RU2454449C1 - Composition for dehydrating and desalinating water-oil emulsions, having corrosion protection effect - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention can be used in oil dehydration during pipeline demulsification on oil collection facilities, oil treatment plants, oil refineries, and in oil deep dehydration and desalination processes. The invention relates to a composition for dehydrating and desalinating water-oil emulsions, containing a nonionic surfactant 35-49 wt %, an ionic surfactant which contains a quaternary nitrogen atom selected from: oleyl amidopropyl betaine, cocamidopropyl betaine, alkylbetaine, cetyltrimethylammonium chloride, oleyl amidopropyl trimethylammonium chloride, oleyl amidopropyl dimethylamino oxide 1-15 wt % and solvent - the balance.

EFFECT: wider range of surfactant compositions for effective dehydration and desalination of water-oil emulsions, protection of the system for collecting, transporting and treating oil from corrosion.

2 cl, 5 tbl, 43 ex

Description

The invention relates to means for destroying a water-oil emulsion while protecting the oil collection, transport and treatment systems from corrosion and can be used for oil dehydration during pipe demulsification at oil recovery facilities, oil treatment plants, refineries and deep oil dehydration and desalination processes.

Known additive for demulsifiers based on nonionic surfactants, where mono- (C ₂ -C ₄ ) -alkyl ether of ethylene glycol or diethylene glycol is used as an additive (see RF Patent No. 2009164, MKI C10G 33/04, publ. March 15, 1994).

The disadvantage of this demulsifier using this additive is its low demulsifying effectiveness and the absence of additional protective properties.

A known composition for dehydration and desalination of an oil emulsion containing 50-55% water-methanol solution of a nonionic block copolymer of ethylene oxide and propylene, a waste product from the production of ethylene glycols and water (see RF Patent No. 2091435, MKI C10G 33/04, publ. 09/27/1997 g .).

Also known is a composition for dehydrating, desalting and regulating the rheological properties of high-viscosity oils and water-oil emulsions containing a nonionic block copolymer of ethylene oxide and propylene, a polyalkylbenzene resin and a solvent (see RF Patent No. 2383583, MKI C10G 33/04, publ. March 10, 2010, )

The disadvantage of these demulsifiers is that they use unstable in composition and molecular weight distribution waste of the production of ethylene glycols and a by-product of the production of isopropylbenzenes. Because of this, the surface active properties of the compositions are significantly impaired. However, these compositions do not have protective properties against corrosion.

The closest to the proposed invention in terms of technical nature and the achieved effect is a demulsifier containing a polyurethane of the general formula HO [(C ₂ H ₄ O) _n (C ₃ H ₆ O) _m (C ₂ H ₄ O) _n CONHRNHCO] _x (OC ₂ H ₄ ) _n (OC ₃ H ₆ ) _m (OC ₂ H ₄ ) _n OH),

where m = 43-60, n = 7-40, x = 1-4,

block copolymer of alkylene oxides of the general formula (1)

BUT (C ₂ H ₄ O) _b (C ₃ H ₆ O) _a , (C ₂ H ₄ O) _b , where a = 34-53, b = 6-35, or (2):

where c = 17-26, d = 6-23, and the solvent (see RF Patent No. 2157398, MKI C10G 33/04, publ. 10.10.2000).

Known demulsifier does not have a high demulsifying ability in the dehydration and desalting of oil-water emulsions.

The objective of the invention is to create a more effective composition for dehydration and desalination of oil, expanding the range of compositions of surfactants, as well as a protective system for collecting, transporting and preparing oil from corrosion.

The problem is solved by creating a composition for dehydration and desalting of water-oil emulsions, including a nonionic surfactant and a solvent, moreover, it additionally contains an ionic surfactant containing a quaternary nitrogen atom in its structure, selected from the group: oleylamidopropyl betaine, cocamidopropyl betaine, alkylbetainide, cetyl methyl tetryl methyl tetryl methyl tetrim oleylamidopropyltrimethylammonium chloride, oleylamidopropyldimethylamino oxide, in the following components, wt.%:

non-inogenic surfactant - 35-49 ionogenic surfactant selected from the specified group - 1-15 solvent - the rest.

In embodiments, the composition as a solvent comprises methanol, isopropanol, propylene glycol, or mixtures thereof or their aqueous solutions.

To prepare the proposed composition as a nonionic surfactant, polyethers of ethylene and propylene oxides are used:

- Laprol - 6003-2B-18 according to TU 2226-020-10488057-94;

- STX-2124 according to TU 2226-002-34751835-97;

oligourethanes (OU) based on polyethers of ethylene and propylene oxides:

- OU-1 - (4202-2B-30 and Laprol - 5003-2B-10);

- OU-2 - (PP 4202-2B-30 and Laprol - 6003-2B-18);

- OU-3 - (Laprol - 6003-2B-18);

- OU-4 - (PP 4202-2B-30);

- OU-5 - (PP 4202-2B-30 and STX-2124).

As an ionic surfactant use:

- oleylamidopropyl betaine (OAPB) according to TU 2480-002-04706205-2004;

- Cocamidopropyl betaine (KAPB) according to TU 2480-002-04706205-2004;

- alkyl betaine (AB) according to TU 2480-002-04706205-2004;

- cetyltrimethylammonium chloride (CTAC) according to TU 2482-004-04706205-2005;

- oleylamidopropyltrimethylammonium chloride (OAPTAH) according to TU 2482-004-04706205-2005;

- oleylamidopropyl dimethylamino oxide (OAPDAO) according to TU 2482-007-04706205-2006.

As a solvent, use:

- methanol according to GOST 2222-95;

- isopropanol according to GOST 9805-84;

- propylene glycols (PGL) according to TU 6-09-2434-81;

- or mixtures thereof;

- or their aqueous solutions.

Commodity forms of nonionic surfactants are 50% solutions. The solvent used is methanol.

Commodity forms of ionic surfactants are solutions with a basic substance content of from 30 to 80 wt.%. The type of solvent is chosen depending on the type of ionic surfactant and in accordance with TU.

In the claimed compositions for dehydration and desalination of oil, the optimal mass ratio of the active bases of nonionic and ionic surfactants is 94: 6.

The proposed compositions for dehydration and desalting of oil-water emulsions are prepared by mixing the reagents used in the claimed amounts.

We give examples of the preparation of the claimed compounds.

Example 1 (the claimed composition).

47 g of a nonionic surfactant - L6003-2B-18, 3.0 g of ionic surfactant - KAPB and 50.0 g of a solvent - a mixture of methanol and water are mixed in a 150 ml conical flask with a ratio of 43: 7. Stirring is carried out at room temperature 20-25 ° C, the stirring time is 10 minutes (see table 1, example 2).

Examples 2-6, 8-11, 13-18, 20-25, 27-29, 31-35, 37-42 are carried out analogously to example 1, changing the types of nonionic surfactants, ionic surfactants and solvent and their quantitative ratio within the claimed.

Examples 1, 7, 12, 19, 26, 30, 36 are prepared by mixing a nonionic surfactant with a solvent.

Example 43 (prototype).

30 g of a polyurethane of the formula HO [(C ₂ H ₄ O) _n (C ₃ H ₆ O) _m (C ₂ H ₄ O) _n CONHRNHCO] _x (OC ₂ H ₄ ) _n (OC ₃ H ₆ ) _m (OC ₂ H ₄ ) _n OH),

where m = 52, n = 29, x = 1,

20 g block copolymer of the formula (2)

where c = 20, d = 18 and 50 g of methanol. Stirring is carried out at room temperature 20-25 ° C, the mixing time is 10 minutes (see table 1).

Composition formulations are tested for demulsifying efficacy using the standard “bottle sample” method. The test composition is dosed into the emulsion, the mixture is shaken on a Wagner laboratory shaker for 20 minutes at room temperature. Then thermostat for 3 hours at 25 ° C and 2 hours at 50 ° C and measure the amount of released water.

In the study, the kinetics of separating the aqueous phase from the emulsion is evaluated, and the residual water content in the oil phase is also determined. The volume of released water is measured every 10 minutes for 0.5 hours, and every 30 minutes for 4-5 hours.

Table 1 No. p / p Composition Components The content of the components of the composition, wt.% The degree of dehydration (vol.%) For the time (min) at a temperature The residual water content, vol.% 25 ° C 50 ° C Nonionic surfactants IPAV Solvent 10 twenty thirty 60 120 180 240 300 one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen one L 6003-2B-18 - methanol 50:50 0 0 0 four 23 40 55 68 22.8 2 L 6003-2B-18 KAPB methanol + water (43: 7) 47: 3: 50 0 four 7 31 52 57 69 79 16,2 3 L 6003-2B-18 OAPB methanol + water + isopropanol (43: 5.3: 1.7) 47: 3: 50 0 0 2 27 45 60 64 73 20,0 four L 6003-2B-18 Ab methanol + water (43: 7) 47: 3: 50 0 0 2 8 38 71 81 81 14.9 5 L 6003-2B-18 CTAG methanol + water (36:14) 43: 7: 50 3 13 32 49 56 58 61 64 25,2 6 L 6003-2B-18 OAPTAH methanol + isopropanol (48.7: 1.3) 45: 5: 50 10 29th 44 58 63 66 71 73 20,2 7 STX-2124 - methanol 50:50 0 2 5 twenty 42 46 48 fifty 31.6 8 STX -2124 KAPB methanol + water (43: 7) 47: 3: 50 0 0 2 fifteen 52 58 69 75 18.8 9 STX-2124 OAPB methanol + water + isopropanol (31.5: 14: 4.5) 40:10:50 0 0 8 27 56 58 60 63 25.5 10 STX -2124 Ab methanol + water (39.7: 10.3) 45: 5: 50 2 5 9 31 51 57 66 68 22.8 eleven STX -2124 OAPTAH methanol + isopropanol (49.75: 0.25) 47: 3: 50 one four 9 28 fifty 60 68 75 18.5

Continuation of table 1 one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen 12 OU-1 - methanol 50:50 fourteen 17 eighteen 24 29th 31 34 35 37.5 13 OU-1 KAPB methanol + water (43: 7) 47: 3: 50 52 67 68 69 71 73 77 83 13.6 fourteen OU-1 OAPB methanol + water + isopropanol (43: 5.3: 1.7) 47: 3:50 24 48 59 63 66 70 73 75 18.8 fifteen OU-1 Ab methanol + water (43: 7) 47: 3: 50 38 56 69 73 75 81 82 85 12,2 16 OU-1 CTAG methanol + water (36:14) 43: 7: 50 19 40 49 54 61 67 71 73 20,2 17 OU-1 OAPTAH methanol + isopropanol (48.7: 1.3) 45: 5: 50 23 44 51 56 65 69 71 73 20,0 eighteen OU-1 OAPDAO methanol + propylene glycol (35:15) 35:15:50 35 56 70 72 74 75 79 81 14.8 19 OU-2 - methanol 50:50 2 5 8 eighteen 25 28 33 38 36,4 twenty OU-2 KAPB methanol + water (43: 7) 47: 3: 50 73 78 79 81 81 81 83 83 13.6 21 OU-2 OAPB methanol + water + isopropanol (45.6: 3.4: 1) 48: 2: 50 four fifteen 24 69 69 70 73 73 20,0 22 OU-2 Ab methanol + water (43: 7) 47: 3: 50 10 35 fifty 69 71 72 78 82 14.2 23 OU-2 CTAG methanol + water (43: 7) 47: 3: 50 8 21 33 60 65 67 74 77 17.5 24 OU-2 OAPTAH methanol + isopropanol (49.75: 0.25) 47: 3: 50 23 38 48 67 70 73 76 79 16.1 25 OU-2 OAPDAO methanol + propylene glycol (38:12) 38:12:50 19 33 42 54 59 66 71 73 20,0

Continuation of table 1 one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen 26 OU-3 - methanol 50:50 0 0 0 3 8 16 29th 35 37.5 27 OU-3 KAPB methanol + water (43: 7) 47: 3: 50 8 17 27 fifty 59 60 67 75 18.8 28 OU-3 CTAG methanol + water (47.7: 2.3) 49: 1:50 0 0 2 fifteen 33 44 58 63 25.7 29th OU-3 OAPDAO methanol + propylene glycol (42: 8) 42: 8: 50 0 0 8 35 52 58 67 73 20,0 thirty OU-4 - methanol 50:50 2 7 eleven twenty 24 25 29th 31 38.9 31 OU-4 KAPB methanol + water (43: 7) 47: 3: 50 10 38 63 71 75 79 81 81 14.9 32 OU-4 OAPB methanol + water + isopropanol (43: 5.3: 1.7) 47: 3: 50 13 35 54 60 69 70 72 73 20,0 33 OU-4 Ab methanol + water (43: 7) 47: 3:50 35 52 67 71 74 75 76 77 17.5 34 OU-4 CTAG methanol + water (43: 7) 47: 3: 50 3 13 32 49 56 58 61 64 25,2 35 OU-4 OAPTAH methanol + isopropanol (48.7: 1.3) 45 :: 50 10 29th 44 58 63 66 71 73 20,2 36 OU-5 - methanol 50:50 four 27 fifty 60 63 65 70 79 16,2 37 OU-5 KAPB methanol + water (43: 7) 47: 3: 50 9 25 43 52 56 61 70 80 15.6 38 OU-5 OAPB methanol + water + isopropanol (43: 5.3: 1.7) 47: 3: 50 fifteen 33 56 63 65 66 71 80 15.6 39 OU-5 Ab methanol + water (41.6: 8.4) 46: 4: 50 10 27 54 66 68 69 73 81 14.9 40 OU-5 CTAG methanol + water (43: 7) 47: 3: 50 four 29th 43 56 60 65 71 79 16.1

Continuation of table 1 one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen 41 OU-5 OAPTAH methanol + isopropanol (49.75: 0.25) 47: 3: 50 fifteen 29th 52 63 65 68 76 81 14.8 42 OU-5 OAPDAO methanol + propylene glycol (41: 9) 41: 9: 50 6 35 48 67 70 73 77 80 15.9 43 (prototype) Polyurethane (with m = 52, n = 29, x = 1) + Block copolymer of formula (2) (c c = 20, d = 18) methanol 30:20:50 four 10 fifteen 38 49 54 60 63 25.7 44 No reagent 0 0 0 0 0 0 0 0 48.0

table 2 Sample No. from Table 1 The degree of dehydration (vol.%) For the time (min.) At temperature The residual water content, vol.% 25 ° C 50 ° C 10 twenty thirty 60 120 180 240 300 one 12 22 34 45 52 58 63 64 42.1 2 28 39 48 58 64 67 85 94 10.8 3 fifteen 27 39 49 72 75 82 87 21,4 four 16 25 31 43 54 60 75 87 21,4 5 12 21 thirty 48 57 66 78 87 21,4 6 fifteen 28 36 54 63 67 75 84 25.0 7 3 10 eighteen 24 thirty 31 42 48 51.5 8 3 13 33 46 51 55 67 75 34.0 9 6 13 39 51 55 61 78 87 21,4 10 eleven 33 49 58 61 63 79 89 18.5 eleven 6 12 22 36 48 57 67 72 36.5 12 7 eleven fifteen eighteen 21 24 40 51 50,0 13 66 75 76 78 79 80 87 90 17.5 fourteen 21 31 42 55 70 81 90 96 8.3 fifteen 49 52 57 61 64 66 84 91 15.4 16 27 34 40 52 64 73 85 90 17.5 17 40 46 51 67 78 85 91 94 10.8 eighteen 19 22 28 48 63 76 84 87 21,4 19 27 33 40 46 51 55 70 73 35.3 twenty 40 49 55 59 63 64 73 76 32,7 21 49 52 55 58 61 64 79 85 23.3 22 72 72 72 74 76 76 88 93 13,2 23 37 40 45 60 67 73 85 90 17.5 24 45 54 61 72 78 81 90 94 10.8 25 31 37 43 51 55 63 78 82 26.7 26 39 45 54 59 63 64 76 82 26.7 27 60 66 69 72 75 79 94 95 9.6 28 69 70 73 78 80 82 93 94 10.8 29th 75 78 81 84 87 89 93 94 10.8 thirty 10 fifteen 21 26 31 36 48 52 49.2 31 49 55 61 64 66 67 78 83 25.8 32 40 48 57 60 64 66 78 84 25.0 33 70 73 75 76 78 79 91 94 10.8 34 46 fifty 55 63 68 73 83 85 23.3 35 49 57 64 75 79 86 90 93 13,2 36 13 16 19 25 28 34 47 53 48.8 37 17 28 37 45 49 51 63 69 38.7 38 22 31 39 46 51 52 62 69 38.9 43 (prototype) 12 17 23 34 45 49 62 68 39.3 No reagent 0 0 0 0 0 0 0 0 67.0

Table 3 No.
p / p Reagent Name The degree of dehydration (% vol.) For the time (min.) At temperature The residual water content,% vol. 20 ° C 45 ° C 10 twenty thirty 60 120 180 240 300 one Sample No. 32 from table 1 42 fifty 52 62 97 98 99 one hundred 0.6 2 STX-5 eighteen 24 37 49 91 93 94 95 7.9 3 STX-8 26 32 43 54 71 78 85 88 18.6 four STX-2124 16 23 38 56 89 92 92 92 12.5 5 Reapon-4V twenty 25 35 57 91 94 95 95 7.9 6 Prototype fourteen twenty 32 42 75 83 88 91 14.6 7 Base reagent 8 eleven eighteen 44 91 95 97 98 2,8 8 No reagent 0 0 0 0 0 0 0 0 65.0

Table 4 Components Na ⁺ + K ⁺ Ca ²⁺ Mg ²⁺ HCO ₃ ^- Сl ^- SO ₄ ² - Content, g / l 60 21.6 5.8 0.11 154.4 0.98 Table 5 Sample No. from Table 1 Dosage, g / t Protective effect against corrosion,% 2 thirty 26 70 48 150 37 3 fifteen fifteen 70 35 150 32 four fifteen 35 thirty 37 70 35 8 thirty 26 70 36 9 fifteen 19 thirty 22 70 38 43 (prototype) fifteen fifteen thirty 21 70 24 150 thirty

A comparative analysis of the demulsifying effectiveness of the proposed compositions is carried out on natural emulsions of oils from the Lugovoye field (NGDU TatRITEKneft) with high aggregate stability, with a water content of 48 vol.% And 67 vol.%. The dosage of the reagents was 150 g / t of oil. The research results are shown in tables 1 and 2. From these tables it follows that the claimed composition is more effective than the known.

When using ionic surfactants in compositions based on data from nonionic surfactants, an increase in the demulsifying effectiveness of the composition is observed, as opposed to using the components separately.

To compare the demulsifying activity of the developed compositions with industrial samples of demulsifiers, tests are carried out by the similar method of "bottle tests" in field conditions on natural oil emulsions of the Penyachinskoye field (OAO Elabuganeft) with a water content of 65 vol.%. Tests are carried out at a basic dosage of 180 g / t of oil. The research results are shown in table 3. As a basic reagent take a mixture of reagents SNPCH-4480 and LML-4312 in a ratio of 1: 1.

Tests of the claimed compounds for corrosion protection are carried out on model formation water in accordance with GOST 9.502-82. As a corrosive medium, a reservoir water model is used that is similar in composition to the reservoir water of the Meadow field of NGDU TatRITEKneft (see table 4).

The effectiveness of the claimed compounds on corrosion activity is evaluated by their protective effect according to the formula

where ΔР - corrosion loss on the sample in a corrosive environment without inhibitor, g;

ΔP ₁ - corrosion loss on the sample in a corrosive environment with an inhibitor,

The presented compositions have protective properties against corrosion with an efficiency of up to 48% at an optimal dosage of 70 g / t (see table 5).

An analysis of the results shows that the use of the proposed compositions allows for effective dehydration and desalination of oil, as well as protection of the collection, transport and preparation of oil from corrosion.

Claims (2)

1. The composition for dehydration and desalting of water-oil emulsions, which has a protective effect against corrosion, including a nonionic surfactant and a solvent, characterized in that it additionally contains an ionic surfactant containing in its structure a Quaternary nitrogen atom selected from the group: oleylamidopropyl betaine, cocamidopropyl betaine, alkyl betaine, cetyltrimethylammonium chloride, oleylamidopropyltrimethylammonium chloride, oleylamidopropyl dimethylamino oxide, with the following content , wt.%:
non-inogenic surfactant 35-49 ionic surfactant 1-15 solvent rest 2. The composition according to claim 1, characterized in that as a solvent it contains methanol, isopropanol, propylene glycol, or mixtures thereof, or their aqueous solutions.