Solid-phase composition for hydrogen sulfide neutralization

FIELD: gas and oil production industry.

SUBSTANCE: invention relates to chemical composition used in treatment of holes, among them, absorbing holes, for decreasing the content of hydrogen sulfide in gaseous space in carrying out repairing, research and other works, and can be used in gas and oil production industry under conditions of normal and low seam pressures. Proposed composition comprises the following components, wt.-%: sodium peroxocarbonate, 10-40; surfactant (surface-active substance), 0.5-10; polyacrylamide, 0.02-0.1; sulfamic acid, 17-53, and sodium nitrite, 21-52. The slid-phase composition can comprise water glass also. Invention provides development of effective and simple in preparing and technological composition used for neutralization of hydrogen sulfide in holes.

EFFECT: improved and valuable properties of composition.

2 cl, 7 tbl, 2 ex

 

The invention relates to chemical compositions for treatment of wells, including absorbing, to reduce the hydrogen sulfide content in the gas space of the wells in repair, research or other work. Can be used in the oil and gas industry under normal conditions and low reservoir pressure.

Widely known compositions for chemical binding of hydrogen sulfide in the wells, which is an aqueous solution of neutralizing agents [1, 2] or suspensions [3, 4]. As the neutralization reagents are frequently used products of interaction of alkanolamines with aldehydes, hydroxides of alkaline and alkaline-earth metals, aqueous suspension of the oxides of manganese (IV) and iron (III).

The main disadvantage of the use of neutralizing agents in the form of solutions and suspensions is a low speed and a small degree of binding of hydrogen sulfide due to the low dispersion of the catalyst of hydrogen sulfide and a small area of contact between catalyst of hydrogen sulfide with hydrogen sulfide in the well bore. In addition, neutralization of hydrogen sulfide solutions of neutralizing agents are not effective in terms of absorbing wells and low formation pressures, when the solution of the neutralizing reagent is spent in absorbing horizons without making useful the th work on the binding of hydrogen sulfide.

Known solid-phase composition obtained by mixing a urea-formaldehyde resins, surfactants (surfactant and reactant - catalyst of hydrogen sulfide [5 - prototype]. Curing urea-formaldehyde resin foam leads to the formation of utverzhdenii gas-liquid - foam - system (OGIS), which is injected into the reservoir with the manifestations of hydrogen sulfide. The urea-formaldehyde resin is also a reagent-foam stabilizer. The large surface of the granules foam provides increased dispersion and increased area of contact of the catalyst of hydrogen sulfide with hydrogen sulfide in the injected volume OGGS and in the wellbore.

The composition is difficult to make, are not sufficiently effective and technologically advanced processing production wells due to the necessity to use special equipment (pump, tanks, dispensers, ejector) for the formation of neutralizing hydrogen sulfide EGGS; the probability of clogging of the bottom-hole formation zone of water-insoluble pellets of foam.

Solved by the invention of the task and the expected technical result consists in developing a more effective, simple to prepare and technological composition for neutralization of hydrogen sulfide in the wells. Eliminates the need to use specialnov the equipment for the formation of neutralizing hydrogen sulfide EGGS (pump, tanks, dispensers, ejector). Provides enhanced neutralizing activity of the catalyst of hydrogen sulfide relative to hydrogen sulphide, which is well in space as in gaseous and dissolved form. The effectiveness of neutralizing hydrogen sulfide reagent compared with the prototype increases due to the greater surface contact with the borehole fluids with dispersed gas uncured foam system.

The problem is solved in that the solid-phase composition comprising neutralizing the hydrogen sulfide reagent, surface-active substances (SAS) and reagent-foam stabilizer, characterized in that it contains as reagent-foam stabilizer - polyacrylamide as a neutralizing hydrogen sulfide reagent - peroxocarbonate sodium and additionally sulfamic acid and sodium nitrite, in the following ratio, wt.%:

PAV0,5-10
polyacrylamide0,02-0,1
peroxocarbonate sodium10-40
sulfamic acid17-53
sodium nitrite21-52.

The composition additionally contains water glass.

The lower limit of the content of surfactant in the composition is 0.5 wt.% obpl is established with representation from the value of the critical micellization concentration (CMC) of surfactants, flow of solid-phase composition and flow of water on its dissolution (from 100 to 2000 DM3). The upper limit of the content of surfactant in the composition 10 wt.% due to the high cost of surfactants and the need for high capacity, the composition of the sulfide. As surfactants can be used, for example, sodium lauryl sulfate or sulfonic acid.

The range of the content of PAA in the composition of 0.02-0.1 wt.% due: the minimum content of the first appearance stabilizersa foam properties; the maximum is the technology of preparation of solid-phase composition with the use of a solution of PAA in water, evaporating after hardening of the composition.

Rest in the composition - peroxocarbonate sodium sulfamic acid and sodium nitrite, in a stoichiometric ratio to the hydrogen sulfide and to each other, respectively, the following equations of chemical reactions.

Solid-phase composition can optionally contain liquid glass in the amount of 5-8 wt.% as the foam stabilizer, generated in water containing high amount of salts of calcium and magnesium. The range of content of liquid glass is due: the minimum content of the first appearance stabilizersa foam properties; the maximum is the technology of preparation of solid compositions using liquid glass.

Raw material for obtaining cordovano the compositions are substances, produced by the chemical industry by the relevant state Standards and Technical conditions, are shown in table 1. Characteristics of the raw materials in table 2-5.

Table 1
Raw materials and regulatory documents (ND) for the production of a composition
No.SubstanceFormulaND
1Peroxocarbonate sodiumNa2CO3*H2O2THE 2144-284-05763441-91
2Sulfamic acidH2NSO2OHTHE 2121-278-00204197-2001
3PolyacrylamideTHE 2216-001-05966916-93
4Surfactant sodium dodecyl sulfateC12H25OSO2ONaTHE 6-09-64-75 or THE 6-09-37-1146-91
5Sodium nitriteNaNO2GOST 4197-74

Table 2
Characteristics of sulfamic acid in THE 2121-278-00204197-2001
No.Name of indicatorThe norm on LP
1AppearanceWhite crystals
2Mass fraction of sulfamic acid,%, not less than86
3Mass fraction of sulfate ion, % not less than6,0

Table 3
Features peroxocarbonate sodium on THE 2144-284-05763441-91
No.Name of indicatorThe norm on LP
Grade aMark
1Appearance, colorSolid white color
2Mass fraction of active oxygen, %13,5±1,0Not less than 8.5
3Mass fraction of sodium carbonate, %66±2At least 63
4Mass fraction of moisture,%, max33
Granulometric composition, %
51.6 mm, no more than1In consultation
0.1 mm, not less than95
% of active oxygen,
released by 10°
6distilled water
- after 1 minute minimum2020
- after 3 minutes - minimum5050
- after 5 minutes - minimum7070

Table 4
Characteristics of polyacrylamide on THE 2216-001-05966916-93
No.Name of indicatorEd.The norm on LP
1Mass fraction of gel-fraction%20-80
2Screen factor of 0.5% aqueous solution of not less than%2
3The swelling properties, not less thancm3/g50

Table 5
Characteristics of sodium lauryl on THE 6-0-64-75
No.Name of indicatorThe norm on LP And
1AppearanceThe white powder
2Mass fraction of sodium salt euryceros acid %98,5-101,0
3Solubility in waterTested
4the pH of a 0.01 molar solution in water5,0-7,5

Table 6
Characteristics of sodium nitrite according to GOST 4197-74
1. AppearanceWhite crystals with a yellowish or grayish tint
2. Mass fraction of NaNO2, %, not less than98,5
3. Mass fraction of water-insoluble substances,%, no more0,01
4. Mass fraction of chlorides Cl%0,01
5. Mass fraction of sulfate (SO4,%0,02
6. Mass fraction of heavy metals Pb, %0,001
7. Mass fraction of iron Fe%0,001
8. Mass fraction of potassium,%0,01

Table 7
Characteristics of liquid glass according to GOST 13078-81
No.Name of indicatorNormal gradeNorma brand
1AppearanceThick liquid yellow or gray without mechanical impurities and inclusions
2Mass fraction of silicon dioxide22,7 is 29.624,3 is 31.9
3Mass fraction of iron oxide and aluminum oxide, %, max0,250,25
4Mass fraction of calcium oxide, %, max0,200,20
5Mass fraction of sulfuric anhydride, %, max0,150,15
6Mass fraction of sodium oxide, %of 9.3 to 12.8of 8.7 to 12.2
7Silicate module2,3-2,62,6-3,0
8Density, g/cm31,36-1,451,36-1,45

All components are solid compositions are solid water-soluble substances; accordingly, the inventive solid-phase composition is soluble in water. It is prepared directly before processing SLE the new well, where is served by flushing its technical water, for example, using the unit of CA-320.

It is known the use of sulfamic acid together with sodium carbonate (patent No. 1760095, 2223298) in solid-phase gas-forming compositions for removal of fluid from downhole wells.

The authors proposed technical solution for the first time established that the peroxide component of peroxocarbonate sodium oxidizes hydrogen sulfide, and carbonate part will neutralize released when sulfuric acid.

The increased dispersion and increased area of contact of the catalyst of hydrogen sulfide with hydrogen sulfide are provided by the process of gassing beginning when contacting with water the solid phase composition, and the presence of a surfactant and a foam stabilizer - PAA. The effectiveness of neutralizing hydrogen sulfide reagent compared with the prototype increases due to the greater surface contact with the borehole fluids with dispersed gas uncured foam system.

The combination of processes of gasification and neutralization of hydrogen sulfide by dissolving the composition in water provides the efficiency and workability of the composition, characterized also by the ease of preparation. This, in turn, provides simplifying and improving the efficiency and technology of neutralization of hydrogen sulfide in the UK is aging.

Foam system with a catalytic Converter, hydrogen sulfide is formed directly by dissolving in water the inventive solid-phase composition.

Contact solid composition with water leads to the initiation of the reaction of sodium nitrite with sulfamic acid with evolution of nitrogen:

NaNO2+(NH2)SO2OH=NaHSO4+N2↑+H2O

2NaNO2+(NH2)SO2OH=Na2SO4+N2↑+H2O+HNO2,

which occurs with formation of large amounts of gaseous products.

Dissolving a surfactant in water and gassing provides the generation of foam. Disperse medium foam system contains dissolved peroxocarbonate sodium, which chemically binds the hydrogen sulfide by the reaction of neutralization:

Na2CO3+H2S=NaHCO3+NaHS

and oxidation reactions of peroxide part of this salt:

4Na2CO3×H2O2+H2S=4Na2CO3+4H2O+H2SO4

4Na2CO3×H2O2+NaHS=4Na2CO3+4H2O+NaHSO4.

Released sulfuric acid and sodium hydrosulphate neutralized by the carbonate part of peroxocarbonate sodium:

2Na2CO3+H2SO4=2NaHCO3+Na2SO4

Na2CO3+NaHSO4=NaHCO3+Na2SO4.

Thus, the image which are corrosive non-hazardous products, not containing the acid in the food and sulfide forms of sulfur and hydrogen sulfide.

The destruction of the uncured foam system leads to a refluxing solution of peroxocarbonate sodium towards the bottom of the borehole, the formation of a protective neutralizing the aqueous layer at the oil-water contact and neutralization of hydrogen sulfide dissolved in the formation water, mixing with her solution peroxocarbonate sodium.

Capacity peroxocarbonate of sodium hydrogen sulphide is 72 g H2S/kg peroxocarbonate sodium, and the variation of its content allows you to control the capacity of the forming foam system with a catalytic Converter of hydrogen sulfide relative to hydrogen sulphide.

The invention is illustrated by the following examples.

Example 1

Production well No. 4653 NGDU "Yamashneft" JSC "Tatneft" has a static water level at a depth of 731 m from the wellhead. The content of hydrogen sulfide in the annular gas is 1,09% (volumetric). Dissolved hydrogen sulfide in the well fluid 174 mg/DM3. Annulus pressure of 3.3 bar.

Before renovations through the annular valve into the well was filed with 3.5 kg of solid-phase composition composition: 0,35 kg peroxocarbonate sodium (10 wt%), 0.14 kg of liquid glass (4 wt%), 1,225 kg sulfamic acid (35 wt%), 0.066 kg surfactant sodium dodecyl sulfate (1.9 wt.%), 1,715 kg nitrite n is Tria (49 wt.%) and 0,004 kg PAA (0.1 wt.%).

The feed composition was carried out by flushing it with water using the unit of CA-320.

The amount of water supplied should be minimal and sufficient for full flow of the composition into the well. Test results on 10 kg of solid-phase composition should be from 50 l (summer) up to 100 l (winter) technical water.

After the filing of the solid-phase composition the well was closed for 2.5 hours. After 2.5 hours, the selected sample of gas from the annulus. The hydrogen sulfide in the gas is not detected. Next was carried out lifting operations in connection with the breakage of the polished rod. The hydrogen sulfide 0.5 metres from the open mouth of the well for 5 hours is not found.

After repairs and pump start the sampling fluid showed the absence of dissolved sulfide in the first 1.5 m3water, which corresponds to the penetration depth of neutralizing hydrogen sulfide reagent 86 meters below the static liquid level in the well.

Example 2

Production well No. 1017 NGDU "Almatret" JSC APK "Tatneft" has a static water level at a depth of 615 m from the wellhead. The content of hydrogen sulfide in the annular gas is 1,17% (volumetric). Dissolved hydrogen sulfide in the well fluid 251 mg/DM3. Annulus pressure of 1.1 ATM.

Before renovations through the annular valve into the well was p is given to 2.0 kg of solid-phase composition composition: 0,8 kg peroxocarbonate sodium (40 wt%), 0.5 kg of sulfamic acid (25 wt.%), 0.01 kg surfactant sodium dodecyl sulfate (0.5%), 0689 kg sodium nitrite (34,45 wt.%) and 0.001 kg PAA (0,05 wt.%).

The feed composition was carried out by flushing it with water using the unit of CA-320.

After the filing of the solid-phase composition the well was closed for 2 hours. After 2 hours the collected sample gas from the annulus. The hydrogen sulfide in the gas is not detected. Next was carried out lifting operations in connection with the breakage of the polished rod. The hydrogen sulfide 0.5 metres from the open mouth of the hole during the 3 days was not found.

After repairs and pump start the sampling fluid showed the absence of dissolved sulfide in the first 3.5 m3water, which corresponds to the penetration depth of neutralizing hydrogen sulfide reagent at 201 ft below the static liquid level in the well.

Sources of information

1. The Fakhri put A.M., R.A. Fakhri put the cleaning Method of oil and gas condensate from hydrogen sulfide. RF patent №2118649, C10G 29/20, C10G 29/24, publ. 1998.

2. The Fakhri put A.M., R.A. Fakhri put, Belkin M.M. Method of purification of liquid hydrocarbon fractions from hydrogen sulfide and mercaptans. RF patent №2107085, C10G 29/24. publ. 1998.

3. Potapov A.G., Sherman ETC. officials A.I., Anan'ev A.N. The method of processing drilling mud. Auth. mon. No. 1253980, SC 7/00, publ. 1986.

4. Kogan B.C., Kotov, A.V., Buyanova NS, Beltukova T.M., Dzhienbaev S., icheva A.D. Method of removing hydrogen sulfide. Auth. mon. No. 1542594, B01D 53/02, publ. 1990.

5. Lame M.A., Figures A.A. Way of neutralization and isolation manifestations of hydrogen sulfide. Auth. mon. No. 1368427, EV 37/00, publ. 1988.

1. Solid-phase composition comprising neutralizing the hydrogen sulfide reagent surfactant surfactant and reactant-foam stabilizer, characterized in that it contains as reagent-foam stabilizer - polyacrylamide as a neutralizing hydrogen sulfide reagent - peroxocarbonate sodium and additionally sulfamic acid and sodium nitrite in the following ratio, wt.%:

PAV0,5-10
polyacrylamide0,02-0,1
peroxocarbonate sodium10-40
sulfamic acid17-53
sodium nitrite21-52

2. Solid-phase composition according to claim 1, characterized in that it contains additional liquid glass.



 

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