EA020481B1 - Demulsifier - Google Patents

Abstract

The invention relates to means of destroying aqueous petroleum emulsions and can be used at flow line facilities, at industrial installations of oil preparation, at oil refining plants, at processes of deep dehydration and oil desalination with simultaneous protection of collection, transportation and oil preparation system against electrochemical and microbiological corrosion. The invention is aimed at working out a complex action composition - an oil demusifier, an inhibitor of corrosion in hydrocarbonaceous mediums and of asphaltene, resin and paraffin deposits providing to carry out separation of aqueous petroleum emulsion effectively, to inhibit corrosion of oil-production equipment and the asphaltene, resin and paraffin deposits. The assigned task is characterized in that the demulsifier comprises nonionic surfactant, diethanolamine amine compound, or triethanoloamine, or diethylamine, or piperidine and methanol, or ethanol, or isopropanol as a solvent, where it comprises glycerol-based block-copolymer of ethylene oxide and propylene oxide as the nonionic surfactant, having a molecular mass 3000-6000 with the following component ratio, wt%: glycerol-based block-copolymer of ethylene oxide and propylene oxide with a molecular mass 3000-6000 - 50-65; amine compound - diethanolamine, or triethanoloamine, or diethylamine, or piperidine - 5.0-8.0; solvent - methanol, or ethanol, or isopropanol - a remaining part.

Description

The invention relates to means for breaking oil-water emulsions and can be used for desalination and dehydration of oil at oil gathering facilities, industrial oil treatment plants, refineries and processes of deep dehydration and desalination of oil while protecting the collection system, transport and preparation of oil from electrochemical and microbiological corrosion .

A known composition for dehydration and desalting of oil, having the trade name Diproxamine-157-65M, which includes a nitrogen-containing block copolymer of ethylene oxide and propylene oxide [1].

The disadvantages of the known composition are its lack of demulsifying efficacy, the absence of inhibitory activity against corrosion of oilfield equipment and asphalt-resin-paraffin deposits.

The closest to the claimed composition is a demulsifier for oil dehydration and desalting, comprising as nonionic demulsifier oxyethylated alkylphenol derived from propylene trimer AF9-12, or polyethylene glycol ether monoalkylphenols based polimerdistillyata OP-10, polyethylene glycol ether or fractions of C ₃ to C ₁₀ synthetic alcohols Oxanol KD-6, an amine selected from the group consisting of monoethanolamine, triethanolamine, diethylamine, tetramethyldipropylene triamine, pyridine, in the following ratio of components with the rest, wt. [2]:

AF9-12 or OP-10 or Oxanol KD-6, 10.0-50.0

An amine selected from the group consisting of monoethanolamine, triethanolamine, diethylamine, tetramethyldipropylenetriamine, pyridine 0.6-5.2

The solvent is methyl, or ethyl, or isopropyl alcohols, or ethylene glycol 17.7 - 67.7

Water up to 100

The composition proposed in the prototype exhibits demulsifying efficacy, activity to inhibit corrosion of oilfield equipment and asphalt-resin-paraffin deposits. However, the addition of water to the solvent leads to the formation of a complex with an amine, and as a result, the composition medium generally becomes basic, and this is a disadvantage of the known composition.

The objective of the invention is to develop a complex action — an oil demulsifier, a corrosion inhibitor in hydrocarbon media and asphalt-tar-paraffin deposits, which allows efficient separation of oil-water emulsions, inhibits corrosion of oilfield equipment and asphalt-tar-paraffin deposits.

The object of the invention is solved in that the demulsifier contains a nonionic surfactant, an amine compound diethanolamine, or triethanolamine, or diethylamine, or piperidine and a solvent, methanol or ethanol or isopropanol, where it contains a block copolymer as a nonionic surfactant ethylene oxide and propylene oxide based on glycerol with a molecular weight of 3000-6000 in the following ratio of components, wt.%:

Block copolymer of ethylene oxide and propylene oxide based on glycerol with a molecular weight of 3000-6000 50-65

The amine compound is diethanolamine or triethanolamine or diethylamine or piperidine 5.0-8.0

Solvent methanol or ethanol or isopropanol the rest

The following laprols were used to prepare the demulsifier as a block copolymer of ethylene oxide and propylene oxide based on glycerol.

1. Laprol-3003 is a simple polyester obtained by alcoholate polymerization of propylene oxide with glycerol followed by block copolymerization with ethylene oxide (TU 6-05-2947-87).

2. Laprol-3603-2-12 is a polyether obtained by alcoholate polymerization of propylene oxide with glycerol followed by block copolymerization with ethylene oxide (TU A3 05757529-77-2003).

3. Laprol-5003-2-15 is a polyether obtained by alcoholate polymerization of ethylene and propylene oxides with glycerin (TU 6-55-62-93).

4. Laprol-6003-2B-18 is a simple polyester obtained by alcoholate polymerization of propylene oxide with glycerol followed by block copolymerization with ethylene oxide (TU 6-05-221-880-86).

Methanol used as a solvent is produced in accordance with GOST 2222-78, ethanol - in accordance with TU 609-1710-77, isopropanol - in accordance with GOST 9805-84.

- 1 020481

Compositions for the destruction of oil-water emulsions, the protection of oilfield equipment and the inhibition of asphalt-resin-paraffin deposits are prepared by simple mixing of the components and are given in table. one.

In the preparation of compositions, unlike the prototype, water is not used. It was determined that the medium (pH) of amine compounds is ~ 9-10. When dissolved in water, the basicity of the medium still rises (pH ~ 11-12). Apparently, during dissolution, the nitrogen atom in the amine transforms into four I +

-Ν-_.

The final state is ¹ -on. To confirm this fact, diethylamine was dissolved in water. It was found that the pH of the aqueous diethylamine solution is ~ 11-12, and the initial diethylamine is ~ 9-10.

Table 1

Composition components Compositions,% May. Glycerol-based block copolymer of ethylene oxide and propylene oxide: I eleven III IV V VI VII VIII IX X Xi XII XIII XIV XV XVI Laprol-3003 53 58 63 65 Laprol-3603-2-12 fifty 55 60 62 65 Laprol-5003-2-15 51 55 58 62 Laprol-6003-2V-18 fifty 55 60 Amine Compound: Diethanolamine 6 6 5 8 Triethanolamine 6 7 5 8 Diethylamine 7 8 5 8 Piperidine 5 8 7 8 Solvent: methanol 45 35 thirty 35 41 thirty Isopropanol thirty 28 39 40 43 37 32 Ethanol 41 36 36

Therefore, during the dissolution of diethylamine in water, the nitrogen atom passes into the quaternary state of Н ₂ П + (С ₂ Н ₅ ) ₂ ^- ОН [3].

The composition of the demulsifier, intended for the destruction of oil-water emulsions, protection of oilfield equipment from corrosion and asphalt-resin-paraffin deposits, is characterized by the following physical and chemical properties:

Appearance clear liquid from yellow to orange-yellow

Density, kg / m ³ (20 ° С) 980-995

Solubility in oil dissolves

Pour point, ° C below minus 30 ° C

Medium (pH) 8-10

The resulting compositions were tested for demulsifying activity, for the effectiveness of inhibiting corrosion of oilfield equipment and asphalt-resin-paraffin deposits.

We give data on the physicochemical characteristics of the oils used in the tests. Oil taken from NGDU Neft Dashlary: density at 20 ° C, kg / m ³ - 887, contains 10.5% water, 530 mg / l chloride salts, 0.081% solids. Oil from the field of NGDU named after N. Narimanov: density at 20 ° С, kg / m ³ - 856, contains 30% water, 650 mg / l of chloride salts, 0.130% of mechanical impurities.

The test demulsifier is metered into the oil-water emulsion and shaken on a laboratory shaker for 10 minutes at room temperature. Dehydration of the water-oil emulsion and purification from mechanical impurities using the compositions are carried out by the methods specified in [4, 5]. The determination of the residual water content in oil is carried out according to GOST 14870-77 by the Dean-Stark method.

The results of tests for the destruction of oil-water emulsions with the compounds claimed for the invention are presented in table. 2.

Analysis of the data presented in the table shows that the demulsifying ability of the compositions is high and when demulsifying with these compositions of oil emulsions NGDU Neft dashlara and them. N. Narimanova containing 10.5 and 30% water, 530 and 650 mg / l of chloride salts, 0.081 and 0.130% of mechanical impurities, the amount of residual water, chloride salts and mechanical impurities in oil after demulsification meets the requirements of TU A3 0136002-29- 97.

The anticorrosive activity of the proposed composition is evaluated by the gravimetric method on a standard model of produced water with a salinity of 190 g / l, a density of 1.122 g / cm ³ , and a content of H _{2 of} 8 - 100 mg / l. The test is carried out for 6 hours in a laboratory setup such as a wheel in a closed system with a speed of movement of the test medium of 0.4 m / s.

The effectiveness of the prevention of asphalt-resin-paraffin deposits (AFS) is evaluated by the following indicators:

for washing the film of oil compositions; the largest dispersion of paraffin in the composition;

- 2,020,481 for laundering paraffin.

The definition of oil washing is carried out in the following order. Oil, treated with a reagent at the rate of 0.005% on an active basis, is poured into a glass tube to a certain mark and left to stand for 20 minutes. Then the oil is poured, and formation water is poured into the test tube up to half, oil is added to the mark. The tube is closed with a polished tube, after which the tube is turned over at the same time as the stopwatch is turned on. Oil and water vary in volume. The area of the washing surface of the test tube occupied with produced water instead of oil is fixed. The result is considered to be excellent if washing of 70% of the area occurs in 30 s, good in 60 s and satisfactory in 180 s.

table 2

Oil-water emulsion extraction field room composition Consumption composition g / t Time contact minute Oil components after demulsification Water, % Chloride salts, mg / l Mechanical impurities,% one 2 3 4 5 6 7 NGDU "Neft twenty thirty 0.3 108.2 0.042 Dashlars » I twenty 60 0.1 97.6 0.038 40 thirty 0.03 12.8 0.013 twenty thirty 0.38 122.3 0.070 P twenty 60 0.25 105.6 0.052 40 thirty 0.05 11.5 0.030 twenty thirty 0.40 117.6 0.065 ΙΠ twenty 60 0.27 98.7 0.043 40 thirty 0.03 10.5 0.022 twenty thirty 0.36 105.3 0.075 IV twenty 60 0.19 88.9 0.053 40 thirty 0.03 14.5 0.029 twenty thirty 0.42 117.6 0.076 V twenty 60 0.23 85.3 0.059 40 thirty 0.06 13.2 0.031 twenty thirty 0.39 122.8 0.069 VI twenty 60 0.20 86.3 0.047 40 thirty 0.06 17.3 0.028 twenty thirty 0.38 117.5 0.073 VII twenty 60 0.20 88.5 0.056 40 thirty 0.03 14.2 0.019 twenty thirty 0.36 103.8 0.065 VIII twenty 60 0.18 91.0 0.043 40 thirty Traces 11.8 0.022 twenty thirty 0.32 98.9 0.065 IX twenty 60 0.19 56.3 0.039 40 thirty Traces 10.5 0.019 twenty thirty 0.42 122.3 0.073 X twenty 60 0.28 95.6 0.049 40 thirty 0.06 17.3 0.027 twenty thirty 0.39 105.6 0.070 Xi twenty 60 0.20 87.3 0.056 40 thirty 0.03 16.8 0.023 twenty thirty 0.38 103.3 0.073 XII twenty 60 0.20 83.6 0.049 40 thirty Traces 12.8 0.018

- 3,020,481

XIII twenty twenty 40 thirty 60 thirty 0.36 0.18 Traces 105.7 82.3 11.9 0.069 0.048 0.020 twenty thirty 0.42 112.3 0.065 XIV twenty 60 0.28 80.8 0.045 40 thirty 0.06 12.3 0.018 twenty thirty 0.39 106.6 0.070 XV twenty 60 0.21 80.3 0.053 40 thirty 0.03 13.6 0.022 twenty thirty 0.36 106.6 0.065 XVI twenty 60 0.18 81.9 0.048 40 thirty Traces 12.3 0.017 twenty thirty 1.5 121.0 0.095 I twenty 60 0.8 103.8 0.061 40 thirty 0.09 36.5 0.036 twenty thirty 1.10 120.8 0.087 NGDU named II twenty 60 0.72 80.3 0.050 N. Narimanova 40 thirty 0.09 33.6 0.028 twenty thirty 0.91 118.3 0.085 III twenty 60 0.46 81.5 0.046 40 thirty 0.06 32.8 0.026 twenty thirty 0.83 115.6 0.080 IV twenty 60 0.42 80.3 0.039 40 thirty 0.06 31.9 0.026 twenty thirty 0.75 106.5 0.085 V twenty 60 0.38 81.2 0.046 40 thirty 0.06 28.3 0.028 twenty thirty 0.73 100.3 0.075 VI twenty 60 0.33 75.6 0.038 40 thirty 0.03 19.8 0.022 twenty thirty 0.65 95.3 0.072 VII twenty 60 0.28 69.7 0.035 40 thirty 0.03 17.3 0.019 twenty thirty 0.53 88.7 0.068 VIII twenty 60 0.19 46.3 0.037 40 thirty 0.03 15.7 0.019 twenty thirty 0.42 85.3 0.065 IX twenty 60 0.21 46.0 0.037 40 thirty Traces 14.9 0.017 twenty thirty 0.78 106.5 0.078 X twenty 60 0.37 93.2 0.046 40 thirty 0.09 23.7 0.028 twenty thirty 0.63 101.3 0.069 Xi twenty 60 0.42 88.6 0.038 40 thirty 0.06 20.4 0.022 twenty thirty 0.45 95.6 0.071 XII twenty 60 0.22 41.3 0.035 40 thirty 0.03 13.7 0.019 twenty thirty 0.43 95.6 0.065 XIII twenty 60 0.20 38.3 0.035 40 thirty ΙζΙοπ 11.6 0.017 twenty thirty 0.65 115.6 0.085 XIV twenty 60 0.38 83.3 0.045 40 thirty 0.09 20.2 0.022 twenty thirty 0.460 106.5 0.075 XV twenty 60 0.35 80.5 0.045 40 thirty 0.06 18.8 0.018 twenty thirty 0.53 106.5 0.075 XVI twenty 60 0.28 79.3 0.040 40 thirty 0.03 17.6 0.018

Dispersion of paraffin and surface washing. These two methods are combined in one laboratory procedure and are carried out in a conical flask, in which 50 ml of produced water is placed, the test reagent is dosed. A paraffin weighing 0.5 g is placed in the same flask. The contents of the flask are heated until paraffin is melted (60-90 ° С), and then cooled by stirring. After cooling to 20-25 ° C, the particle size of the paraffin dispersion and the surface area of the flask not coated with (coated) ASPO are measured.

According to the methodology, the result is considered to be excellent with a dispersion value of 0.1-1 mm, good with a dispersion value of 1-2 mm, satisfactory with a dispersion value of 2-5 mm, unsatisfactory with a dispersion value> 5 mm. When evaluating the method of washing the ARPD from the surface, the result is considered to be excellent if the percentage of surface washing from the ARPD in% is 90-100, good 80-90, satisfactory 50-80 and bad <50. The test results of the proposed composition are given in table. 3. Tests conducted with oil selected from NGDU Neft Dashlary.

Table 3

room composition Protective effect against corrosion,%, C = 40 mg / l AFS Prevention Effect Oil film wash Middle the size dispersed particles, mm The proportion of washing off the paraffin from the surface,% % / sec Rating I 86 70/60 OK 3 96 and 88 75/60 OK 2 97 III 89 80/60 OK 2 99 IV 91 70/30 fine one one hundred V 88 80/60 OK 2 98 VI 90 85/60 OK 2 98 VII 92 70/30 fine 2 99 VIII 95 80/30 fine one one hundred IX 98 90/30 fine one one hundred X 88 80/60 OK 2 97 Xi 90 Ί 85/60 OK 2 98 hee 93 75/30 FINE one one hundred XIII 95 80/30 fine one one hundred XIV 88 80/60 OK 2 98 XV 91 80/30 fine one one hundred XVI 94 85/30 fine one one hundred

Analysis of the data presented in the table shows that the claimed composition allows you to effectively protect oilfield equipment from corrosion and paraffin.

Literature

1. A.s. 1773932, IPC S10O 33/04.

2. Patent KI 2036952, IPC С10О 33/04 (prototype).

3. Azabou Ζ.Η., Atsa- / abe Α.Ό., Aishaboua S.A., Yazloua Z.M., Ka Каshou K.A., Anueua O.Z. Zuplje515 oR zhTae-aeuy e1yesh apb ez1eg8 Lazeb op (b1) she1yu1ashto e! Yapo1 apb rgoruepe oh1be // Seog§1a syesh1sa1] igpa1. 2003, wo1. 3, Io 3, p. 205-211.

4. Levchenko D.M. and others. Emulsions of oil with water and methods for their destruction. M., Chemistry, 1967, 133 p.

5. Dekhterman A.Sh. Laboratory assistant oil refinery. M .: Chemistry, 1989, 80 pp.

Claims (1)

CLAIM The composition of the demulsifier containing a non-ionic surfactant, an amine compound selected from the group consisting of diethanolamine, triethanolamine, diethylamine and piperidine, and a solvent selected from methanol, ethanol or isopropanol, characterized in that as a non-ionic surfactant contains block copolymer of ethylene oxide and propylene oxide based on glycerin with a molecular weight of 3000-6000 in the following ratio, wt.%: A block copolymer of ethylene oxide and propylene oxide based on glycerin with a molecular weight of 3000-6000 50-65 Amine compound selected from the group consisting of diethanolamine, triethanolamine, diethylamine and piperidine 5.0-8.0 The solvent selected from methanol, ethanol or isopropanol the rest