RU2320693C1 - Composition for prevention of asphalt-resinous-paraffin deposits - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to compositions used for prevention of precipitating asphalt-resinous-paraffin deposits from petroleum on oil field equipment, in critical zone of oil holes and in oil pipelines. Invention describes a composition used for prevention of asphalt-resinous-paraffin deposits that comprises oxyalklylated product of successive adding ethylene oxide and propylene oxide to alkyl phenol, modifying additive and organic solvent. As a modifying additive method involves using N-[alkylphenoxypoly(ethyleneoxy)-carbonylmethyl]ammonium chlorides or N,N'-bis-{[alkylphenoxypoly(ethyleneoxy)carbonylmethyl]ammonium}-propane dichlorides, or N-[alkylphenoxypoly(ethyleneoxy)carbonylmethyl]morpholinium chlorides in the following ratio of components, wt.-%: oxyalkylated product of successive adding ethylene oxide and propylene oxide to alkyl phenol, 20.0-25.0; modifying additive, 0.5-2.5, and organic solvent, the balance. Invention provides the effective prevention of precipitation of asphalt-resinous-paraffin deposits from petroleum.

EFFECT: improved and valuable properties of composition.

2 cl, 13 ex

Description

The invention relates to organic chemistry, in particular to compositions for preventing loss of oil from asphalt tar and paraffin deposits in oilfield equipment, in the bottomhole zone of oil wells, as well as oil pipelines. It can be used in the oil and other industries related to oil production, transportation and storage.

Currently, to prevent the loss of oil from asphalt-resin-paraffin deposits (AFS), a wide range of substances from various classes of organic compounds, as well as compositions based on them, are used.

Known inhibitor of asphalt-resin-paraffin deposits, which is a product of sequential addition of 1-3 wt.h. ethylene oxide and 3-9 parts by weight propylene oxide to 1 parts by weight alkyl phenols [Autosvid. USSR No. 1118659, MKI S09K 3/00, 1984]. The disadvantage of this inhibitor of asphalt-resin-paraffin deposits is the selectivity of its action, which consists in the fact that it exhibits inhibitory effectiveness only for certain types of oils. In addition, it is a highly viscous reagent at 20 ° C. Its use in winter without heating is not possible, since it has a pour point of +5: + 8 ° C.

Known composite inhibitor of asphalt-resin-paraffin deposits, which is a composition obtained by mixing hydroxyethylated fatty alcohol, aliphatic alcohol and aromatic solvent [Autosvid. USSR No. 981335, MKI S09K 3/00, 1982]. The disadvantage of this inhibitor is its low effectiveness for paraffinic, slightly resinous oils and the high dosage used (0.02-0.04% by weight for oil).

The closest in technical essence and the achieved result is a composition for preventing the deposition of paraffin from oil to oil equipment, including an oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to alkyl phenol; a modifying additive, which is used as di- (alkylpolyoxyethylene) phosphate of the formula:

[C _n H _{2n + 1} O (C ₂ H ₄ O) _m ] ₂ POOH

where: n = 8-10; m is 6;

and aromatic solvent (xylene fraction).

[RF patent 2074217, MKP S09K 3/00, L. Olenev, G. Zapeklaya and others. A method of obtaining an inhibitor of paraffin deposits. 1993].

However, the inhibitory composition of the prototype does not satisfy oil industry workers due to insufficiently high efficiency, since for a number of oils it is used in dosages of at least 0.02% by weight (200 mg / l) and, in addition, for some types of oils the inhibitory effect is low .

The basis of the present invention is the task of developing a new composition to prevent the loss of paraffin from oil, expanding the range of known products.

EFFECT: effective prevention of loss of asphalt-resin-paraffin deposits from oil.

The technical result is achieved by using the inventive composition, including an oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to alkyl phenol, a modifying additive and an organic solvent that differs from the prototype in that N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride is used as a modifying additive [Patent RF1531416, RF patent 2221777, autosvid. USSR 1361945] formulas:

Where:

R = alkyl C ₈ -C ₁₂ ;

n is the average degree of hydroxyethylation equal to 6-12;

R ¹ = R ² = H, CH ₃ , CH ₂ CH ₂ OH;

R ³ = C ₆ H ₅ , alkyl C ₁₀ -C ₁₆ , alkyl C ₁₇ -C ₂₀ ,

CH ₂ CH ₂ O — C (O) —R ⁴ ,

where: R ⁴ = alkyl C ₁₀ -C ₁₆ ;

or N, N′-bis {[alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichlorides of the formula:

Where:

R = alkyl C ₈ -C ₁₂ ;

n is the average degree of hydroxyethylation equal to 3-10;

R ¹ = R ³ = R ⁴ = H;

R ² = C ₁₂ H ₂₅ , alkyl C ₁₀ -C ₁₆ ;

or N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chlorides of the formula:

Where:

R = alkyl C ₈ -C ₁₂ ;

n is the average degree of hydroxyethylation equal to 3-12;

in the following ratio of components, wt.%:

oxyalkylated sequential product addition of ethylene oxide and propylene oxide to alkyl phenol 20.0-25.0 modifying additive 0.5-2.5 organic solvent rest.

A comparative analysis of the features of the invention with the prototype allows us to conclude that the totality of the claimed essential features of the composition is previously unknown.

N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chlorides of the formula:

Where:

R = alkyl C ₈ -C ₁₂ ;

n is the average degree of hydroxyethylation equal to 3-12;

and N, N′-bis {[alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichlorides of the formula:

Where:

R = alkyl C ₈ -C ₁₂ ;

R ¹ = R ³ = R ⁴ = H;

R ² = C ₁₂ H ₂₅ , alkyl C ₁₀ -C ₁₆

n = average degree of hydroxyethylation equal to 3-10,

are new compounds. They are obtained by the interaction of alkylphenoxypolyethylene glycols of the general formula:

Where:

R = aliphatic hydrocarbon radical containing 8-12 carbon atoms;

n = average degree of hydroxyethylation equal to 3-12;

with monochloroacetic acid in the presence of an acid catalyst, for example, the K ⁺ -8-8 H ⁺ form of a KU-2-8 cation exchange resin in a boiling organic solvent with azeotropic removal of the resulting water and subsequent treatment of the resulting reaction product with amino compounds. Moreover, to obtain N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chlorides, morpholine is used as the amino compound at molar ratios of the reactants — alkylphenoxypolyethylene glycol: monochloroacetic acid: morpholine = 1: (1.0-1.1) :( 1.0: 1 ,one). To obtain N, N′-bis {[alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichlorides, N-alkyltrimethylenediamines of the general formula are used as amino compounds:

where: R ¹ = R ³ = R ⁴ = H;

R ² = C ₁₂ H ₂₅ , alkyl C ₁₀ -C ₁₆ ,

when the molar ratios of the reactants are alkylphenoxypolyethylene glycol: monochloroacetic acid: N-alkyltrimethylenediamines = 1: (1.0-1.1) :( 0.5-0.55).

As initial alkylphenoxypolyethylene glycols, along with individual compounds, various technical products manufactured by the petrochemical industry can be used - ethoxylated nonylphenols of the grades:

Neonol AF ₉ -6 (TU 2483-077-05766801-98);

Neonol AF ₉ -9 (TU 2483-077-05766801-98);

Neonol AF ₉ -10 (TU 2483-077-05766801-98);

Neonol AFB ₉ -10 (TU 2483-077-05766801-98);

Neonol AF ₉ -12 (TU 2483-077-05766801-98);

Neonol AFB ₉ -12 (TU 2483-077-05766801-98);

Oxyethylated alkyl phenols grades:

Neonol Alpha-12 (TU 38.507-63-0302-93);

Neonol Alfa-14 (TU 38.507-63-0302-93).

Monochloracetic acid is used as an individual compound or technical product according to TU 2431-288-05763441-99.

Cation exchange resin is available in accordance with GOST 20298-74.

An organic solvent for the reaction of the interaction of alkylphenoxypolyethylene glycol with monochloracetic acid is an aromatic hydrocarbon solvent, for example toluene, xylenes, Nefras A-120/200.

Morpholine is used as an individual compound, or a technical product according to TU, or a morpholine-containing technical product, for example, a morpholine resin, of the following composition:

Morpholine more than 20%; Amino Acid Resin more than 20%; Diethylene glycol 5-10%; Water 5-15%.

Aliphatic low molecular weight alcohols, for example ethanol or isopropanol, are used as a polar organic solvent for the reaction of morpholine or N-alkyltrimethylenediamines with the reaction product of alkylphenoxypolyethylene glycols with monochloracetic acid.

As an oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to alkyl phenol, you can use the imported reagent Prevocel NCE 10/16 of the formula:

where: R is alkyl C ₈ -C ₁₀ ;

m is 9-11;

k = 15-17,

as well as domestic reagents Deparols SNPCH-720, which are substances with the same general formula as Prevocel NCE 10/16. Differences between these reagents can be due to fluctuations in the average degree of hydroxyethylation m and the average degree of hydroxypropylation k [Olenev LM New domestic paraffin inhibitors // Review. inform .: Ser. Technique and technology of oil production and arrangement of oil fields. M .: VNIIONG, 1990, - 52 p.].

For the preparation of the claimed composition, preventing the loss of asphalt-resin-paraffin deposits in the oil industry, as well as for the synthesis of modifying additives used in these compositions, a heavy oil solvent (Nefras A-120/200) (TU 38.101809-90), Nefras solvent are used as an organic solvent A 120/200 (TU 38.101809-80), which is a mixture of aromatic hydrocarbons (ortho-, meta-, paraxylene, propylbenzenes, ethyltoluenes, mesitylene, pseudocumene, hemimelitol, methylnaphthalenes) [Bedrik B.G., Chulkov P.V., Kalashniko in S.I. Solvents and compositions for cleaning machines and mechanisms. Directory. M .: Chemistry, 1989, p. 69-70; Glaziers. Directory. Hydrocarbon solvents. Properties, production, application. 1986, 120 pp.].

From the prior art, no inventions have been found that are similar to the essential features of the claimed composition for preventing the deposition of paraffin oil, which would lead to a higher technical result than the claimed composition, which allows us to conclude that the claimed composition meets the criteria of “novelty” and “inventive” level".

EXAMPLE 1

To 20.0 g of the oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to an alkyl phenol sold under the name Prevocel NCE 10/16, 2.5 g of N-alkyl (C ₁₇ -C ₂₀ ) -N- [alkyl (C ₈ - C ₁₂ ) phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride (as a modifying additive) with an average degree of hydroxyethylation equal to 10, and the organic solvent, which is used Nefras A 120/200, bring the total weight of the composition to 100 g. The mixture is stirred to obtaining a homogeneous composition. The resulting inhibitor to prevent the loss of oil from asphalt-resin-paraffin deposits (AFS) has the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 2.5 wt.%; organic solvent rest.

EXAMPLE 2

The composition for preventing the deposition of paraffin oil is prepared analogously to example 1 from an oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to alkyl phenol, sold under the name Deparol SNPCH-720; modifying additives, which use N, N-dimethyl-N-alkyl (C ₁₀ -C ₁₆ ) -N- [alkyl (C ₈ -C ₁₂ ) phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride with an average degree of hydroxyethylation equal to 6 ; and xylene (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 25.0 wt.%; modifying additive 0.5 wt.%; organic solvent rest.

EXAMPLE 3

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N, N-dimethyl-N-alkyl (C ₁₀ -C ₁₆ ) -N-isononylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride with an average degree of hydroxyethylation equal to 10; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 1.0 wt.%; organic solvent rest.

EXAMPLE 4

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; a modifying additive, which is used N, N-dimethyl-N-alkyl (C ₁₀ -C ₁₆ ) -N- [isononylphenoxypoly (ethyleneoxy) carbonylmethyl] -ammonium chloride with an average degree of hydroxyethylation equal to 12; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 0.5 wt.%; organic solvent rest.

EXAMPLE 5

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N, N-dimethyl-N-alkyl (C ₁₇ -C ₂₀ ) -N- [alkyl (C ₈ -C ₁₂ ) phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride with an average degree of hydroxyethylation equal to 7 ; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 0.5 wt.%; organic solvent rest.

EXAMPLE 6

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; a modifying additive, which is used N- [alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chloride with an average degree of hydroxyethylation equal to 3; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 1.0 wt.%; organic solvent rest.

EXAMPLE 7

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N, N-di (2-hydroxyethyl) -N- [alkanoyl (C ₁₀ -C ₁₆ ) -oxyethyl] -N- [alkyl (C ₈ -C ₁₂ ) phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chloride with an average degree of hydroxyethylation equal to 10; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 2.5 wt.%; organic solvent rest.

EXAMPLE 8

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N-dodecyl-N, N′-bis {[alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichloride with an average degree of hydroxyethylation equal to 7; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 2.5 wt.%; organic solvent rest.

EXAMPLE 9

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; a modifying additive, which is used N-alkyl (C ₁₀ -C ₁₆ ) -N, N′-bis {[alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} -propane dichloride with an average degree of hydroxyethylation equal to 3; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 2.5 wt.%; organic solvent rest.

EXAMPLE 10

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N- [alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chloride with an average degree of hydroxyethylation equal to 12; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 1.0 wt.%; organic solvent rest.

EXAMPLE 11

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which use N- [alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chloride with an average degree of hydroxyethylation equal to 6; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 1.0 wt.%; organic solvent rest.

EXAMPLE 12

The composition is prepared analogously to example 1 of Prevocel NCE 10/16; modifying additives, which are used as N-dodecyl-N, N′-bis {[alkyl (C ₈ -C ₁₂ ) -phenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichloride with an average degree of hydroxyethylation equal to 10; and Nefras A-120/200 (as an organic solvent) in the following ratio of components:

oxyalkylated sequential product joining ethylene oxide and propylene oxide to alkylphenol 20.0 wt.%; modifying additive 2.5 wt.%; organic solvent rest.

EXAMPLE 13

Tests of the claimed compositions according to examples 1-12 as inhibitors of asphalt-resin-paraffin deposits (paraffin).

For testing, the prototype composition for preventing paraffin treatment according to RF patent 2074217 [IPC S09K 3/00, Olenev L.M., Zapeklaya G.N. and others. A method of obtaining an inhibitor of paraffin deposits, 1993].

The tests are carried out on paraffinic low-resinous oils of the Tarasovskoye field having the following component composition:

paraffins - 3.73 wt.%; pitches - 4.08 wt.%; asphaltenes - 0.40 wt.%;

which corresponds to the following ratio - paraffins: resins: asphaltenes = 1: 1.09: 0.11.

Determining the effectiveness of inhibiting the deposition of paraffin is carried out by the method of "cold" disk [Charles J.G., Marcinew R.P. Unigue paraffin inhibition technigue reduces well maintenance // J. Canadian Petroleum Technology. 1986. v.25, N4, P.40-44].

The effectiveness of paraffin inhibitors is determined by the difference in the mass of deposits on the surface of the "cold" disk before and after treatment with the inhibitor. Prepare two beakers with 100 ml of oil saturated with paraffin. In one of them, a dosed amount of the inhibitor is injected with a microsyringe and mixed. For comparative tests, the dosage of the tested inhibitors was chosen equal to 100 mg / l (0.01% of the mass.).

Oil saturated with paraffin, from a glass to the surface of the "cold" disk comes from a hose connected to a peristaltic pump. The surface temperature of the disk is maintained below the temperature at which crystallization of paraffin from oil begins. After the oil drains from the disk, the paraffin is removed with a spatula in a previously weighed cuvette. The effectiveness of inhibiting the deposition of paraffin from oil is determined by the formula:

where: I - the inhibition of paraffin inhibitor inhibitor,%:

M _about - the mass of paraffin in the control experiment without the use of an inhibitor, g;

M _and - the mass of paraffin when using an inhibitor, g

To compare the effectiveness of the studied inhibitors with respect to the prototype inhibitor, the comparative efficiency of E inhibition is calculated by the formula:

where: E is the comparative effectiveness of the studied inhibitor,

I _and - the amount of inhibition of paraffin tested by the inhibitor,%;

I _p - the amount of inhibition of paraffin inhibitor prototype inhibitor,%

As can be seen from this formula, the comparative effectiveness of E shows how many times the proposed inhibitor is more active than the prototype inhibitor. The results are shown in table 1. The data in table 1 indicate that the proposed inhibitors of deposition of paraffin are superior to the inhibitor prototype in 3,51-7,63 times.

Thus, the presented results on the inhibition of the deposition of asphalt-tar-paraffin deposits from oil show that the claimed compositions exhibit higher efficiency and have clear advantages over the prototype inhibitor used in the oil industry.

Claims (2)

1. The composition for preventing asphalt-resin-paraffin deposits, including the oxyalkylated product of sequential addition of ethylene oxide and propylene oxide to alkyl phenol, a modifying additive and an organic solvent, characterized in that N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium chlorides are used as a modifying additive,

where R is alkyl C ₈ -C ₁₂ ; n is the average degree of hydroxyethylation equal to 6-12; R ¹ = R ² = H, CH ₃ , CH ₂ CH ₂ OH; R ³ is C ₁₀ -C ₁₆ alkyl, C ₁₇ -C ₂₀ alkyl, CH ₂ CH ₂ OC (O) -R ⁴ , where R ⁴ is alkyl C ₁₀ -C ₁₆ ; or N, N′-bis {[alkylphenoxypoly (ethyleneoxy) carbonylmethyl] ammonium} propane dichlorides of the formula

where R is alkyl C ₈ -C ₁₂ ; n is the average degree of hydroxyethylation equal to 3-10; R ¹ = R ³ = R ⁴ = H; R ² - C ₁₂ H ₂₅ , alkyl C ₁₀ -C ₁₆ or N- [alkylphenoxypoly (ethyleneoxy) carbonylmethyl] morpholinium chlorides of the formula

where R is alkyl C ₈ -C ₁₂ ; n is the average degree of hydroxyethylation equal to 3-12; in the following ratio of components, wt.%: oxyalkylated sequential product addition of ethylene oxide and propylene oxide to alkyl phenol  20.0-25.0 modifying additive  0.5-2.5 organic solvent  rest 2. The composition according to claim 1, where Precocel NCE10 / 16 or Deparol SNPCH-720 is used as the ethoxylated product of the sequential addition of ethylene oxide and propylene oxide to alkyl phenol.