RU2811605C1 - Composition for neutralization of hydrogen sulfide and mercaptans and method of its use - Google Patents

Abstract

FIELD: neutralization of hydrogen sulfide.

SUDSTANCE: invention relates to the neutralization of hydrogen sulfide and mercaptans present in hydrocarbon media, and is recommended for use in oil and gas production, oil and gas processing and other industries. The invention relates to a composition for the neutralization of hydrogen sulfide and mercaptans containing, by wt.%: alkali metal hydroxide and / or organic base 10-60, catalyst 0.01-2, complexon 0.1-15, surfactant 0.1-15, solvent - the rest. The invention also concerns methods for cleaning oilfield media from hydrogen sulfide and mercaptans.

EFFECT: technical result is an increase in the efficiency of the neutralizer, which has high manufacturability and neutralizing ability, compatibility with reservoir fluids, the ability to inhibit corrosion processes in oilfield media and suppress the growth of sulfate-reducing bacteria.

4 cl, 1 tbl

Description

The invention relates to the neutralization of hydrogen sulfide and mercaptans present in hydrocarbon environments and is recommended for use in oil and gas production, oil and gas refining and other industries.

The presence of hydrogen sulfide and light mercaptans in produced and processed oil causes serious technological complications during the collection, preparation, transportation of oil and gas, as well as when pumping wastewater into productive horizons. The production of many production wells contains hydrogen sulfide, the release of which poses a serious danger to operating personnel and the environment, leading to premature corrosion destruction of oilfield equipment, pipelines and tanks.

Hydrogen sulfide, when added to unsaturated compounds in oil, forms mercaptans, which are extremely aggressive and toxic chemical poisons. They significantly worsen the properties of oil refining catalysts and intensify the processes of tar formation, precipitation and sedimentation from oil. This makes the problem of their removal from oil of particular relevance. Strict requirements for the content of hydrogen sulfide and light mercaptans GOST R 51858-2002 make the problem of introducing effective technologies for field purification of hydrocarbon raw materials more relevant and pressing for all enterprises producing hydrogen sulfide-containing oils and gas condensates.

Despite the fact that a significant amount of research has been carried out in this area, the need to improve oil purification technology based on new reagents, allowing to bring the quality of oil to the requirements of modern standards, and to develop the technology for producing these reagents remains an urgent task. Requirements dictate the need to use reagents that react irreversibly with hydrogen sulfide and mercaptans to form non-corrosive, non-volatile, easily recyclable and low-toxic sulfur compounds.

There is a known method for purifying oil, gas condensate and their fractions from mercaptans and hydrogen sulfide (RF patent No. 2121492, IPC C10G 29/20, published on November 10, 1998), containing products of the interaction of formaldehyde with mono-and/or diethanolamine.

The disadvantages of this composition are the insufficiently high absorption capacity with respect to hydrogen sulfide, and the water content (about 40%) leads to an increase in the water content in the oil treated with the neutralizer.

There is a known method for purifying oil and petroleum products from hydrogen sulfide and mercaptans (US Pat. No. 5213680, C10G 29/20, 1993), containing an aqueous solution of hexamethylenetetramine (HMTA) at a temperature of 100-350°F. In this case, HMTA is predominantly used in the form of a ~ 40% aqueous solution, previously obtained by reacting ammonia with a ~ 37% aqueous solution of formaldehyde (formalin) in a molar ratio of about 1:1.5

The neutralizer used in this method has low reactivity and does not provide effective purification of oil from hydrogen sulfide at normal temperatures, as a result of which the purification process is required at elevated temperatures (above 80-100°C) and high consumption of the neutralizer. The high water content (~ 60%) in the composition of the specified neutralizer and its increased consumption for purification lead to an increase in the water content in the treated oil above the level of modern requirements (GOST R 51858-2002 with amendment 1 of 01/01/2006) and to the need carrying out additional dehydration of refined oil.

A known means for neutralizing hydrogen sulfide in oil and petroleum products, which is a product of the interaction of an alkylene polyamine, predominantly diethylenetriamine, with formaldehyde in a molar ratio from 1:1 to 1:14, preferably from 1:1 to 1:3 (US Pat. No. 5284576, C10G 29/20, 1994).

The disadvantage of this composition is that it can only be used to remove hydrogen sulfide; there is no data on the removal of mercaptans. The composition does not have a sufficiently high neutralizing ability against hydrogen sulfide.

The closest in technical essence is a reagent for neutralizing hydrogen sulfide (RF patent 2532019 IPC C10G 29/20. publ. October 27, 2014 Bull. No. 10), including hemiformal(s) of lower aliphatic alcohol(s), an organic base and/or an alkali metal hydroxide, a nitrogen-containing cationic surfactant, preferably a quaternary ammonium salt, and polyethylene glycol.

The disadvantages of this reagent are the presence in its composition of salts of quaternary ammonium bases that can decompose to form organochlorine compounds, as well as the lack of data on the possibility of its use for the removal of mercaptans.

The technical problem to which the claimed invention is aimed is to expand the range of available, non-toxic, stable and effective neutralizers that are compatible with mineralized formation waters, have high reactivity towards hydrogen sulfide and mercaptans, providing effective neutralization of hydrogen sulfide and mercaptans, both in conventional and and elevated temperatures in various oilfield environments, reducing corrosiveness and suppressing the growth of bacteria in oilfield environments.

The problem is solved by the fact that the composition for neutralizing hydrogen sulfide and mercaptans contains an alkali metal hydroxide and/or an organic base, a catalyst, a complexone, a surfactant, a solvent in the following ratio of components, wt.%

Alkali metal hydroxide

and/or organic base - 10.0-60.0

Catalyst – 0.01-2

Complexon 0.1-15

Surfactant 0.1-15

Solvent - the rest

The stated task of increasing the degree of purification of oil field (water, water-oil and oil) media from hydrogen sulfide and mercaptans is solved by treating the feedstock with a neutralizer of the above composition and additionally pumping unsaturated and/or carbonyl compounds in a solvent, the ratio by weight of the chemical composition according to claim 1 to unsaturated and /or carbonyl compounds in the solvent is 9:1-1:9

The stated task of increasing the degree of purification of oil field (water, water-oil and oil) media from hydrogen sulfide and mercaptans is solved by treating the feedstock with a neutralizer of the above composition, and additionally pumping in unsaturated and/or carbonyl compounds, the ratio by weight of the chemical composition according to claim 1 to unsaturated and/ or carbonyl compounds is 9:1-1:9

In an embodiment, the composition according to claim 1 and unsaturated and/or carbonyl compounds in the solvent are pumped simultaneously.

To prepare a composition for neutralizing hydrogen sulfide and mercaptans, the following components are used:

As an alkali metal hydroxide and/or organic base, a component or mixture of components from the following is used:

lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, 1,3,5-hexahydrotriazine, methenamine, methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine , monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, dimethylbenzylamine, ethylenediamine (EDA), diethylenetriamine (DEET), triethylenetetramine (TETA), polyethylenepolyamine (PEPA), aminoethylpiperazine (AEP).

A component or mixture of components from the following is used as a catalyst:

copper phthalocyanine and its derivatives, cobalt phthalocyanine and its derivatives, iron phthalocyanine and its derivatives, nickel phthalocyanine and its derivatives, manganese phthalocyanine and its derivatives, zinc phthalocyanine and its derivatives, nickel 2-ethylhexanoate, cobalt 2-ethylhexanoate, copper 2-ethylhexanoate , manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt sulfate, cobalt chloride, cobalt nitrate, nickel sulfate, nickel chloride, nickel nitrate, copper chloride, copper nitrate, copper acetate, copper sulfate.

A component or mixture of components from the following is used as a complexone:

Polyaminocarboxylic acids (nitrilacetic, ethylenediaminetetraacetic, N-ethylethylenediamine-N,N',N'-triacetic, o-phenylenediaminetetraacetic, 2-hydroxy-1,3-diaminopropylene-N,N,N',N'-tetraacetic, ethylentriaminepentaacetic) and their salts, phosphonic acids (aminotrimethylenephosphonic acid, oxyethylene dicarboxylic acid, hydroxyphosphonocarboxylic acid, ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), phosphonobutanetricarboxylic acid, polyaminopolyethermethylenephosphonic acid, hexamethylenediaminetetra(methylenephosphonic acid), bis (hexamethylene triaminepenta(methylenephosphonic acid))) and their salts, polycarboxylic acids (polyacrylic acid, copolymer of acrylic and maleic acids, copolymer of acrylic acid and 2-acrylamido-2-melitipropanesulfonic acid, phosphinocarboxylic acid) and their salts.

A component or mixture of components from the following is used as a surfactant:

ethoxylated nonylphenols (neonol AF 9-6, neonol AF 9-9, neonol AF 9-10, neonol AF 9-12 and their analogues), polyether PP-3003, polyether PP-4202, polyether PP-4504, polyester simple PP-5503, simple polyether PP-5003, simple polyether PP-6003, simple polyether PP-5004, ethoxylated cocoamines, oxyethylated tallow amines, oxyethylated fatty acids, oxyethylated fatty alcohols (syntanols and their analogues), alkylbenzenesulfonic acid, sulfonol, sodium lauryl sulfate , sodium laureth sulfate, tall oil, sunflower oil, ZhKTM, ZhKRM, cocoamidopropyl betaine, fatty acid diethanolamides.

The solvent used is: component or mixture of components:

water, methanol, ethanol, isopropanol, propanol, butanol, isobutanol, 2-ethylhexanol ethylene glycol, propylene glycol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, butyl alcohol distillation bottoms (BORB).

To improve the absorption capacity of hydrogen sulfide and mercaptans, a second component is introduced into the composition - unsaturated and/or carbonyl compounds in a solvent or unsaturated and/or carbonyl compounds without a solvent

The following component or mixture of components is used as unsaturated and/or carbonyl compounds:

glyoxal, glutaraldehyde, acrolein, crotonaldehyde, cinnamaldehyde, propargylaldehyde, acetaldehyde, benzaldehyde, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methyl cyanoacrylate , ethyl cyanoacrylate, vinyl acetate, vinyl formate, acrylamide, dimethyl acrylamide , diethyl acrylamide, methacrylamide, dimethyl methacrylamide, acrylonitrile, methacrylonitrile, ethacrylonitrile, maleic anhydride, dimethyl maleate, diethyl maleate, furfural, phthalic anhydride, acetone, methyl ethyl ketone, acetophenone, acetylacetone, benzalacetone, allyl nitrite, methyl vinyl ketone, benzoquinone, on Phtoquinone.

The following component or mixture of components is used as a solvent:

water, methanol, ethanol, isopropanol, propanol, butanol, isobutanol, 2-ethylhexanol ethylene glycol, propylene glycol, ethylcellosolve, butylcellosolve, methylcarbitol, ethylcarbitol, butylcarbitol, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate, dimethyl sulfoxide, dimethylformamide, dimethyl carbonate, pro Pylene carbonate, pentane, hexane , heptane, isooctane, benzene, toluene, white spirit, naphtha, gas condensate, gasoline, kerosene, diesel fraction, straight-run gas oil.

A number of laboratory and pilot industrial tests of the compositions were carried out to assess the effectiveness of their action.

Testing the reagent for the effectiveness of neutralizing hydrogen sulfide and mercaptans.

The compositions under study are tested on an oil sample with an initial content of hydrogen sulfide of 700 ppm and mercaptans of 3200 ppm. 100 g of oil is loaded into the test cell and the appropriate neutralizing composition is dosed: neutralizer or neutralizer and an additional component in a 1:1 ratio. The mass ratio of neutralizing composition: (hydrogen sulfide + mercaptans) in the reaction mixture ranges from 1:1 to 6:1. The oil is then shaken for 1 minute and kept at 20°C for 2 hours. A quantitative analysis of oil is carried out for the content of residual hydrogen sulfide and mercaptans and the degree of neutralization of hydrogen sulfide is calculated. The results obtained are shown in Table 1.

Testing the reagent for bactericidal activity.

Laboratory tests of reagent samples according to examples 1-21 for the effectiveness of suppressing the growth of SRB are carried out according to the MVI 2.01-05765670-006-2016 “Methodology for determining the level of contamination of oil field systems by various groups of microorganisms and assessing the bactericidal effect of reagents of JSC NIIneftepromkhim”. The quantitative composition of SRB is determined by the method of limiting 10-fold dilutions using Postgate nutrient medium (OST 39-151-83). An active enrichment culture of SRB is isolated from the production fluid of the Malyka field by RN-Uvatneftegaz LLC. After diluting the SRB, the sample is subcultured 3 more times into a fresh nutrient medium. For testing, a 4-5 day old SRB culture is used, which gives blackening in 24 hours when dosing 1 cm3 into the nutrient medium. In a series of labeled glass penicillin vials with Postgate medium, 1 cm ³ of an enrichment culture of SRB is injected with a sterile syringe and the test reagent is dosed in an amount that provides the required concentration in mg/l. The vials are mixed and thermostated at 32-35°C. For each reagent concentration, 3 parallel tests are carried out. Similar samples without the addition of a reagent are used as a control. Thermostated vials at 32-35°C are observed for 15 days, noting the appearance of a black color. The effectiveness of the bactericidal action of the reagent is assessed by the appearance or absence of hydrogen sulfide. The presence of hydrogen sulfide is determined by the formation of a black precipitate of iron sulfides. The results obtained are shown in Table 1.

Testing the reagent for the effectiveness of its protective action against corrosion.

The protective effect in mineralized hydrogen sulfide-containing aqueous environments is determined in accordance with OST 39-099-79 “Corrosion inhibitors. A method for assessing the effectiveness of the protective action of corrosion inhibitors in oilfield wastewater." The determination is carried out by the gravimetric method in circulation cells in an inhibited standard model of formation water containing 100 mg/l of hydrogen sulfide.

From the results given in Table 1, the high efficiency of the proposed neutralizer is noted in comparison with traditionally used neutralizers.

Thus, the proposed neutralizer of hydrogen sulfide and mercaptans is highly effective at low concentrations, does not have a negative effect on oil preparation processes, is able to suppress the growth of sulfate-reducing bacteria, is effective in inhibiting equipment corrosion, and is compatible with mineralized formation waters. The neutralizer does not contain organochlorine compounds, salts of quaternary ammonium bases that can decompose to form organochlorine compounds, as well as substances and mixtures of substances that lead to an increase in the content of organic chlorides in oil. Exceeding the maximum permissible concentration of organochlorine compounds negatively affects the quality of oil and negatively affects its export, which in turn has unpleasant consequences for the economy of the enterprise and the industry as a whole.

Sample number component composition, % Degree of neutralization Bactericidal effect relative to SRB at reagent dosage, mg/l Degree of corrosion protection at a dosage of 50 mg/l, % neutralizer additional reagent Alkali metal hydroxide and/or organic base catalyst Complexon Surfactant Solvent unsaturated and/or carbonyl compounds Solvent hydrogen sulfide,% mercaptans, % 100 300 1 sodium hydroxide-30 Copper phthalocyanine-0.05 EDTA-3.45 ABSC-1.5 water-50
methanol-15 - - 97 81 incomplete suppression complete suppression 92 2 Potassium hydroxide-30 Cobalt phthalocyanine-0.05 OEDF-2.95 Cocoamine OE15 -2 water-50
methanol-15 - - 97 78 incomplete suppression complete suppression 92 3 diethylamine-50 Copper sulfate-0.02 EDTA-0.98 neonol AF 9-10 -4 KORBS-45 - - 96 70 incomplete suppression complete suppression 93 4 monoethanolamine-50 Zinc phthalocyanine-0.05 NTF-2.45 neonol AF 9-9 -2.5 isopropanol-45 - - 95 69 incomplete suppression complete suppression 93 5 sodium hydroxide-15
diethanolamine-15 Iron phthalocyanine-0.05 AA/MA-2.95 sodium laureth sulfate-2 water-40
ethanol-25 - - 97 74 incomplete suppression complete suppression 93 6 Potassium hydroxide-15
methenamine-15 Iron phthalocyanine-0.05 EDTA-2.95 ABSC-2 water-40
methanol-25 - - 97 73 incomplete suppression complete suppression 94 7 sodium hydroxide-30 Nickel phthalocyanine-0.05 DTPA-2.45 neonol AF 9-12 -0.5 water-50
methanol-17 propargyl aldehyde-100 - 100 94 complete suppression complete suppression 92 8 monoethanolamine-50 Zinc phthalocyanine-0.05 HPAA-2.95 PP-5004-2 isopropanol-45 acrolein-100 - 100 91 complete suppression complete suppression 94 9 Potassium hydroxide-30 Cobalt phthalocyanine-0.02 DTPA-3.48 PP-4202-1.5 water-50
methanol-15 acrylonitrile-100 - 100 96 incomplete suppression complete suppression 94 10 Potassium hydroxide-15
methenamine-15 Copper phthalocyanine-0.05 PAA-2.95 PP-6003-2 water-40
methanol-25 methyl methacrylate-100 - 100 90 incomplete suppression complete suppression 95 eleven DETA-30 Copper nitrate-0.5 EDTA-4.5 PP-4202-5 methanol-60 crotonaldehyde-100 - 97 88 complete suppression complete suppression 96 12 ammonia-20 Nickel sulfate-0.3 NTF-2,2 Cocoamine OE15 -7.5 water-55
methanol-15 methyl vinyl ketone-100 - 95 65 incomplete suppression complete suppression 95 13 triethanolamine-40 Cobalt 2-ethylhexanoate - 0.3 OEDF-2.7 PP-5004-7 ethylcarbitol-50 ethyl acrylate-100 - 97 73 incomplete suppression complete suppression 96 14 Urotropin-35 Cobalt 2-ethylhexanoate - 0.3 OEDF-3.2 PP-4202-6.5 water-25
ethylene glycol-30 maleic anhydride-30 butylcellosolve-40
methanol-30 95 68 incomplete suppression complete suppression 97 15 Ethylamine-40 Copper nitrate-0.5 PCA-3.5 PP-6003-6 Ethylcellosolve-50 glutaraldehyde-50 water-50 95 65 complete suppression complete suppression 95 16 sodium hydroxide-30 Nickel 2-ethylhexanoate - 0.1 EDTA-2.4 sulfonol-2.5 water-50
methanol-15 acrolein-80 nafta-20 100 97 complete suppression complete suppression 94 17 sodium hydroxide-15
triethylamine-15 Cobalt 2-ethylhexanoate - 0.2 PAPEMP-2,3 sodium laureth sulfate-2.5 water-40
ethanol-25 acrylic acid-80 methanol-20 100 90 incomplete suppression complete suppression 92 18 Potassium hydroxide-30 Nickel 2-ethylhexanoate - 0.1 NTF-2,4 PP-6003-2.5 water-50
methanol-15 acrylamide-70 ethylcellosolve-30 99 72 incomplete suppression complete suppression 94 19 Potassium hydroxide-15
diethylamine-15 Nickel phthalocyanine-0.05 OEDF-2.95 neonol AF 9-12 -2 water-40
ethanol-25 benzaldehyde-80 toluene-20 98 74 complete suppression complete suppression 95 20 lithium-15 hydroxide
ethylenediamine-15 Zinc phthalocyanine-0.05 PAA-2.95 Cocoamine OE15 -2 water-40
ethanol-25 Methacrylonitrile-80 isooctane-20 100 84 incomplete suppression complete suppression 95 21 Triethylamine-25
Urotropin-20 Cobalt phthalocyanine-0.05 DTPA-2.45 sulfonol-2.5 water-15
ispropanol-35 glyoxal-40 water-60 96 76 complete suppression complete suppression 94 prototype* sodium hydroxide-0.1
dimethylethanolamine-4.9
hemiformal methanol-75 KATAPAV S.80-18 PEG-2 - - 92 n.d. suppression suppression 93

Claims (5)

1. Composition for neutralizing hydrogen sulfide and mercaptans, including an alkali metal hydroxide and/or an organic base, a solvent, a catalyst, a complexone, a surfactant in the following ratio of components, wt.%: Alkali metal hydroxide and/or organic base 10.0-60.0 Catalyst 0.01-2 Complexon 0.1-15 Surface-active substance 0.1-15 Solvent rest 2. A method for purifying oilfield media from hydrogen sulfide and mercaptans by treating the feedstock with the chemical composition according to claim 1, characterized in that unsaturated and/or carbonyl compounds are additionally pumped in a solvent, and the ratio by weight of the chemical composition according to claim 1 to unsaturated and/or or carbonyl compounds in the solvent is 9:1-1:9. 3. A method for purifying oilfield media from hydrogen sulfide and mercaptans by treating the feedstock with the chemical composition according to claim 1, characterized in that unsaturated and/or carbonyl compounds are additionally pumped, and the ratio by weight of the chemical composition according to claim 1 to unsaturated and/or carbonyl compounds connections is 9:1-1:9. 4. The method according to claim 2, characterized in that the injection of the chemical composition according to claim 1 and unsaturated and/or carbonyl compounds in the solvent is carried out simultaneously.