Petroleum demulsifier

Abstract

The invention relates to a composition containing petroleum, water and a demulsifier, and in particular to a method for demulsifying emulsions composed of petroleum and water.

Claims

1. A process for demulsification of a water and petroleum emulsion comprising contacting the emulsion with a demulsifier comprising at least one mannosylerythritol lipid, wherein the total quantity of mannosylerythritol lipid(s) is comprised between 0.5 ppm and 100 ppm, with respect to the weight of the emulsion.

2. The process according to claim 1, in which the quantity of petroleum is comprised between 15 and 80% by volume with respect to the volume of the emulsion.

3. The process according to claim 2, in which the demulsifier further comprises at least one triglyceride and/or at least one fatty acid.

4. The process according to claim 2, in which the demulsifier further comprises a surfactant other than a mannosylerythritol lipid.

5. The process according to claim 1, in which the demulsifier further comprises at least one triglyceride and/or at least one fatty acid.

6. The process according to claim 5, in which the demulsifier further comprises a surfactant other than a mannosylerythritol lipid.

7. The process according to claim 1, in which the demulsifier further comprises a surfactant other than a mannosylerythritol lipid.

Description

EXAMPLE 1: PREPARATION OF MIXTURES OF MELS, OF A COMPOSITION ACCORDING TO THE INVENTION AND DEMULSIFICATION

(1) a) Obtaining MELs

(2) The MELs were obtained by a fermentation process comprising the following steps: conversion of a carbon-containing substrate such as a vegetable (rapeseed) oil by a yeast strain such as Pseudozyma aphidis in order to obtain the MELs; and separating the MELs thus obtained.

(3) The step of separating the MELs was carried out by filtration, centrifugation and evaporation.

(4) At the end of the step of separating the MELs, a first mixture comprising MELs (mixture of MELs 1A) is obtained, which has the following features: Content of MELs: 55% by weight Content of other components: 45% by weight (including 42% by weight of fatty acids and triglycerides and 3% by weight of water and strain),

(5) the percentages by weight being given with respect to the total weight of the mixture obtained.

(6) An additional separation step applied to the mixture of MELs 1A was then carried out by adsorption chromatography on a silica column. A second mixture of MELs (mixture of MELs 1B) was thus obtained, which has the following features: Content of MELs: >98% by weight Content of other components: <2% by weight (including fatty acids and triglycerides).

(7) The composition of the MELs in the mixture of MELs 1B was analysed by high performance liquid chromatography (HPLC).

(8) For this analysis, 50 mg of the mixture of MELs were weighed and 3 mL of chloroform acidified to 0.2% with formic acid (80%) were added. Once the mixture of MELs has dissolved, the solution is filtered on a 0.2 m filter or on 3 filters with a diameter of 0.45 m. 50 L of clear filtrate is taken, to which 950 L of acidified chloroform is added in a 2 mL analytical vial. 10 L of this solution is injected into a Shimadzu LC-20 AD HPLC system provided with an ELSD Sedex 90 detector, equipped with a Nova-Pak silica column 60A, 1503.9 mm 4 m and a Nova-Pak silica pre-column 60A, 203.9 mm 4 m. The analysis temperature is 30 C.

(9) The MELs comprise MELs-A (52% by weight), MELs-B (12% by weight), MELs-C (35% by weight), and MELs-D (1% by weight), the percentages by weight being given with respect to the weight of the total quantity of MELs.

(10) b) Preparation of a Composition According to the Invention and Demulsification Process

(11) For this example, a French petroleum was used.

(12) The water content is 25%, determined with a Karl Fisher reagent according to the method ASTM D1744-92.

(13) In the present application, unless stated otherwise, when a standard is indicated it is the one in force at the filing date.

(14) Its dynamic viscosity at 25 C. is 50 mPa.Math.s, determined using a Stabinger SVM 300/G2 viscometer from Antor Parr according to the standard ASTM D 7042-04 of 2004.

(15) Its content of asphaltenes is 0.8% by weight, measured according to the standard ASTM D2007-03 of 2008.

(16) 100 ppm of a mixture of MELs 1A is added to 100 mL of this petroleum. The mixture is stirred for 5 minutes at 500 revolutions per minute (rpm) then introduced into a 100 mL graduated cylinder.

(17) After 1 hour at ambient temperature, a separation of the aqueous and oil phases is observed and 21 mL of water are recovered.

EXAMPLE 2: EFFECT OF MEL ON A WATER-IN-PETROLEUM EMULSION AFTER SETTLING FOR 1 HOUR

(18) The objective of this example is to show the effect of MEL on emulsions of water in different petroleums, with different water/petroleum ratios, as well as the effect of the quantity of MEL introduced into the emulsion.

(19) a) Products Used

(20) The products which were used in this example are the following: the mixtures of MELs 1A and 1B prepared in Example 1 the petroleums: extra-light, sweet, paraffinic Pennsylvania petroleum medium-heavy sour Alaska petroleum (North Slope Prudhoe Bay) Parisian Basin petroleum sour Texas petroleum sweet North Dakota petroleum demineralized water.

(21) The Table 1 below shows the values of the features of the petroleums used in Example 2.

(22) TABLE-US-00001 TABLE 1 Features of the petroleums used in Example 2 Petroleum Extra-light sweet Medium-heavy, Sour PETROREP Texas Unrefined North Dakota paraffinic Crude Oil Alaska Crude Oil Crude Oil Crude Oil Unrefined Crude Oil Supplier ONTA ONTA PETROREP JANULUS JANULUS Origin Pennsylvania Alaska North Slope Parisian basin Texas North Dakota Prudhoe Bay Colour Brown green Jet black Dark brown Yellow brown/ Yellow brown green black API density () 43.2 26.8 36 39.6 40-43 Dynamic viscosity at 3.06 32.86 30.75 25.74 2.13 20 C. (mPa .Math. s) Acid value 0.344 2.22 0.18 0.04 0.06 (mg KOH/g) Contents of: Sulphur (mg/kg) 650 10400 1860 16400 500 Nitrogen (mg/kg) <40 100 860 1000 160 Asphaltenes 41.4 6.4 32.9 28.9 49.6 (% by weight) Paraffins 44.0 62.7 37.9 30.0 36.7 (% by weight) Polar compounds 1.0 11.4 4.6 5.2 0.8 (% by weight) Aromatics 13.6 19.5 24.6 35.9 12.9 (% by weight)

(23) The API densities are given by the supplier with the corresponding petroleums.

(24) The dynamic viscosities were determined using a Stabinger SVM 300/G2 viscometer from Anton Paar according to the standard ASTM D 7042-04 of 2004.

(25) The acid values were determined according to the standard NF EN ISO 660 of September 2009.

(26) The sulphur contents were determined according to the standard ASTM 5453 of 2012.

(27) The nitrogen contents were measured according to the standard ASTM D5762 of January 2012.

(28) The contents of asphaltenes, paraffins, polar compounds and aromatics, were measured according to the standard ASTM D2007-03 of 2008.

(29) b) Process for the Preparation of Different Emulsions

(30) A certain quantity of a mixture of MELs is introduced into 100 mL of demineralized water and the whole is stirred until the solution is homogeneous. The quantity of the mixture of MELs is adjusted according to the content of MELs desired in the emulsion.

(31) According to the desired water/petroleum ratio, the required quantities of demineralized water containing the MELs (from 80 to 20 mL) and of petroleum (from 20 to 80 mL respectively) were introduced into a container, and the mixture was stirred with an Ultra-Turrax type homogenizer at 11,600 rpm for 2 minutes. Each emulsion obtained was poured into a 100 mL graduated cylinder in order to monitor the separation of the petroleum and water at ambient temperature.

(32) c) Results of Demulsification with Petroleum Originating from the Parisian Basin

(33) The emulsions were prepared according to the protocol described above with petroleum from the Parisian basin and according to the quantities indicated in Tables 2 to 4 hereafter.

(34) Reading the volumes of water is carried out after settling for 1 hour at ambient temperature. The percentages of water recovered correspond to the volumes of water read on the graduated cylinder relative to the volumes of aqueous solutions introduced. The tests are carried out in triplicate.

(35) TABLE-US-00002 Quantity of the mixture of MELs 1B in the water-in-petroleum emulsion = 80/20 0 80 ppm 40 ppm 8 ppm 0.8 ppm % of water recovered 0 >98 >98 >98 >70

(36) TABLE-US-00003 Quantity of the mixture of MELs 1A in the water-in-petroleum emulsion = 80/20 0 80 ppm 16 ppm % of water recovered 0 >80 >80

(37) TABLE-US-00004 Quantity of the mixture of MELs 1A in the water-in-petroleum emulsion = 50/50 0 50 ppm 10 ppm % of water recovered 0 >70 >70

Tables 2 to 4: Results of Demulsification of Water-Petroleum Emulsion from the Parisian Basin

(38) The tests were reproduced using sea water. The separations of the water and the petroleum were obtained more rapidly, in 30 minutes at ambient temperature.

(39) d) Results of Demulsification with Petroleum Originating from the Parisian Basin, Pa., Alaska and Texas

(40) The water-in-petroleum emulsions of this example were prepared according to the protocol described in Example 2 b) with petroleums originating from the Parisian basin, Pennsylvania, Ak. and Texas and according to the quantities indicated in Table 5.

(41) The volumes of water are read after settling for 1 hour at ambient temperature. The percentages of water recovered correspond to the volumes of water read on the graduated cylinder relative to the volumes of aqueous solutions introduced. The tests are carried out in triplicate.

(42) TABLE-US-00005 TABLE 5 Results of demulsification of water- petroleum emulsion of various origins Water-in-petroleum emulsion (50/50) Pennsyl- Parisian vania Alaska Texas water recover- <55 <15 <85 <75 ed (%) without the addition of demulsifier Quantity of the 5 25 5 25 5 25 5 25 mixture of MELs 1B in the emulsion (ppm) water recover- >50 >80 >98 >90 >95 >90 >80 >80 ed (%)

(43) d) Results of Demulsification with Petroleum Originating from Dakota

(44) The water-in-petroleum emulsions of this example were prepared according to the protocol described in Example 2 b) with petroleum originating from Dakota and according to the quantities indicated in Table 6.

(45) The volumes of water were read after settling for 1 hour at ambient temperature. The percentages of water recovered correspond to the volumes of water read on the graduated cylinder relative to the volumes of aqueous solutions introduced. The tests are carried out in triplicate.

(46) TABLE-US-00006 TABLE 6 Results of demulsification of water- petroleum emulsion from Dakota Water-in-petroleum emulsion (20/80) Dakota Quantity of the 2 10 mixture of MELs 1B in the emulsion (ppm) water recovered (%) >98 >98

(47) Without MEL, similar results are obtained at the end of 20 hours.

EXAMPLE 3: EFFECT OF A DEMULSIFIER COMPRISING A MEL AND ANOTHER SURFACTANT ON A WATER-IN-PETROLEUM EMULSION

(48) a) Products Used

(49) The products which were used in this Example are the following: the mixture of MELs 1B prepared in Example 1, the surfactant other than a MEL: nonylphenol polyethylene glycol ether, (Tergitol NP-11 marketed by Dow Chemical), demineralized water, sour Texas petroleum.

(50) b) Process for the Preparation of the Emulsions

(51) The protocol is identical to that described in Example 2 b). For this example, three aqueous solutions were necessary, one containing the mixture of MELs 1B, another containing the surfactant other than a MEL and another containing the mixture of MELs 1B with the surfactant other than a MEL, this surfactant being indicated above.

(52) Two readings of the volumes of water were carried out, one after settling for 1 hour and the other after settling for 20 hours at ambient temperature. The percentages of water recovered correspond to the volumes of water read on the graduated cylinder relative to the volumes of aqueous solutions introduced. The tests are carried out in triplicate.

(53) c) Results: % of Water Recovered

(54) TABLE-US-00007 TABLE 7 Result of comparative test Water-in-petroleum emulsion (50/50) water recovered (%) Settling time 1 h 20 h +0 ppm of MEL <85% <85% +50 ppm of nonylphenol polyethylene glycol ether +25 ppm of MELs >90% >90% +25 ppm of nonylphenol polyethylene glycol ether +50 ppm of MELs <85% <85% +0 ppm of nonylphenol polyethylene glycol ether

(55) By way of indication, starting from a water-in-Texas petroleum emulsion (50/50) without demulsifier, less than 75% of water is recovered after settling for 1 hour at ambient temperature and less than 80% of water is recovered after 20 hours. The presence of MEL improves the demulsification observed with the use of a single surfactant other than a MEL.

EXAMPLE 4: COMPARATIVE EXAMPLE

(56) The water-in-petroleum emulsion in this example was prepared according to the protocol described in Example 2 b) with petroleum originating from Alaska and according to the quantities indicated in Table 8.

(57) The volume of water is read after 1 hour at ambient temperature. The percentage of water recovered corresponds to the volume of water read on the graduated cylinder relative to the volume of aqueous solution introduced. The tests are carried out in triplicate.

(58) TABLE-US-00008 TABLE 8 Result of non-demulsification of water- in-Alaska petroleum emulsion Water-in-petroleum emulsion (50/50) Alaska Quantity of the mixture 250 of MELs 1B in the emulsion (ppm) water recovered (%) 0

(59) The addition of too large a quantity of MEL has the effect of stabilizing the emulsion. No separation between the petroleum and water is observed.