RU2549534C1 - Composition for breaking down water-oil emulsions and protecting oil field equipment from corrosion - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a composition containing a glycerine-based block-copolymer of ethylene and propylene oxides (15.0-50.0 wt %), an ethylenediamine-based block-copolymer of ethylene and propylene oxides (15.0-50.0 wt %), a condensation product of oxyethylated nonylphenol with a different oxyethylation degree with polyoxymethylene and a carbonic acid diamide (1.0-5.0 wt %), a mixture of oxyethylated nonylphenol and a triethanolamine salt of a sulphoethoxylate of oxyethylated nonylphenol (1.0-5.0 wt %), a water-alcohol solution of alkyl phosphates (1.0-5.0 wt %) in a solvent - mixture of nefras with methanol or methanol and fresh water (the balance).

EFFECT: faster and complete breakdown of emulsions with simultaneous protection of oil field equipment from corrosion.

4 tbl, 5 ex

Description

The invention relates to the field of oil preparation at oil and gas fields, and in particular to compositions for the destruction of oil-water emulsions stabilized by iron sulfide and coagulated asphaltenes formed by mixing different types of oils, while protecting oilfield equipment from corrosion.

A known composition for the destruction of persistent oil-water emulsions, comprising 20-60% of the product of the interaction of the block copolymer of ethylene oxides and propylene with phosphorus or phosphorus and nitrogen compounds, 20-60% of the hydroxyalkylated product of the condensation of alkyl phenol with a formaldehyde-containing component, oil-soluble active nonionic surface-active - the rest [1]. However, this composition is not effective for the destruction of water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes, which are formed by mixing different types of oils.

A known composition for dehydration and desalting of water-oil emulsions, including 9.85-44.00% of oxyalkylated ethylenediamine - Diproxamine-157, where the number of propylene oxide units 4 m = 60-61, and the number of ethylene oxide units 4 n = 27-28, and 11, 00-55.15% of an oxyalkylated alkyl phenol compound, which is used as the ethoxylated isononyl phenol formaldehyde resin of the formula:

,

,

where R is isononyl, m is an integer from 2 to 9, k is an integer from 2 to 4 with a mass ratio of the components of the mixture 1: 0.25-5.6, respectively, the organic solvent is the rest. The demulsifying composition has universal properties, because provides not only demulsification of oil during its dehydration, but also desalination [2]. However, the known composition is not effective enough for the destruction of water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes, formed by mixing different types of oils, forms intractable interphase layers and has a selective effect.

The closest in technical essence (prototype) is a composition for breaking an oil-water emulsion, comprising 17-19% of a block copolymer of ethylene and propylene oxides based on glycerol, 33-37% of a block copolymer of ethylene and propylene oxides based on ethylene diamine in a solvent, and in as a solvent, it contains 30-35% methanol and water (the rest) and additionally includes 5-6% demulsifier. As a demulsifier, the composition contains the following mixture of components, wt.%: Dimethyl phosphite 0.35-0.5, amine or triethanolamine 0.35-0.5, alkyl phenol 14.0-19.0, phosphenox-H-6 9.0 -25.0, diproxamine-157 or diproxamine 157-65M 15-30, the rest is the solvent [3]. However, the known composition does not have a sufficient demulsification effect upon the destruction of oil-water emulsions stabilized by iron sulfide and coagulated asphaltenes, which are formed by mixing different types of oils.

The objective of this invention is to provide a demulsifying composition that is highly effective in the destruction of water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes, which are formed when different types of oils are mixed, and which prevents the formation of interfacial layers, while protecting oilfield equipment from corrosion.

The problem is solved in that the composition for the destruction of water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes formed when different types of oils are mixed, and at the same time protect oilfield equipment from corrosion, containing a block copolymer of ethylene and propylene oxides based on glycerol - Laprol 6003-2B -18, a block copolymer of ethylene and propylene oxides based on ethylene diamine - Diproxamine 157-65M and the solvent - a mixture of nephras with methanol in a ratio of 7: 3 or methanol and fresh water in a ratio 3: 1, additionally contains Neftenol KS, which is a condensation product of hydroxyethylated nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic diamide, VVD Neftenol, which is a mixture of ethoxylated nonylphenol and triethanolamine salt of sulfoethoxylate, hydroxyethylenol, ethylenedioethylenone, ethylenedioethylenated, ethylenediamine alcohol solution of alkyl phosphates in the following ratio of components, wt.% .:

Block copolymer of ethylene and propylene oxides based on glycerin: Laprol 6003-2B-18 15.0-50.0 Block copolymer of ethylene and propylene oxides based on ethylenediamine: Diproxamine 157-65M 50.0-15.0 Oxyethylated Condensation Product nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic diamide: Neftenol KS 1.0-5.0 A mixture of ethoxylated nonylphenol and triethanolamine salt of sulfoethoxylate hydroxyethylated nonylphenol Neftenol VVD 1.0-5.0 Aqueous alcohol solution of alkyl phosphates SAW ND 80 1.0-5.0

Solvent:

A mixture of nephras with methanol in a ratio of 7: 3 or methanol and fresh water in a ratio of 3: 1 rest

To obtain the proposed composition and prototype in laboratory conditions, the following substances were used.

1. The block copolymer of ethylene oxide and propylene based on glycerol is a simple polyester - Laprol 6003-2B-18, manufactured according to TU 2226-020-10488057-94.

2. The block copolymer of ethylene oxide and propylene based on ethylene diamine - Diproxamine 157-65M, is produced according to TU 2483-194-00203335-2010.

3. The condensation product of ethoxylated nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic acid diamide - Neftenol KS, is produced according to TU 2221-036-17197708-97.

4. A mixture of water-soluble hydroxyethylated alkyl phenols and their sulfoethoxylates in the form of salts with triethanolamine - Neftenol VVD, is produced according to TU 2483-015-17197708-97.

5. A water-alcohol solution of alkyl phosphates - surfactant ND 80, is produced according to TU 2483-138-54651030-2013.

6. Fosphenox N6 is produced according to TU 2484-537-05763441-2011.

7. Oxyethylated alkyl phenol (Neonol AF 9-6) is available in accordance with TU 2483-077-05766801-98.

8. Dimethyl phosphite is produced according to TU 2435-430-05763441-2004.

9. Triethanolamine is produced according to TU 2423-061-05807977-2002.

10. Toluene is produced in accordance with GOST 14710-78.

11. Oil solvent (Nefras A130 / 150), produced according to GOST 10214-78.

12. Technical methanol, produced according to GOST 2222-95.

13. Fresh water.

A new set of claimed essential features will allow to obtain a new technical result, namely, to obtain an effective composition of complex action for the destruction of oil-water emulsions stabilized by iron sulfide and coagulated asphaltenes that are formed when different types of oils are mixed, and to prevent the formation of interphase layers while protecting oilfield equipment from corrosion .

The proposed compositions in laboratory conditions were prepared as follows.

Example 1

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 250 g (50 wt%) of Diproxamine 157-65M, 75 g (15 wt%) of Laprol 6003-2B-18, 5 g (1 wt%) are charged. ) Neftenol KS, 25 g (5% wt.) Neftenol VVD, 5 g (1% wt.) Surfactant ND 80, 140 g (28% wt.) A mixture of methanol and fresh water in a ratio of 3: 1 and stirred for 20 minutes.

Example 2

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 250 g (50 wt%) of Diproxamine 157-65M, 80 g (16 wt%) of Laprol 6003-2B-18, 5 g (1 wt%) are charged. ) Neftenol KS, 5 g (1% wt.) Neftenol VVD, 25 g (5% wt.) Surfactant ND 80, 135 g (27% wt.) A mixture of methanol and fresh water in a ratio of 3: 1 and stirred for 20 minutes.

Example 3

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 140 g (28% wt.) Of a mixture of nephras with methanol in a ratio of 7: 3, 15 g (3% wt.) Neftenol KS, 200 g (40% wt.) .) Laprol 6003-2B-18, 125 g (25% wt.) Diproxamine 157-65M, 10 g (2% wt.) Neftenol VVD, 10 g (2% wt.) Surfactant ND 80 and stirred for 20 minutes .

Example 4

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 130 g (26% wt.) Of a mixture of Nefras with methanol in a ratio of 7: 3, 25 g (5% wt.) Neftenol KS, 250 g (50% wt.) .) Laprol 6003-2B-18, 75 g (15% wt.) Diproxamine 157-65M, 5 g (1% wt.) Neftenol VVD, 15 g (3% wt.) Surfactant ND 80 and mix for 20 minutes .

Example 5 (prototype)

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 85 g (17% by weight) of Laprol 6003-2B-18, 170 g (34% by weight) of Diproxamine 157-65M, 30 g (6% by weight) are charged. ) demulsifier, 215 g (43% by weight) of a mixture of methanol and fresh water in a ratio of 3: 1 and stirred for 20 minutes.

The demulsifier for example 5 is prepared by sequential mixing of 0.5 g (0.5% wt.) Of Dimethylphosphite with 19 g (19% wt.) Of Neonol AF9 in a reactor equipped with a stirrer with a speed of 60 rpm at 100 ° C for 30 minutes. The resulting mixture was cooled to 20 ° C and 0.5 g (0.5 wt%) of triethanolamine was added thereto with stirring at 20 ° C for 10 minutes, then 25 g (25 wt%) of Phosphenox was added to the mixture with stirring H-6 for 10 minutes, then add 20 g (20% of the mass.) Diproxamine 157-65M with stirring for 10 minutes. The resulting mixture was dissolved in 35 g (35% by weight) of a solvent mixture (methanol: toluene: water = 1: 1: 1) with stirring for 40 minutes.

The resulting compositions were tested for demulsifying activity on real water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes, formed by mixing oils of the Ganino-Yangulsky and Yakushkinsky fields of the Northern group of fields of OJSC Samaraneftegaz in a ratio of 40:60. Physico-chemical characteristics of the oil Ganino-Yangul and Yakushkinsky fields are shown in table 2.

Under the existing infield gathering system of the Northern group of fields TsPNG-1 of OJSC Samaraneftegaz, well products containing hydrogen sulfide are mixed with products whose produced waters contain iron ions, which leads to the formation of iron sulfide. A sharp increase in the stability of such emulsions is observed when the concentration of iron sulfide is more than 100 g / t of oil.

The demulsifying activity of the compounds was determined by the method of the bottle test ("Bottle Test"). Evaluation of the demulsifying activity of the reagents was carried out by the effectiveness of the destruction of the emulsion according to the following indicators:

- the dynamics of the allocation of water from the emulsion (demulsifying efficiency,%),

- the quality of the released water (transparency, turbidity, the amount of oil products),

- the quality of the oil-water phase separation (the presence of an interfacial layer).

The oil-water emulsion was poured into 100 ml into graduated test tubes with a volume of 150 ml. The calculated amount of 10% solutions of the studied compounds and the prototype was dosed into the samples using a microdoser. The tubes were closed and the samples were mixed for 60 minutes. Sludge was carried out in a water thermostat at a temperature of 60 ° C. Then, the amount of freely released water was measured, a visual assessment of the quality of the released water was made, and the interface was evaluated (the presence of an interfacial layer). The test results are shown in table 3.

The degree of corrosion protection was evaluated by the gravimetric method according to GOST 9.506-87 on the model of formation water (density - 1.41 g / cm ³ , mineralization - 261 g / dm ³ , pH - 5.78), H ₂ S content - 200 mg / dm ³ . The tests were carried out for 6 hours in hermetically closed circulation cells. The test results are shown in table 3.

For an additional assessment of the quality of the prepared water and the presence of interfacial layers, studies were carried out on samples of water-oil emulsions with a volume of 2 l.

The degree of wastewater treatment was evaluated by the oil content in the settled water according to the method of OST 39-133-182 ″ Water for flooding oil reservoirs. Determination of oil content in field wastewater ″. The presence of an interfacial layer was evaluated visually. The results are presented in table 4.

From the data presented in the tables it can be seen that the claimed composition for the destruction of water-oil emulsions stabilized by iron sulfide and coagulated asphaltenes, formed by mixing different types of oils, is more effective than the composition of the prototype, capable of deep dehydration at the first discharge (after 15 minutes of sedimentation ), and also allows you to effectively treat wastewater from oil products, while ensuring the almost complete absence of the formation of an interphase layer with simultaneous protection of oil field equipment against corrosion.

table 2 Physico-chemical characteristics of the oil-water emulsion Name of indicator unit of measurement Test method The value of the indicator for oil field Ganino-Yangulskoe Yakushkinsky Mass fraction of water % of the mass. GOST 2477-65 80 54 Oil Density at 20 ° C kg / m ³ GOST 3900-85 855 879 Kinematic oil viscosity at 20 ° C mm ² / s GOST 33-2000 eleven 36 Total sulfur content in oil % of the mass. GOST 51947-2002 1.97 2.15 Oil asphaltene content % of the mass. VNIINP technique 1,5 4,5 The content of silica gel resins in oil % of the mass. VNIINP technique 6.0 10.5 Paraffin content in oil % of the mass. GOST 11851-85 5.2 3.2 Mass fraction of methyl and ethyl mercaptans in total mn ^-1 (ppm) GOST 50802-95 less than 2 563 Mass fraction of hydrogen sulfide mn ^-1 (ppm) GOST 50802-95 less than 2 74 The content of iron sulfide in the prepared mixture of emulsions g / t RD 39-30-898-83; GOST3040 4-2000 454.15

Table 3 The effectiveness of the compounds Example composition Consumption, g / t The demulsifying effectiveness of the compositions during the sludge min,% Quality monitoring after sludge The degree of protection,% when the content of H ₂ S 200 mg / DM ³ 0 fifteen thirty 60 water interfacial layer one 130 0 81 83 89 gray lack of 84 2 130 0 80 81 86 gray lack of 84 3 130 0 85 85 93 gray lack of 91 four 130 0 84 85 90 gray lack of 86 5 (prototype) 130 0 72 72 80 gray Availability 84

Table 4 The effectiveness of the compounds Example composition Consumption, g / t Observation of water quality after sludge the presence of petroleum products, mg / DM ³ interfacial layer sump walls one 130 25 lack of clean 2 130 45 lack of clean 3 130 twenty lack of clean four 130 fifteen lack of clean 5 (prototype) 130 47 Availability clean

Sources of information taken into account:

1. Lebedev N.A., Yudina T.V., Safarov R.R., Varnavskaya O.A. and others. The composition for the destruction of persistent oil-water emulsions and the protection of oilfield equipment from asphaltene-resin-paraffin deposits and corrosion. RF patent 2227154 (C10G 33/04), published April 20, 2004 - analogue.

2. Grechukhina A.A., Kabirova L.A., Diyarov I.N., Aleksandrov D.A. Composition for dehydration and desalination of oil Polynod-D. RF patent 2139317 (C10G 33/04), published on 10/10/1999 - analogue.

3. Zotova A.M., Maltseva II, Zotov S.R., Zotova N.R. and others. The composition for the destruction of oil-water emulsions and wastewater treatment, having the effect of inhibiting hydrogen sulfide, carbon dioxide corrosion and asphaltene-resin-paraffin deposits. RF patent 2213123 (C10G 33/04), published September 27, 2003 - a prototype.

Claims (1)

Composition for breaking oil-water emulsions stabilized by iron sulfide and coagulated asphaltenes, which are formed when different types of oils are mixed, and at the same time protecting oilfield equipment from corrosion, containing a glycerol-based block copolymer of ethylene and propylene oxides, and ethylene-diamine-based block copolymer of ethylene and propylene oxides and a solvent, characterized in that it further comprises Neftenol KS, which is a condensation product of hydroxyethylated nonylphenol with various degrees for hydroxyethylation with polyoxymethylene and carbonic acid diamide, VVD Neftenol, which is a mixture of ethoxylated nonylphenol and triethanolamine salt of ethoxylated nonylphenol sulfate, and ND80 surfactant, which is a water-alcohol solution of glycol-alkylene-propylene copolymethylene copolymer, is used as Laprol 6003-2B-18, as a block copolymer of ethylene and propylene oxides based on ethylene diamine - Diproxamine 157-65M, and as a solvent - a mixture of nephras with m Tanoli in a ratio of 7: 3 or methanol and fresh water in a ratio of 3: 1, with the following component ratio,% wt .:.
Block copolymer of ethylene and propylene oxides based on glycerin: Laprol 6003-2B-18 15.0-50.0 Block copolymer of ethylene and propylene oxides based on ethylenediamine: Diproxamine 157-65M 50.0-15.0 Oxyethylated Condensation Product nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic diamide: Neftenol KS 1.0-5.0 A mixture of ethoxylated nonylphenol and triethanolamine salt of sulfoethoxylate hydroxyethylated nonylphenol: Neftenol VVD 1.0-5.0 Aqueous alcohol solution of alkyl phosphates SAW ND 80 1.0-5.0 Solvent: A mixture of nephras with methanol in a ratio of 7: 3 or methanol and fresh water in a ratio of 3: 1 rest