RU2549538C1 - Composition for breaking down water-oil emulsions - 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 (15.0-70.0 wt %), a condensation product of oxyethylated nonylphenol with a different oxyethylation degree with polyoxymethylene and a carbonic acid diamide (1.0-10.0 wt %) in a solvent - mixture of nefras with methanol or methanol and fresh water (the balance).

EFFECT: faster and complete breakdown of an emulsion stabilised with a finely dispersed mechanical impurity.

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 a finely divided mechanical impurity.

A known composition for dehydration and desalting of oil, comprising 35-40% of a nonionic demulsifier based on ethoxylated and oxypropylated propylene glycol or ethylene glycol and ethoxylated and oxypropylated alcohol; 30-40% demulsifier based on ethoxylated and hydroxypropylated ethylenediamine; 10-15% oil soluble nonionic surfactant; 0.5-5.0% C ₂ -C ₄ ethylene or diethylene glycol ether and 10-16.5% aromatic solvent based on aromatic hydrocarbons C ₈ -C ₉ - Nefras A 120/200 [1]. However, this composition is not effective for the destruction of water-oil emulsions stabilized by a finely dispersed mechanical impurity, forms intractable interphase layers, and also does not allow to achieve a high degree of wastewater treatment, released during the destruction of such emulsions.

A known composition for dehydration and desalting of oil, containing a block copolymer of ethylene and propylene oxides based on glycols and a solvent, optionally containing the product of the interaction of a polyether with toluene diisocyanate [2]. The known composition has a sufficiently high demulsifying activity, but is not effective for the destruction of oil-water emulsions stabilized by a finely divided mechanical impurity.

The closest in technical essence (prototype) is a composition for breaking an oil-water emulsion, including a block copolymer of ethylene and propylene oxides based on glycerol, a block copolymer of ethylene and propylene oxides based on ethylene diamine in a solvent [3]. However, the known demulsifier does not have a sufficient demulsification effect in the destruction of oil-water emulsions stabilized by a finely divided mechanical impurity.

The objective of the invention is the creation of a demulsifying composition with high efficiency in the destruction of water-oil emulsions stabilized by a finely divided mechanical impurity, and preventing the formation of interfacial layers.

The problem is solved in that the composition for the destruction of water-oil emulsions stabilized by a finely divided mechanical impurity, and wastewater treatment, 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 solvent - a mixture of nephras with methanol in a ratio of 7: 3 or methanol and fresh water in a ratio of 3: 1, additionally contains Neftenol KS, which is a condensation product of ethoxylated nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic acid diamide, in the following 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 70.0-15.0

Oxyethylated Condensation Product

nonylphenol with varying degrees of hydroxyethylation

with polyoxymethylene and carbonic diamide:

Neftenol KS 1.0-10.0

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

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

6. Fresh water.

A new set of claimed essential features will make it possible to obtain a new technical result, namely, to obtain an effective composition of complex action for the destruction of oil-water emulsions stabilized by a finely dispersed mechanical impurity, and to prevent the formation of interfacial layers.

The proposed compositions in laboratory conditions were prepared as follows.

Example 1

At a temperature of 30 ° C, a three-necked flask equipped with a stirrer and a thermometer is charged with 350 g (70% by weight) of Diproxamine 157-65M, 75 g (15% by weight) of Laprol 6003-2B-18, 5 g (1% by weight). ) Neftenol KS, 70 g (14% by weight) of 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, 255 g (51 wt%) of Diproxamine 157-65M, 80 g (16 wt%) of Laprol 6003-2B-18, 25 g (5 wt%) are charged. ) Neftenol KS, 140 g (28% by weight) of a mixture of methanol and fresh water in a ratio of 3: 1 and stirred for 20 minutes.

Example 3

At a temperature of 30 ° C, a three-necked flask equipped with a stirrer and a thermometer is charged with 150 g (30% by weight) of a mixture of nephras and methanol in a ratio of 7: 3, 25 g (5% by weight) Neftenol KS, 200 g (40% by weight) .) Laprol 6003-2B-18, 125 g (25% wt.) Diproxamine 157-65M 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, 155 g (31% wt.) Of a mixture of nephras with methanol in a ratio of 7: 3, 20 g (4% wt.) Neftenol KS, 250 g (50% wt.) .) Laprol 6003-2B-18, 75 g (15% wt.) Diproxamine 157-65M and stirred for 20 minutes.

Example 5 (prototype)

In a three-necked flask equipped with a stirrer and a thermometer, at a temperature of 30 ° C, 200 g (40% by weight) of Laprol 6003-2B-18, 125 g (25% by weight) of Diproxamine 157-65M, 175 g (35% by weight) are charged. ) a mixture of nefras with methanol in a ratio of 7: 3 and stirred for 20 minutes.

The resulting compositions were tested for demulsifying activity on a real water-oil emulsion of the Vankorskoye field stabilized by a finely divided mechanical impurity. Physico-chemical characteristics of the emulsion are shown in table 2.

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 9 minutes. Sludge was carried out in a water thermostat at a temperature of 40 ° 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.

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 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 a finely divided mechanical impurity 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 petroleum products, while ensuring an almost complete absence of the formation of an interfacial layer.

table 2 Physico-chemical characteristics of the oil-water emulsion of the Vankor field Name of indicator unit of measurement Test method Indicator value Mass fraction of water % of the mass. GOST 2477-65 thirty Solids content % of the mass. GOST 6370-83 0.04-0.07 The content of fine particulate matter (size less than 20 microns) % of the mass. from the total amount of fur. impurities Microtrac S3500 Laser Scanning Method for Light Scanning 31,2 Density of oil at a temperature of 20 ° C kg / m ³ GOST 3900-85 881.8 Kinematic oil viscosity at a temperature of 20 ° C mm ² / s GOST 33-2000 31,889 Mass fraction of hydrogen sulfide ^-1 million (ppm) GOST R 50802-95 less than 2 Mass fraction of methyl and ethyl mercaptans in total ^-1 million (ppm) GOST R 50802-95 less than 2 Total sulfur content in oil % of the mass. GOST R 51947-2002 0.152 Oil asphaltene content % of the mass. VNIINP technique 0.108 The content of silica gel resins in oil % of the mass. VNIINP technique 6.62 Paraffin content in oil % of the mass. GOST 11851-85 2,38 Paraffin Melting Point ° C GOST 23683-89 52 Paraffin saturation temperature ° C OST 39.034-76 22.0

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 0 fifteen thirty 60 120 water interfacial layer one thirty 0 83 83 86 86 epiphany. lack of 2 thirty 0 89 89 89 92 epiphany. lack of 3 thirty 0 83 83 89 89 epiphany. lack of four thirty 0 59 77 80 86 epiphany. lack of 5 (prototype) thirty 0 33 55 76 81 epiphany. Availability

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 thirty 12 lack of clean 2 thirty 2 lack of clean 3 thirty 7 lack of clean four thirty fifteen lack of clean 5 (prototype) thirty twenty Availability slobber.

Information sources

1. Lebedev N.A., Yudina T.V., Yanov A.I., Parfinenko I.A. Composition for dehydration and desalination of oil. RF patent 2019555 (C10G 33/04), published September 15, 1994 - analogue.

2. Tudrii G.A., Varnavskaya O.A., Yudina T.V., Khvatova L.K. Composition for dehydration and desalting of oil and protection of oilfield equipment from corrosion. RF patent 98103496 (C10G 33/04), published on 04/27/1999 - analogue.

3. Zotova A.M., Nikolaev V.F., Maltseva I.I., Vishnevsky A.V. and others. The composition for the destruction of oil-water emulsions and wastewater treatment, having the effect of inhibiting hydrogen sulfide and carbon dioxide corrosion and asphaltene-resin-paraffin deposits. RF patent 2152425 (C10G 33/04), published July 10, 2000 - a prototype.

Claims (1)

Composition for breaking oil-water emulsions stabilized by a finely divided mechanical impurity, containing a block copolymer of ethylene and propylene oxides based on glycerol, a block copolymer of ethylene and propylene oxides based on ethylene diamine and a solvent, characterized in that it additionally contains Neftenol KS, which is an oxyethylated condensation product nonylphenol with varying degrees of hydroxyethylation with polyoxymethylene and carbonic diamide, and as a block copolymer of ethylene and propylene oxides based on glycerol, Laprol 6003-2B-18 is used, Diproxamine 157-65M as a block copolymer of ethylene and propylene oxides based on ethylene diamine, and a mixture of nephras with methanol in a ratio of 7: 3 or methanol and fresh water in a ratio of 3: 1, in the following ratio of components,% mass .:
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 70.0-15.0
Oxyethylated Condensation Product
nonylphenol with varying degrees of hydroxyethylation
with polyoxymethylene and carbonic diamide:
Neftenol KS 1.0-10.0
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