an organic solvent for the synergistic additive, wherein the synergistic additive may contain surfactants in an amount of 2-3 wt.% and alkali in an amount of more than wt.%, gas condensate is used as an organic solvent for the synergistic additive, while the synergistic additive contains surfactants in an amount of 2-3 wt.% and alkali in an amount of no more than 10 wt.%, before removing sulfur-containing compounds, dehydration of oil, petroleum product or gas condensate can be carried out.

The technical result is achieved by removing sulfur-containing compounds from oil or gas condensate by introducing an additive containing acrylonitrile or at least one acrylonitrile-based compound; introducing a synergistic additive containing at least one base, wherein the additive containing acrylonitrile or at least one acrylonitrile-based compound contains 25-100 wt.% acrylonitrile or an acrylonitrile-based compound and 0-75 wt.% a gasoline fraction of hydrocarbons, and sodium isobutoxide dissolved in an organic solvent is used as the synergistic additive, diesel fraction of hydrocarbons or solvents containing aromatic hydrocarbons can be used as the organic solvent for dissolving sodium isobutoxide, benzene, toluene, xylene can be used as the organic solvent containing aromatic hydrocarbons, the synergistic additive can additionally contain a surfactant, before removing the sulfur-containing compounds, dehydration of oil or gas condensate can be performed.

The technical result is achieved in that the additive containing acrylonitrile, or at least one compound based on acrylonitrile, reacts with sulfur-containing compounds and ensures their removal. The compound based on acrylonitrile can be a compound with the general formula R-C=C-C≡N where R is an alkyl, phenyl, naphthenic, or other radical.

For example, 2-butenenitrile (CH3-CH=CH-CN), 2-pentenenitrile (C2H5-CH=CH-CN) can be used as a compound based on acrylonitrile.

The technical result is achieved in that the specified content of acrylonitrile, or at least one compound based on acrylonitrile, and at least one hydrocarbon with a boiling point in the range of 30-380°C or a fraction of hydrocarbons of various structures with a boiling point in the range of 30-380°C in the additive composition ensures effective dissolution of the additive in oil, petroleum product or gas condensate while maintaining the effective rate of reaction with sulfur-containing compounds. Such fractions are not very expensive and are available in the production of petroleum products.

The following can be used as hydrocarbon fractions of various structures with a boiling point in the range of 30-380°C: gasoline fraction of hydrocarbons with a final boiling point of 205-215°C, gas condensate, diesel fraction with initial boiling point of 170°C and final boiling point of 360°C, liquid pyrolysis products containing benzene, toluene, xylenes in a total amount of up to 90 wt.% and other options.

The technical result is achieved in that the specified content of acrylonitrile, or at least one compound based on acrylonitrile, and the gasoline fraction of hydrocarbons in the additive composition ensures effective dissolution of the additive in oil, petroleum product or gas condensate while maintaining the effective rate of reaction with sulfur-containing compounds.

The technical result is achieved in that an additive containing acrylonitrile, or at least one compound based on acrylonitrile, in pure form or in solution with liquid hydrocarbons, effectively dissolves in oil, petroleum product or gas condensate, while a synergistic additive with sodium hydroxide dissolved in an organic solvent and alcohol (acting as an intermediate solvent) also effectively dissolves in oil or gas condensate, which ensures contact of the substances and the reaction of removing sulfur-containing compounds.

The technical result is achieved in that the specified content of acrylonitrile, or at least one compound based on acrylonitrile, and the gasoline fraction of hydrocarbons in the additive composition ensures effective dissolution of the additive in oil or gas condensate while maintaining the effective rate of reaction with sulfur-containing compounds. The compound based on acrylonitrile can be a compound with the general formula R-C=C-C≡N, where R is an alkyl, phenyl, naphthenic, or other radical.

For example, 2-butenenitrile (CH3-CH=CH-CN), 2-pentenenitrile (C2H5-CH=CH-CN) can be used as a compound based on acrylonitrile.

The technical result is achieved by the fact that the use of sodium hydroxide provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or acrylonitrile-based compounds, and also ensures the reaction between sodium hydroxide and sulfur-containing substances. Both of the above factors provide a synergistic effect and increase the efficiency of removing sulfur-containing substances.

The technical result is achieved by using dipropylamine as a base, which provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or compounds based on acrylonitrile, and also ensures the reaction between dipropylamine and sulfur-containing substances.

The technical result is achieved by using ethanolamine as a base, which provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or compounds based on acrylonitrile, and also ensures the reaction between ethanolamine and sulfur-containing substances.

The technical result is achieved by using sodium methylate as a base, which provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or compounds based on acrylonitrile, and also ensures the reaction between sodium methylate and sulfur-containing substances.

The technical result is achieved by using sodium as a base, which provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or compounds based on acrylonitrile, and also ensures the reaction between sodium and sulfur-containing substances.

The technical result is achieved by using sodium oxide as a base, which provides a catalytic effect in the reaction of sulfur-containing substances and acrylonitrile or compounds based on sodium oxide, and also ensures the reaction between ethanolamine and sulfur-containing substances.

The technical result is achieved by the fact that the method uses available substances, including those obtained in parallel during the operation of the oil refinery, which reduces the cost of the process of refining oil or gas condensate.

The technical result is achieved by the fact that for more effective dissolution of sodium hydroxide, it can be pre-crushed to a fraction of less than 2 mm (preferably less than 0.25 mm), and for these purposes, the solution can be heated when dissolving sodium hydroxide.

The technical result is achieved by the fact that liquid hydrocarbons, which are an accessible substance, including those obtained in parallel during the operation of the oil refinery, can be used as an organic solvent for the synergistic additive.

The technical result is achieved by the fact that isobutanol can be used as an alcohol for the synergistic additive, which allows for the effective dissolution of sodium hydroxide, and it also has a low cost.

The technical result is achieved by the fact that isopropanol can be used as an alcohol for the synergistic additive, which allows for the effective dissolution of sodium hydroxide, and it also has a low cost.

The technical result is achieved by the fact that before removing sulfur-containing compounds, dehydration of oil or gas condensate can be carried out, which has a positive effect on the efficiency of cleaning and reduces the consumption of additives, since it prevents stratification of the mixture and dissolution of additives in water.

The technical result is achieved by the fact that the alkali content in the synergistic additive may not exceed 19%, this ensures the liquid form of the synergistic additive, which is convenient for some options of its supply.

The technical result is achieved in that a diesel fraction of hydrocarbons can be used as an organic solvent for the synergistic additive, while the synergistic additive can contain surfactants in an amount of 2-3 wt.% and alkali in an amount of more than 19 wt.%, which makes it possible to use the synergistic additive in the form of a suspension, which is convenient for some variants of using the method.

The technical result is achieved in that gas condensate can be used as an organic solvent for the synergistic additive, while the synergistic additive can contain surfactant in an amount of 2-3 wt.% and alkali in an amount of no more than 10 wt.%, which makes it possible to use the synergistic additive in the form of a suspension, which is convenient for some variants of using the method.

The technical result is achieved by using sodium isobutoxide dissolved in an organic solvent as a synergistic additive. Unlike alkali, isobutoxide is partially soluble in hydrocarbons, which ensures that the reaction is carried out in a homogeneous medium, and there is no need to add additional alcohol or surfactants.

The technical result is achieved by the fact that diesel fraction of hydrocarbons or solvents containing aromatic hydrocarbons can be used as an organic solvent for dissolving sodium isobutylate. Benzene, toluene, xylene can be used as an organic solvent containing aromatic hydrocarbons; these substances are suitable for effective dissolution of sodium isobutylate and have a low cost, which makes them especially suitable for the purposes of the invention.

The technical result is achieved in that the additive containing acrylonitrile or a compound based on acrylonitrile is introduced separately from the synergistic additive, which makes it possible to avoid polymerization of acrylonitrile or a compound based on acrylonitrile upon contact with alkali, which reduces the consumption of reagents.

List of tables

Table 1. Results of analysis of the obtained samples (Example 1).

Table 2. Results of analysis of the obtained samples (Example 2).

Table 3. Results of analysis of the obtained samples (Example 3).

Table 4. Results of analysis of the obtained samples (Example 4).

Table 5. Results of analysis of the obtained samples (Example 5).

Table 6. Results of analysis of the obtained samples (Example 6).

Table 7. Results of analysis of the obtained samples (Example 7).

Table 8. Results of analysis of the obtained samples (Example 8).

Table 9. Results of analysis of the obtained samples (Example 9).

Table 10. Results of analysis of the obtained samples (Example 10).

Table 11. Results of analysis of the obtained samples (Example 11).

Table 12. Results of analysis of the obtained samples (Example 12).

Table 13. Results of analysis of the obtained samples (Example 13).

Table 14. Results of analysis of the obtained samples (Example 14).

Table 15. Results of analysis of the obtained samples (Example 15).

Table 16. Results of analysis of the obtained samples (Example 16).

Table 17. Results of analysis of the obtained samples (Example 17).

Table 18. Results of analysis of the obtained samples (Example 18).

Table 19. Results of analysis of the obtained samples (Example 19).

Table 20. Results of analysis of the obtained samples (Example 20).

Table 21. Results of analysis of the obtained samples (Example 21).

Table 22. Results of analysis of the obtained samples (Example 22).

Table 23. Results of analysis of the obtained samples (Example 23).

Table 24. Results of analysis of the obtained samples (Example 24).

Table 25. Results of analysis of the obtained samples (Example 25).

Table 26. Results of analysis of the obtained samples (Example 26).

Table 27. Results of analysis of the obtained samples (Example 27).

Table 28. Results of analysis of the obtained samples (Example 28).

Table 29. Results of analysis of the obtained samples (Example 29).

Table 30. Results of analysis of the obtained samples (Example 30).

Table 31. Results of analysis of the obtained samples (Example 31).

Table 32. Results of analysis of the obtained samples (Example 32).

Table 33. Results of analysis of the obtained samples (Example 33).

Table 34. Results of analysis of the obtained samples (Example 34).

Table 35. Results of analysis of the obtained samples (Example 35).

Table 36. Results of analysis of the obtained samples (Example 36).

Table 37. Results of analysis of the obtained samples (Example 37).

Table 38. Results of analysis of the obtained samples (Example 38).

Table 39. Results of analysis of the obtained samples (Example 39).

Table 40. Results of analysis of the obtained samples (Example 40).

Table 41. Results of analysis of the obtained samples (Example 41).

Table 42. Results of analysis of the obtained samples (Example 42).

Table 43. Results of analysis of the obtained samples (Example 43).

Table 44. Results of analysis of the obtained samples (Example 44).

Table 45. Results of analysis of the obtained samples (Example 45).

Table 46. Results of analysis of the obtained samples (Example 46).

Table 47. Results of analysis of the obtained samples (Example 47).

Table 48. Results of analysis of the obtained samples (Example 48).

Table 49. Results of analysis of the obtained samples (Example 49).

Table 50. Results of analysis of the obtained samples (Example 40).

Table 51. Results of analysis of the obtained samples (Example 51).

Table 52. Results of analysis of the obtained samples (Example 52).

Table 53. Results of analysis of the obtained samples (Example 53).

In its most general form, the method of the present invention can be implemented as follows, but is not limited to it:

1.1. Prepare the first additive, using acrylonitrile or an acrylonitrile-based compound, or a solution of acrylonitrile or an acrylonitrile-based compound in at least one hydrocarbon with a boiling point in the range of 30-380°C or hydrocarbon fractions of different structures with a boiling point in the range of 30-380°C as the first additive, for which the components are mixed in a given proportion.

2.2. A synergistic additive is prepared by dissolving the base with stirring in a solution of alcohol (e.g., isobutanol) and/or an organic solvent (e.g., in a diesel fraction of hydrocarbons), or the synergistic additive is prepared by dissolving sodium isobutylate in an organic solvent (e.g., in a diesel fraction of hydrocarbons).

3.3. To stabilize the base solution, surfactants are used.

4.4. Separate introduction of additives into oil or gas condensate is carried out.

The proposed method has been tested and illustrated by the following specific, but not limiting, examples.

Example 1

50 ml of oil were placed in a container, the container was hermetically sealed and stirred using a magnetic stirrer with heating to 30°C.

Without opening the container, a given amount of acrylonitrile was injected into the container and mixed on a magnetic stirrer for 30 seconds.

Without opening the container, a synergistic additive was injected into the container and mixed on a magnetic stirrer for 30 seconds.

The synergistic additive was sodium hydroxide in a solution of isobutanol and diesel fraction of hydrocarbons, the alkali content of the solution was less than 19 wt.%, and the synergistic additive was a liquid.

After mixing was completed, the solution was left for 1 hour and analyzed.

The results of the analysis are presented in Table 1.

Table 1 - Results of analysis of the obtained samples (Example 1)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 916 816 1997 Used 101 mg
additives containing acrylonitrile 3.8 79.2 295.5 141 mg of an additive containing acrylonitrile were used 0.7 79.2 174.9 222 mg of an additive containing acrylonitrile were used 1.6 70.4 128.7

Example 2

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that instead of pure acrylonitrile, an additive containing 75 wt.% of the gasoline fraction of hydrocarbons and 25 wt.% of acrylonitrile was injected into the container.

The results of the analysis of samples obtained after the cleaning process are presented in Table 2.

Table 2 - Results of analysis of the obtained samples (Example 2)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 912 863 1905 Used 216 mg
acrylonitrile + 648 mg gasoline fraction. 5.8 10.4 65.3

Example 3

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that instead of pure acrylonitrile, an additive containing 50 wt.% of the gasoline fraction of hydrocarbons and 50 wt.% of acrylonitrile was injected into the container.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 3.

Table 3 - Results of analysis of the obtained samples (Example 3)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 908 872 1892 Used 216 mg
acrylonitrile + 216 mg gasoline fraction. 6.2 12.7 64.3

Example 4

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that gas condensate was used instead of oil.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 4.

Table 4 - Results of analysis of the obtained samples (Example 4)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 905 825 2012 Used 219 mg
acrylonitrile. 5.9 3.8 34.9

Example 5

The process of purification from sulfur compounds was carried out similarly to Example No. 2, with the difference that gas condensate was used instead of oil.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 5.

Table 5 - Results of analysis of the obtained samples (Example 5)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 916 851 1951 Used 218 mg
acrylonitrile + 654 mg gasoline fraction. 6.3 11.2 58.9

Example 6

The process of purification from sulfur compounds was carried out similarly to Example No. 3, with the difference that gas condensate was used instead of oil.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 6.

Table 6 - Results of analysis of the obtained samples (Example 6)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 903 807 1856 Used 211 mg
acrylonitrile + 211 mg gasoline fraction. 6.3 11.2 58.9

Example 7

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 7.

Table 7 - Results of analysis of the obtained samples (Example 7)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 842 743 2082 Used 263 mg
2-butenenitrile. 8.2 12.5 64.3

Example 8

The process of purification from sulfur compounds was carried out similarly to Example No. 2, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 8.

Table 8 - Results of analysis of the obtained samples (Example 8)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 839 726 2058 Used 260 mg
2-butenenitrile + 780 mg gasoline fraction. 7.9 10.4 63.1

Example 9

The process of purification from sulfur compounds was carried out similarly to Example No. 3, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of samples obtained after the cleaning process are presented in Table 9.

Table 9 - Results of analysis of the obtained samples (Example 9)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 862 750 2075 Used 266 mg
2-butenenitrile + 266 mg gasoline fraction. 8.5 11.2 68.4

Example 10

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that 2-butenenitrile was used instead of acrylonitrile, and gas condensate was purified instead of oil.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 10.

Table 10 - Results of analysis of the obtained samples (Example 10)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 782 824 2006 Used 256 mg
2-butenenitrile. 3.1 6.5 58.2

Example 11

The process of purification from sulfur compounds was carried out similarly to Example No. 2, with the difference that 2-butenenitrile was used instead of acrylonitrile, and gas condensate was purified instead of oil.

The results of the analysis of samples obtained after the cleaning process are presented in Table 11.

Table 11 - Results of analysis of the obtained samples (Example 11)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 806 784 1932 Used 254 mg
2-butenenitrile + 762 mg gasoline fraction. 2.7 5.2 67.2

Example 12

The process of purification from sulfur compounds was carried out similarly to Example No. 3, with the difference that 2-butenenitrile was used instead of acrylonitrile, and gas condensate was purified instead of oil.

The results of the analysis of samples obtained after the cleaning process are presented in Table 12.

Table 12 - Results of analysis of the obtained samples (Example 12)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 819 807 1978 Used 259 mg
2-butenenitrile + 259 mg gasoline fraction. 3.4 6.3 65.8

Example 13

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of samples obtained after the cleaning process are presented in Table 13.

Table 13 - Results of analysis of the obtained samples (Example 13)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 843 739 1878 202 mg of acrylonitrile were used 4.5 8.4 54.1

Example 14

The process of purification from sulfur compounds was carried out similarly to Example No. 2, with the difference that sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of samples obtained after the cleaning process are presented in Table 14.

Table 14 - Results of analysis of the obtained samples (Example 14)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 819 784 1943 Used 203 mg
acrylonitrile + 609 mg gasoline fraction. 2.8 6.4 63.4

Example 15

The process of purification from sulfur compounds was carried out similarly to Example No. 3, with the difference that sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 15.

Table 15 - Results of analysis of the obtained samples (Example 15)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 838 795 1921 Used 205 mg
acrylonitrile + 205 mg gasoline fraction. 3.2 7.5 58.7

Example 16

The process of purification from sulfur compounds was carried out similarly to Example No. 13, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of samples obtained after the cleaning process are presented in Table 16.

Table 16 - Results of analysis of the obtained samples (Example 16)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 904 878 2041 Used 279 mg
2-butenenitrile 3.5 10.4 67.9

Example 17

The process of purification from sulfur compounds was carried out similarly to Example No. 14, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of samples obtained after the cleaning process are presented in Table 17.

Table 17 - Results of analysis of the obtained samples (Example 17)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 876 798 2019 Used 269 mg
2-butenenitrile + 807 mg gasoline fraction. 4.3 8.4 58.3

Example 18

The process of purification from sulfur compounds was carried out similarly to Example No. 15, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 18.

Table 18 - Results of analysis of the obtained samples (Example 18)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 950 834 1987 Used 282 mg
2-butenenitrile + 282 mg gasoline fraction. 5.2 9.7 63.7

Example 19

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that gas condensate was used instead of oil, and sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of samples obtained after the cleaning process are presented in Table 19.

Table 19 - Results of analysis of the obtained samples (Example 19)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 811 835 1987 Used 205 mg
acrylonitrile. 5.4 8.7 67.5

Example 20

The process of purification from sulfur compounds was carried out similarly to Example No. 2, with the difference that gas condensate was used instead of oil, and sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 20.

Table 20 - Results of analysis of the obtained samples (Example 20)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 838 841 2047 Used 211 mg
acrylonitrile + 633 mg gasoline fraction. 4.1 8.3 72.4

Example 21

The process of purification from sulfur compounds was carried out similarly to Example No. 3, with the difference that gas condensate was used instead of oil, and sodium isobutoxide dissolved in the diesel fraction of hydrocarbons was used as a synergistic additive.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 21.

Table 21 - Results of analysis of the obtained samples (Example 21)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 794 847 1985 Used 204 mg
acrylonitrile + 204 mg gasoline fraction. 3.4 7.9 64.7

Example 22

The process of purification from sulfur compounds was carried out similarly to Example No. 19, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 22.

Table 22 - Results of analysis of the obtained samples (Example 22)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 798 805 2054 Used 258 mg
2-butenenitrile 3.8 9.8 73.4

Example 23

The process of purification from sulfur compounds was carried out similarly to Example No. 20, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 23.

Table 23 - Results of analysis of the obtained samples (Example 23)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 816 832 1997 Used 260 mg
2-butenenitrile + 780 mg gasoline fraction. 4.2 7.2 68.3

Example 24

The process of purification from sulfur compounds was carried out similarly to Example No. 21, with the difference that 2-butenenitrile was used instead of acrylonitrile.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 24.

Table 24 - Results of analysis of the obtained samples (Example 24)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 784 798 2063 Used 256 mg
2-butenenitrile + 256 mg gasoline fraction. 4.1 10.3 72.9

Example 25

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that in order to accelerate the process of dissolution of sodium hydroxide, it was ground in a ball mill to a fraction of less than 0.25 mm, and in the process of mixing with alcohol and the diesel fraction of hydrocarbons, the solution was heated to 95°C.

Table 25 - Results of analysis of the obtained samples (Example 25)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 878 746 2051 Used 214 mg
acrylonitrile 4.8 3.0 28.5

Example 26

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that the content of sodium hydroxide in the synergistic additive was about 19-22 wt.%, while surfactants were additionally added in an amount of 2-3 wt.%, after active mixing the synergistic additive was a suspension.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 26.

Table 26 - Results of analysis of the obtained samples (Example 26)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 918 776 2033 Used 218 mg
acrylonitrile 4.4 2.1 36.3

Example 27

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that gas condensate was used as an organic solvent for the synergistic additive, while surfactant was mixed into the synergistic additive in an amount of 2-3 wt.%, the alkali content did not exceed 10 wt.%, and after active mixing the synergistic additive was a suspension.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 27.

Table 27 - Results of analysis of the obtained samples (Example 27)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 866 795 1903 Used 210 mg
acrylonitrile 3.1 0.7 34.0

Example 28

The process of purification from sulfur compounds was carried out similarly to Example No. 13, with the difference that a mixture of liquid pyrolysis products was used as an organic solvent for dissolving sodium isobutoxide.

Table 28 - Results of analysis of the obtained samples (Example 28)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 810 713 1856 Used 199 mg
acrylonitrile 2.6 0.7 24.8

Example 29

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that before purification, the residual water was not removed from the oil.

The results of the analysis of the samples obtained after the cleaning process are presented in Table 29.

Table 29 - Results of analysis of the obtained samples (Example 29)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1125 646 3022 Used 680 mg
acrylonitrile 8.8 1.4 38.4

Example 30

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that instead of sodium hydroxide, dipropylamine was used as a synergistic additive.

Table 30 - Results of analysis of the obtained samples (Example 30)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1002 670 2104 Used 220 mg
acrylonitrile 7.7 2.1 37.4

Example 31

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that instead of sodium hydroxide, metallic sodium was used as a synergistic additive.

Table 31 - Results of analysis of the obtained samples (Example 31)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 997 664 2072 Used 216 mg
acrylonitrile 0.2 0.7 31.1

Example 32

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that instead of sodium hydroxide, sodium oxide was used as a synergistic additive.

Table 32 - Results of analysis of the obtained samples (Example 32)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 706 802 1896 Used 188 mg
acrylonitrile 0.2 0.7 39.3

Example 33

The process of purification from sulfur compounds was carried out similarly to Example No. 30, with the difference that gas condensate was used instead of oil.

Table 33 - Results of analysis of the obtained samples (Example 33)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 618 722 1906 Used 175 mg
acrylonitrile 7.7 2.1 37.4

Example 34

The process of purification from sulfur compounds was carried out similarly to Example No. 31, with the difference that gas condensate was used instead of oil.

Table 34 - Results of analysis of the obtained samples (Example 34)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 602 789 1797 Used 170 mg
acrylonitrile 3.3 1.7 36.6

Example 35

The process of purification from sulfur compounds was carried out similarly to Example No. 32, with the difference that gas condensate was used instead of oil.

Table 35 - Results of analysis of the obtained samples (Example 35)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 584 709 1853 Used 120 mg
acrylonitrile 0.6 0.9 40.1

Example 36

The process of purification from sulfur compounds was carried out similarly to Example No. 30, with the difference that 2-butenenitrile was used instead of acrylonitrile.

Table 36 - Results of analysis of the obtained samples (Example 36)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 947 886 2200 Used 295 mg
2-butenenitrile 6.6 6.2 55.4

Example 37

The process of purification from sulfur compounds was carried out similarly to Example No. 31, with the difference that 2-butenenitrile was used instead of acrylonitrile.

Table 37 - Results of analysis of the obtained samples (Example 37)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 704 866 2002 Used 246 mg
2-butenenitrile 2.1 1,1 52.8

Example 38

The process of purification from sulfur compounds was carried out similarly to Example No. 32, with the difference that 2-butenenitrile was used instead of acrylonitrile.

Table 38 - Results of analysis of the obtained samples (Example 38)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 707 857 2000 Used 241 mg
2-butenenitrile 4.9 0.9 60.3

Example 39

The process of purification from sulfur compounds was carried out similarly to Example No. 36, with the difference that gas condensate was used instead of oil.

Table 39 - Results of analysis of the obtained samples (Example 39)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 599 712 1978 Used 219 mg
2-butenenitrile 8.2 1.9 52.8

Example 40

The process of purification from sulfur compounds was carried out similarly to Example No. 37, with the difference that gas condensate was used instead of oil.

Table 40 - Results of analysis of the obtained samples (Example 40)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 599 712 1978 Used 208 mg
2-butenenitrile 9.4 3.6 48.9

Example 41

The process of purification from sulfur compounds was carried out similarly to Example No. 38, with the difference that gas condensate was used instead of oil.

Table 41 - Results of analysis of the obtained samples (Example 41)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 552 640 1812 Used 200 mg
2-butenenitrile 9.9 3.1 62.2

Example 42

The process of purification from sulfur compounds was carried out similarly to Example No. 30, with the difference that monoethanolamine was used instead of dipropylamine.

Table 42 - Results of analysis of the obtained samples (Example 42)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 854 482 2112 Used 202 mg
acrylonitrile 8.2 14.2 92.3

Example 43

The process of purification from sulfur compounds was carried out similarly to Example No. 33, with the difference that monoethanolamine was used instead of dipropylamine.

Table 43 - Results of analysis of the obtained samples (Example 43)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 582 683 1865 Used 168 mg
acrylonitrile 7.4 17.7 88.7

Example 44

The process of purification from sulfur compounds was carried out similarly to Example No. 36, with the difference that monoethanolamine was used instead of dipropylamine.

Table 44 - Results of analysis of the obtained samples (Example 44)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 880 696 1873 Used 259 mg
2-butenenitrile 13.8 18.4 102.6

Example 45

The process of purification from sulfur compounds was carried out similarly to Example No. 39, with the difference that monoethanolamine was used instead of dipropylamine.

Table 45 - Results of analysis of the obtained samples (Example 45)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Gas condensate before processing 546 671 1810 Used 204 mg
2-butenenitrile 11.5 10.5 87.9

Example 46

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that the synergistic additive additionally contained 2 wt.% of ionogenic surfactant.

Table 46 - Results of analysis of the obtained samples (Example 46)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1056 847 2020 Used 239 mg
acrylonitrile 6.2 2.4 35.6

Example 47

The process of purification from sulfur compounds was carried out similarly to Example No. 1, with the difference that the synergistic additive additionally contained 2 wt.% of non-ionic surfactant.

Table 47 - Results of analysis of the obtained samples (Example 47)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1032 851 2004 Used 237 mg
acrylonitrile 6.7 1.7 33.8

Example 48

The process of purification from sulfur compounds was carried out similarly to Example No. 7, with the difference that the synergistic additive additionally contained 2 wt.% of ionogenic surfactant.

Table 48 - Results of analysis of the obtained samples (Example 48)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1015 844 1995 Used 293 mg
2-butenenitrile 7.8 9.9 58.2

Example 49

The process of purification from sulfur compounds was carried out similarly to Example No. 7, with the difference that the synergistic additive additionally contained 2 wt.% of non-ionic surfactant.

Table 49 - Results of analysis of the obtained samples (Example 49)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 1080 862 2081 Used 307 mg
2-butenenitrile 9.2 14.1 72.2

Example 50

The process of purification from sulfur compounds was carried out similarly to Example No. 42, with the difference that the synergistic additive additionally contained 2 wt.% of ionogenic surfactant.

Table 50 - Results of analysis of the obtained samples (Example 50)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 973 762 1876 Used 219 mg
acrylonitrile 5.8 11.1 53.3

Example 51

The process of purification from sulfur compounds was carried out similarly to Example No. 42, with the difference that the synergistic additive additionally contained 2 wt.% of non-ionic surfactant.

Table 51 - Results of analysis of the obtained samples (Example 51)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 990 768 1915 Used 222 mg
acrylonitrile 4.1 9.8 74.6

Example 52

The process of purification from sulfur compounds was carried out similarly to Example No. 44, with the difference that the synergistic additive additionally contained 2 wt.% of ionogenic surfactant.

Table 52 - Results of analysis of the obtained samples (Example 52)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 763 486 1745 Used 223 mg
2-butenenitrile 3.0 4.1 73.2

Example 53

The process of purification from sulfur compounds was carried out similarly to Example No. 44, with the difference that the synergistic additive additionally contained 2 wt.% of non-ionic surfactant.

Table 53 - Results of analysis of the obtained samples (Example 53)

_H2S content, ppm MeSH content, ppm EtSH content, ppm Oil before processing 560 384 1415 Used 171 mg
2-butenenitrile 7.2 0.9 42.2

Sources of information used

Russian Federation Patent No. 2230095. C10G 19/02, C10G 27/06. Method for purifying oil from hydrogen sulfide / Fakhriev Akhmatfail Magsumovich, Fakhriev Rustem Akhmatfailovich. Prior. 27.03.2003, published 10.06.2004.

Russian Federation Patent No. 2202595. C10G 27/00, C10G 27/04, C10G 27/06, C10G 29/20. Method for purifying oil and gas condensate from hydrogen sulfide and mercaptans / Fakhriev Akhmatfail Magsumovich, Fakhriev Rustem Akhmatfailovich. Prior. 02.02.1999, published. 20.12.2000.

US Patent US 9896616B2. C09K8/52. Acrylonitrile-based sulfur removers and methods for using them in oilfield operations / Liu Shi, Funian Zhao, Lianwei Qu, Michael Harless, Ron Hoppe. Prior. 23.12.2014, published 20.02.2018.

Canadian Patent CA 2965625C. C09K8/52. Acrylonitrile-based sulfur scavenging agents for use in oil field operations / Liu Shi, Funian Zhao, Lianwei Qu, Michael Harless, Ron Hoppe. Prior. 23.12.2014, published 03.07.2018.

US Patent US 11078403B2. C09K8/54. Synergistic Sulfide Removal Additives for Use in Oilfield Operations / Liu Shi, Funian Zhao, Lianwei Qu, Edward Corrin. Prior. 12/16/2019, published 08/03/2021.

Canadian Patent CA 2964076C. C09K8/54. Synergistic sulfide removal additives for use in oilfield operations / Liu Shi, Funian Zhao, Lianwei Qu, Edward Corrin. Prior. 22.12.2014, published 04.02.2020.

Claims (5)

1. A method for removing sulfur-containing compounds from oil or gas condensate, comprising introducing an additive containing acrylonitrile or at least one acrylonitrile-based compound; introducing a synergistic additive containing at least one base, characterized in that the additive containing acrylonitrile or at least one acrylonitrile-based compound contains 25-100 wt.% acrylonitrile or an acrylonitrile-based compound and 0-75 wt.% gasoline fraction of hydrocarbons, and sodium isobutoxide dissolved in an organic solvent is used as the synergistic additive. 2. The method according to paragraph 1, characterized in that the diesel fraction of hydrocarbons or solvents containing aromatic hydrocarbons are used as an organic solvent for dissolving sodium isobutylate. 3. The method according to paragraph 2, characterized in that benzene, toluene, or xylene are used as the organic solvent containing aromatic hydrocarbons. 4. The method according to claim 1, characterized in that the synergistic additive additionally contains a surfactant. 5. The method according to paragraph 1, characterized in that before removing sulfur-containing compounds, dehydration of oil or gas condensate is carried out.