DISPERSING ADDITIVE FOR ASPHALTENES AND ITS USES

Abstract

Use of an alkylphenol-aldehyde resin modified by at least one alkylamine in a composition of crude oils or in a product derived from a composition of crude oils as dispersing additive for asphaltenes. Process for the treatment of a composition of crude oils or a derived product which makes it possible to prevent the precipitation of asphaltenes, in particular in crude oils and the products which result therefrom by refining and/or extraction processes. Bituminous compositions including an alkylphenol-aldehyde resin modified by at least one alkylamine.

Claims

1-23. (canceled)

24. Method for dispersing asphaltenes and/or for preventing and/or delaying and/or stopping and/or reducing the precipitation of asphaltenes comprised in a composition of crude oils or in a product derived from a composition of crude oils comprising adding to said composition or product at least one modified alkylphenol-aldehyde resin, the said modified alkylphenol-aldehyde resin being capable of being obtained by a Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having between 1 and 30 carbon atoms, the said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation of at least one alkylphenol substituted by at least one linear or branched alkyl group having from 1 to 30 carbon atoms, with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms.

25. Method according to claim 24, for its employment in a composition of crude oils or in a product derived from a composition of crude oils and comprising asphaltenes subjected to one or more of the following conditions: a rise in pressure, a rise in temperature, a mixing with at least one other fluid.

26. Method according to claim 24, wherein the modified alkylphenol-aldehyde resin is capable of being obtained from p-nonylphenol, formaldehyde and at least one hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine group.

27. Method according to claim 24, wherein the modified alkylphenol-aldehyde resin is employed diluted in a solvent.

28. Method according to claim 24, applied to a composition of crude oils or to a hydrocarbon fraction of crude oils comprising asphaltenes.

29. Method according to claim 28, executed in an equipment chosen from: a tank, a refining plant, a pipeline, a drilling well, an item of transportation equipment or a filter.

30. Method according to claim 24, applied to a product derived from a composition of crude oils chosen from bituminous binders, bituminous mixes and asphalts.

31. Method according to claim 30, for reducing the preparation temperature and/or the processing temperature of the bituminous binder and/or for reducing the manufacturing, processing and/or compacting temperatures during the preparation of a bituminous mix and/or for reducing the manufacturing and/or processing temperatures during the preparation of an asphalt.

32. Composition comprising asphaltenes chosen from: bitumen compositions, bituminous binders, bituminous mixes and asphalts, the said composition comprising at least one modified alkylphenol-aldehyde resin capable of being obtained by a Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having between 1 and 30 carbon atoms, the said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation of at least one alkylphenol substituted by at least one linear or branched alkyl group having from 1 to 30 carbon atoms, with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms.

33. Composition according to claim 32, wherein the modified alkylphenol-aldehyde resin is obtained from at least one alkylmonoamine or from at least one alkylpolyamine having at least one primary amine group.

34. Composition according to claim 33, wherein the modified alkylphenol-aldehyde resin is obtained from at least one alkylmonoamine or from at least one alkylpolyamine which all the amine groups are primary amines.

35. Composition according to claim 32, wherein the alkylamine is a fatty alkylmonoamine having from 12 to 24 carbon atoms.

36. Composition according to claim 32, wherein the alkylamine is a fatty alkylpolyamine having from 12 to 24 carbon atoms.

37. Composition according to claim 32 which is a bituminous binder comprising from 0.1 to 5% by weight of modified alkylphenol-aldehyde resin, with respect to the total weight of binder.

38. Composition according to claim 32, which is a bituminous mix comprising from 1 to 10% by weight of bituminous binder, wherein the modified alkylphenol-aldehyde resin is obtained from at least one alkylmonoamine or from at least one alkylpolyamine having at least one primary amine group, and from 90 to 99% by weight of aggregates, with respect to the total weight of the mix.

39. Composition according to claim 32, which is an asphalt comprising from 1 to 20% by weight of bituminous binder, wherein the modified alkylphenol-aldehyde resin is obtained from at least one alkylmonoamine or from at least one alkylpolyamine having at least one primary amine group, and from 80 to 99% of fillers, with respect to the total weight of the asphalt.

40. Method according to claim 24, for the treatment of a composition of crude oils or of a product derived from a composition of crude oils and comprising asphaltenes, this method comprising at least: (i) the introduction of at least one modified alkylphenol-aldehyde resin into the composition of crude oils or into the product derived from the composition of crude oils and comprising asphaltenes, (ii) a treatment stage chosen from a rise in pressure, a rise in temperature or a mixing with at least one other fluid, the said modified alkylphenol-aldehyde resin being capable of being obtained by a Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having between 1 and 30 carbon atoms, the said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation of at least one alkylphenol substituted by at least one linear or branched alkyl group having from 1 to 30 carbon atoms, with at least one aldehyde and/or one ketone having from 1 to 8 carbon atoms.

41. Method according to claim 40, wherein stage (ii) is chosen from an extraction of a crude oil from a reservoir, a stage of refining a crude oil or a derived product, a transportation of a crude oil or of a derived product, a filtration of a crude oil or of a derived product, an injection of gas into a crude oil or into a derived product, a mixing of crude oils or of derived products, or a mixing of a crude oil or of a derived product with a solvent.

42. Method according to claim 40, which is employed in an equipment chosen from: a tank, a drilling well, a refining plant, a pipeline, a storage vessel, a transportation equipment or a filter.

43. Method according to claim 40 for the preparation of a bituminous binder, comprising a stage (ii) of mixing the bitumen and the modified alkylphenol-aldehyde resin in which the temperature at which this mixing is carried out is between 100 C. and 170 C.

44. Method according to claim 40 for the preparation of a mix, comprising a stage (ii) of mixing the bituminous binder and the aggregates, the mixing temperature being between 100 C. and 150 C.

45. Method according to claim 40 for the preparation of an asphalt, comprising a stage (ii) of mixing the bituminous binder and the fillers, the mixing temperature being between 140 C. and 180 C.

Description

FIGURE

[0165] FIG. 1: Schematic representation of the pilot-scale unit for pressure performance evaluation.

EXPERIMENTAL PART

[0166] AMaterials and Methods

[0167] Crude Oils:

[0168] Three crude oils having different compositions were used:

[0169] CO1: Oil comprising 15% by weight of asphaltenes, characterized by an ASCI grade of 9

[0170] CO2: Oil comprising 10% by weight of asphaltenes, characterized by an ASCI grade of 11

[0171] CO3: Oil comprising 5% by weight of asphaltenes, characterized by an ASCI grade of 12

[0172] The ASCI (Asphaltene Solubility Class Index) method is described in N. Passade Boupat et al., SPE-164184-MS, Society of Petroleum Engineers, 2013; M. Rondon-Gonzalez et al., SPE-171891-MS, Society of Petroleum Engineers, 2014.

[0173] Additives:

[0174] Ad1: Modified nonylphenol-aldehyde resin prepared according to the procedure No. 1 Stage 1 followed by Stage 2 belowformulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type) at a concentration of 50% by weight of active material.

[0175] Ad2: Polyisobutylenesuccinimide, sold by Total ACS (Total Marketing & Services)formulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type) at a concentration of 50% by weight of active material.

[0176] Ad3: Octadecylsuccinimidesold by Total ACS under the reference HFAS 100formulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type) at a concentration of 27.5% by weight of active material.

[0177] Ad4: Unmodified nonylphenol-aldehyde resinformulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type)obtained by the procedure No. 1 Stage 1 described below.

[0178] Ad5: Unmodified nonylphenol-aldehyde resin of low weightformulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type)obtained by the procedure No. 1 Stage 1 described below.

[0179] The characteristics of the resins Ad4 and Ad5 are listed in the following Table 1:

TABLE-US-00001 Active material Reference Alkyl chain content (*) Mw (Da) (**) Ad4 C.sub.9 67.10% 5000 Ad5 C.sub.9 70.60% 2500 (*) % by weight, in solution in toluene (**) weight-average molar mass
Ad6: C.sub.12-C.sub.14 polyacrylates, with a weight-average molar mass Mw=12 000 Daformulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type) at a concentration of 35% by weight of active material.
Ad7: C.sub.18-C.sub.22 polyacrylates, with a weight-average molar mass Mw=12 000 Daformulated in a C.sub.10 aromatic solvent (of the Solvarex 10 type) at a concentration of 35% by weight of active material.

Procedure No. 1: Synthesis of the Modified Alkylphenol-Aldehyde Resin

Stage 1:

[0180] In a first stage, an alkylphenol-aldehyde resin is prepared by condensation of para-nonylphenol and formaldehyde (for example according to the procedure described in EP 857 776), with a viscosity at 50 C. of between 1800 and 4800 mPa.Math.s (viscosity measured at 50 C. using a dynamic rheometer with a shear rate of 10 s.sup.1 on the resin diluted with 30% by weight of aromatic solvent (Solvesso 150 )).

Stage 2:

[0181] In a second stage, the alkylphenol-aldehyde resin resulting from the first stage is modified by a Mannich reaction by addition of 2 molar equivalents of formaldehyde and 2 molar equivalents of tallow dipropylenetriamine, known under the name N-(tallowalkyl)dipropylenetriamine and sold, for example, under the name Trinoram S, with respect to the alkylphenol-aldehyde resin resulting from the first stage.

[0182] The characteristics of the resin obtained on conclusion of Stage 2 are listed in the following Table 2:

TABLE-US-00002 TABLE 2 Solids content Viscosity at Alkylamine (1 g/30 min/ 50 C. Resin No. used 200 C.) (mPa .Math. s) (*) N.sub.Phe (**) Ad1 Trinoram S 70.10% 4855 14.1 (*) Viscosity at 50 C.: measured on a resin diluted with 70% by weight of Solvesso 150, shear rate of 10 s.sup.1, using a Haake RheoWin rheometer. (**) Evaluation of the mean number of phenol nuclei per resin molecule or N.sub.Phe: measured by proton nuclear magnetic resonance.

BExperiments:

[0183] Study of Resistance to Clogging:

[0184] The study is carried out in a pilot-scale unit (1), the different components of which are illustrated in FIG. 1.

[0185] The objective of the test is the study of the kinetics of precipitation and of clogging of asphaltenes in a capillary tube under continuous flow conditions. The principle of the measurement consists of the injection into a capillary tube of a mixture of crude oil and solvent at a predetermined and constant flow rate. The drop in pressure along the capillary tube is measured. The difference in pressure AP (in Pa) is related to the flow (in m.sup.3/s) by the Hagen-Poiseuille law:

[00001]$.Math..Math.P=\frac{8.Math..Math.n}{.Math..Math.R^4}.Math.\mathrm{LQ}$

in which R and L respectively represent the radius (in metres) and the length (in metres) of the capillary and n represents the viscosity of the fluid (in Pa.Math.s). When a deposit of asphaltenes is formed in the capillary, R decreases, which results in an increase in P. The pumps are equipped with a safety system which halts the injection when the pressure reaches 8 bar.

[0186] The sample can be composed of crude oil, solvent and additives in varied proportions. The precipitation of the asphaltenes can be brought about by the mixing of a light aliphatic solvent with the crude oil.

[0187] The experimental device represented in FIG. 1 comprises four syringes actuated by pumps (PHD Ultra 4400, Harvard Apparatus) which converge in a static mixer (4) located at the inlet (5.1) of the capillary. The pump (2) is used to inject the crude oil. The pumps (3.1) and (3.2) are used to respectively inject a solution of additive (in toluene) and a solvent, such as heptane. The final pump (3.3) is used to clean the circuit or to calibrate the system with toluene. Before entry into the static mixer (4), the crude oil, the additive(s) and the solvents are conditioned in the oven (7) at a controlled temperature of 45 C. The combined materials are mixed using the static mixer (4) and then injected at the inlet (5.1) of the capillary tube (5) with a length of 3 m and a diameter of 0.38 mm. The entire device is placed in the oven (7), so as to maintain a controlled temperature of 45 C. The pressure drop between the inlet (5.1) and the outlet (5.2) of the capillary (5) is measured in real time using piezoelectric transducers (6) connected to the ends (5.1) and (5.2) of the capillary.

Principle of the Test:

[0188] In a first test (Protocol 1), a determination is carried out of the Oil/Heptane ratio prior to the capillary test in order to determine the conditions for precipitation of the asphaltenes. Subsequently, the oil and the nonadditivated heptane are injected into the capillary (5) with the heptane/oil ratio identified in the first stage, which makes it possible to determine an initial blocking time of the capillary (5). Subsequently (Protocol 2), by virtue of the additive, this blocking time is shifted to greater times.

Protocol 1: Additive Concentration Scanning Test

[0189] In this test, the additive is injected into the capillary (5) in several stages, along a decreasing gradient of additive concentration with respect to the oil. The additive is in solution in heptane and the solution of additive dissolved in heptane exhibits a fixed concentration. Firstly, toluene is injected, followed by the heptane and the oil.

[0190] The crude oil/heptane ratio is kept constant during the test and the additive solution/heptane ratio decreases at each stage, as is summarized in Table 3. Each stage has a duration of 210 minutes. The objective of this experiment is to determine the additive concentration ranges within which the additive has an effect on the dispersion of the asphaltenes.

[0191] For the crude oil tested (CO2, but this protocol can be employed with any crude oil), the start of precipitation of the crude oil (control) was determined as a ratio of 3 volumes of heptane per one volume of oil: Heptane/Oil=3.

TABLE-US-00003 TABLE 3 Flow rates (L/min) Amount of Solution of Duration additive Crude additive in Stage (min) (ppm) Toluene oil Heptane heptane 1 90 0 150 0 0 0 2 210 10 000 0 50 50 100 3 210 3000 0 50 120 30 4 210 1000 0 50 140 10 5 210 300 0 50 147 3

[0192] Protocol 2: Test at a Fixed Concentration of Additive

[0193] After an analysis of the limiting concentration, a given concentration for each additive can be selected for which the threshold performances are identified. Thus, for this part of the test, for the additive according to the invention Ad1, a constant flow of 1000 ppm of the additive dissolved in heptane is injected into the capillary with the crude oil, the volume ratio 3:1 heptane:crude oil being retained. The corresponding flow rates are summarized in Table 4. The temperature was fixed at 45 C. in each test. The objective of this test is to determine the action of the additive over time, at a given dose, under flow conditions. The time at the end of which the pressure of 8 bar is reached is measured.

TABLE-US-00004 TABLE 4 Flow rates (L/min) Duration Amount of additive Crude Additive Stage (min) (ppm) Toluene oil solution 1 90 0 150 0 0 2 840 1000 0 50 150

[0194] The time at the end of which the pressure of 8 bar is reached is subsequently determined for different concentrations and for varied additives. The greater the time in order to reach this pressure of 8 bar, the greater the effectiveness of the additive as dispersant for asphaltenes.

CResults:

[0195] The results are given in Tables 5, 6 and 7 below:

TABLE-US-00005 TABLE 5 Results of the pressure performance test for the oil CO1 CO1 Additive Additive dosage Oil concentration as active material Additive (*) (ppm) Result (h) Without 3.5 additive Ad1 50% 1000 8 Ad1 50% 700 9.5 Ad2 50% 1000 3.5 Ad3 27.5% 550 6.2 Ad3 27.5% 1000 7 Ad4 67.1% 1000 5.3 Ad5 70.6% 1000 3

TABLE-US-00006 TABLE 6 Results of the pressure performance tests for the oil CO2 CO2 Additive Additive dosage Oil concentration as active material Additive (*) (ppm) Result (h) Without 3.5 additive Ad1 50% 1000 >12 Ad1 50% 700 Ad2 50% 1000 9 Ad3 27.5% 700 Ad3 27.5% 550 4.5 Ad4 67.1% 700 Ad5 70.6% 700 Ad6 35% 700 Ad7 35% 700 9

TABLE-US-00007 TABLE 7 Results of the pressure performance tests for the oil CO3 CO3 Additive Additive dosage Oil concentration as active material Additive (*) (ppm) Result (h) Without 3 additive Ad1 50% 1000 >12 Ad2 50% 1000 9 Ad3 27.5% 550 7 Ad7 35% 700 8 (*) concentration by weight of the additive in the solvent

[0196] The modified alkylphenol-aldehyde resins according to the present invention are noteworthy in that they are particularly effective in dispersing the asphaltenes and/or in preventing and/or delaying and/or stopping and/or reducing the precipitation of the asphaltenes over a broad range of crude oils, in comparison with the dispersing additives for asphaltenes of the prior art.