Mixtures of triglycerides and of alkylesters from vegetable oil and applications

Abstract

A mixture of alkylesters of fatty acids is provided, wherein the fatty acids have the following composition: at least 56% of saturated C12 chains, at least 23% of saturated C14 chains, at most 8% of saturated C16 chains, at most 5% of saturated C6-10 chains, at most 5% of monounsaturated C18 chains, at most 2% of saturated C18 chains, at most 0.8% of diunsaturated C18 chains, and at most 0.2% of saturated C20 chains. The percentages are an average percentage expressed in number of moles per total number of moles of alkylesters, and the use of these mixtures is as a viscosity agent.

Claims

1. An additive for petroleum products comprising a mixture of alkylesters of fatty acids having respectively saturated C12 chains, saturated C14 chains, saturated C16 chains, saturated C6-10 chains, monounsaturated C18 chains, saturated C18 chains, di-unsaturated C18 chains and saturated C20 chains, wherein the fatty acids have the following composition: at least 56% of saturated C12 chains, at least 23% of saturated C14 chains, at most 8% of saturated C16 chains, at most 5% of saturated C6-10 chains, at most 5% of monounsaturated C18 chains, at most 2% of saturated C18 chains, at most 0.8% of di-unsaturated C18 chains, and at most 0.2% of saturated C20 chains, the percentages being expressed in number of moles per total number of moles of alkylesters.

2. An additive for petroleum products comprising a mixture of alkylesters of fatty acids, said mixture comprising: 50-70 weight % of a mixture as defined in claim 1, and 30-50 weight % of a mixture of alkylesters of fatty acids having respectively monounsaturated C18 chains, di-unsaturated C18 chains, saturated C6-18 chains and saturated C20 chains, wherein the fatty acids have the following composition: at least 74% of monounsaturated C18 chains, at most 13% of di-unsaturated C18 chains, at most 13% of saturated C6-18 chains, at most 1% of saturated C20 chains, the percentages being expressed in number of moles per total number of moles of alkylesters.

3. The additive of claim 2, wherein the fatty acids have the following composition: 35.60-42.15% of monounsaturated C18 chains, 27.60-31.40% of saturated C12 chains, 10.50-13.70% of saturated C14 chains, 5.80-7.30% of diunsaturated C18 chains, 3.50-5.15% of saturated C16 chains, 2.70-4.50% of saturated C6-C10 chains, 0.70-1.25% of saturated C18 chains, and 0.50-1.15% of saturated C20 chains.

4. The additive of claim 2, wherein the fatty acids have the following composition: 36.30-42.50% of saturated C12 chains, 20.60-27.30% of monounsaturated C18 chains, 14.60-17.30% of saturated C14 chains, 5.30-6.40% of saturated C16 chains, 3.80-4.75% of diunsaturated C18 chains, 2.50-3.70% of saturated C6-C10 chains, 1.05-1.80% of saturated C18 chains, and 0.50-1.15% of saturated C20 chains.

5. The additive of claim 1, wherein the unsaturations of the mono- and diunsaturated chains are cis.

6. The additive of claim 2, wherein the unsaturations of the mono- and diunsaturated chains are cis.

7. The additive of claim 1, wherein said fatty acid alkylesters are provided by at least one oil selected from palm kernel oil, palm oil and candlenut oil.

8. The additive of claim 2, wherein said fatty acid alkylesters are provided by at least one oil selected from palm kernel oil, palm oil and candlenut oil.

9. A method for treating contaminated soils, said method comprising contacting the contaminating soils with a mixture of alkylesters of fatty acids having respectively saturated C12 chains, saturated C14 chains, saturated C16 chains, saturated C6-10 chains, monounsaturated C18 chains, saturated C18 chains, di-unsaturated C18 chains, and saturated C20 chains, wherein the fatty acids have the following composition: at least 56% of saturated C12 chains, at least 23% of saturated C14 chains, at most 8% of saturated C16 chains, at most 5% of saturated C6-10 chains, at most 5% of monounsaturated C18 chains, at most 2% of saturated C18 chains, at most 0.8% of di-unsaturated C18 chains, and at most 0.2% of saturated C20 chains, the percentages being expressed in number of moles per total number of moles of alkylesters.

10. An additive for fuel comprising a mixture of alkylesters of fatty acids having respectively saturated C12 chains, saturated C14 chains, saturated C16 chains, saturated C6-10 chains, monounsaturated C18 chains, saturated C18 chains, di-unsaturated C18 chains, and saturated C20 chains, wherein the fatty acids have the following composition: at least 56% of saturated C12 chains, at least 23% of saturated C14 chains, at most 8% of saturated C16 chains, at most 5% of saturated C6-10 chains, at most 5% of monounsaturated C18 chains, at most 2% of saturated C18 chains, at most 0.8% of di-unsaturated C18 chains, and at most 0.2% of saturated C20 chains, the percentages being expressed in number of moles per total number of moles of alkylesters, for decreasing combustion-engine exhaust gas, said mixture being in a proportion ranging from 0.5-5% (w/w) with regard to said fuel.

11. The additive for petroleum products according to claim 1, being a viscosity additive effective in the absence of any other viscosity agent, in a proportion ranging from 0.5-5% (w/w) with regard to said petroleum product.

12. The additive for petroleum products according to claim 1, being a lubricating additive effective in the absence of any other lubricating agent, in a proportion ranging from 0.5-5% (w/w) with regard to said petroleum product.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The disclosure and its advantages are illustrated in the following examples in support of the FIGURE.

(2) The FIGURE illustrates the decrease in viscosity (expressed in centiStokes) as a function of the temperature (expressed in ° C.) of a petroleum sample (petroleum from the Fort McMurray deposit in Canada) [.diamond-solid.] and a sample of the same petroleum containing an additive of the disclosure in a proportion of 2% (v/v) [.square-solid.].

DETAILED DESCRIPTION OF THE DISCLOSURE

Example 1

Performances of an Additive of the Disclosure

(3) An additive of the disclosure is prepared from palm kernel oil by saponification and comprises a mixture of fatty acid alkylesters having the following composition:

(4) Saturated C6-C10 chains—5%

(5) Saturated C12 chains—56%

(6) Saturated C14 chains—23%

(7) Saturated C16 chains—8%

(8) Saturated C18 chains 0-2%

(9) Monounsaturated C18 chains—5%

(10) Diunsaturated C18 chains—0.8%

(11) Saturated C20 chains—0.2%

(12) the percentages of the hydrocarbon chains being an average percentage expressed in number of moles per total number of moles of alkylester.

(13) The performances of this additive are tested on petroleum from the Fort McMurray deposit in Canada, by comparison between a petroleum sample and a petroleum sample containing 2% (v/v) of said additive.

(14) Density, API gravity and viscosity are determined for each sample. The lighter a petroleum is, the lower are its density and viscosity and the higher is its API gravity.

(15) The density is measured on a glass pycnometer, at 25° C., it is expressed in kg/m.sup.3.

(16) The API gravity allows expressing the gravity of a crude petroleum from the gravity by the following formula:

(17) $\mathrm{API}\mathrm{gravity}\left(\mathrm{expressed}\mathrm{in}\mathrm{degrees}\mathrm{API°}=\frac{141.5}{\left(\mathrm{gravity}\mathrm{at}{60}^{\circ }F.\right)}-131.5\right)$

(18) Viscosity is measured with a Brookfield HBDV-II+Pro apparatus and a Brookfield LVDV-III Ultra apparatus used according to the prescribed instructions for using these viscometers.

(19) The table below presents the results of these measurements.

(20) TABLE-US-00001 TABLE 1 % Density API Viscosity additive at 25° C. Gravity (cSt) (v/v) (Kg/m.sup.3) (° API) at 20° C. at 50° C. at 80° C. 0 1.0229 6.71 793 821.49 14 338.32 1 200.51 2 0.9970 10.43 341 023.07 9 294.55 966.90 Viscosity reduction rate (%) 57 35 19.5

(21) It is observed that at a content as low as 2% (v/v), the additive of the disclosure allows increasing the API gravity by 4° AP and lowering the viscosity by up to 57% when it is measured at 20° C.; These results demonstrate the performances of an additive of the disclosure and pave the way for a promising future for it in particular in the petroleum industry.

Example 2

Viscosity and AIP Gravity Reduction of a Crude Oil and Crude Oil and Naptha Mixtures, Comprising an Additive of the Disclosure

(22) In this example, the additive of Example 1 is used in a petroleum product (PP) comprising a crude oil as a fuel and/or naptha as specified in Table 2 below. Naphta is generally used as a thinner to allow for crude oil to be moved through pipeline.

(23) The viscosity and the API gravity are measured for each sample in conditions similar to those of the measurement in Example 1.

(24) Table 2 below presents the results of these measurements.

(25) TABLE-US-00002 TABLE 2 Constituents API Gravity (°API) Viscosity PP Cude oil Naphta Additive At 15.5° C. At 26° C. (en cP) 1 1000 0 0 7.4 8.4 4702.3 2 95 4.5 0.5 14.3 15.3 1442.8 3 95 4.25 0.75 15.4 16.4 876.8 4 95 4 1 16.4 17.4 809.8 5 95 3.75 1.25 17.9 19 658.6 6 95 3.5 1.5 18.3 19.4 634.8 7 95 3.25 1.75 19.2 20.3 563.5 8 95 3 2 19.2 21.7 553.5

(26) These results confirm the observations of Example 1 and evidence the capacity of an additive of the disclosure to increase he API gravity and decrease the viscosity of a petroleum product.

Example 3

Viscosity Reduction of Crude Oil by an Additive of the Disclosure

(27) Crude oils were collected from three different wells in Ebok oilfield (Ebok-11, Ebok-14 and Ebok-44) which is located in an oil mining lease (OML 67), offshore Nigeria.

(28) For each crude oils, 500 mL-samples were prepared, containing the crude oil only and increasing quantities of an additive of the disclosure, respectively, and their viscosity measured for two temperatures, 29° C. corresponding to room temperature and one between 34° C. and 48° C. corresponding to the flowline temperature (temperature at which the crude oils is carried in the pipes).

(29) The additive of Example 1 is used.

(30) A viscometer usually employed in crude oil technology is used. It was calibrated with a R4 spindle over temperature range of 20-25° C. and at viscosity value not exceeding 3,333 mPa.

(31) The results are reported in table 3 below.

(32) TABLE-US-00003 TABLE 3 Crude oil (mL)/ % additive Crude oil Additive (mL) (v/v) Viscosity (mpas) EBOK-11 At 29° C. At 48° C. 500/0 0 3333 990 497.5/2.5 0.5 3333 905 495/5 1 3333 710 492.5/7.5 1.5 3045 610  490/10 2 2950 555  485/15 3 2240 450 EBOK-14 At 29° C. At 44° C. 500/0 0 3333 520 497.5/2.5 0.5 3250 480 495/5 1 3090 380 492.5/7.5 1.5 2890 340  490/10 2 2640 310  485/15 3 2210 270 EBOK-44 At 29° C. At 34° C. 500/0 0 885 310 497.5/2.5 0.5 790 300 495/5 1 720 260 492.5/7.5 1.5 705 240  490/10 2 655 220  485/15 3 550 200

(33) EBOK-11:

(34) Viscosity measurements at atmospheric temperature without the additive in the crude oil recorded very high value (+3,333 mPas) in excess of the maximum range the viscometer is calibrated to operate.

(35) Usually outside the maximum range of value the viscometer will record no value. Similarly no value viscosity values were recorded for sample at 0.5% and 1% additive, respectively, suggesting also out of range.

(36) However at 1.5%, the viscosity reduced to 3,045 mPas. At 2% and 3% additive, the crude oil viscosity further reduced to 2,950 mPas and 2,240 mPas, respectively. This suggests that viscosity of the crude oil was actually reduced by more than 33% recorded, if the initial actual viscosity value without additive were measured.

(37) At flowing temperature, the crude oil viscosity was reduced by 55%.

(38) In overall, the additive has demonstrated its capability to reduce EBOK-11 crude oil viscosity by more than 50% at application of 3% additive to the crude oil volume.

(39) EBOK-14:

(40) At atmospheric temperature, the viscosity of the crude oil (without additive) was higher than the range (3,333 mPas) that the viscometer in the field was calibrated to

(41) handle. However with introduction of 0.5% additive, the viscosity reduced to 3,250 mPas. Further reduction in viscosity was measured with addition of more volume of additive. At 3% BNO-1 addition for example, the crude oil viscosity reduced to 2,210 mPas. This indicates that EBOK-14 crude oil viscosity was actually reduced by more than 34% recorded if the initial viscosity value were recorded.

(42) At flowing temperature, the crude oil viscosity was reduced by 48%. Following the test results shown above, additive has demonstrated its capability to lower the viscosity of EBOK-14 crude oil by 48%.

(43) EBOK-44:

(44) The viscosity measurements show that EBOK-44 has less viscous crude oil compared to EBOK-11 and EBOK-14.

(45) At atmospheric temperature, the viscosity value of the crude oil without additive is 885mPas. At 3% additive addition, the crude oil viscosity reduced to 550 mPas, representing 38% reduction in viscosity.

(46) At flowing temperature, the crude oil viscosity also reduced from 310 mPas (crude oil without additive) to 200 mPas (crude oil with 3% additive), thus indicating 36% reduction in viscosity.

(47) In conclusion, the additive of the disclosure has the ability to reduce viscosity of crude oil in EBOK field and helps increase production.

Example 4

Gas-Emission Reduction Of Diesel Engines Supplied with a Crude Oil Containing an Additive of the Invention

(48) A diesel generator (250 KVA) was powered by supplying diesel and diesel containing an additive of the disclosure and the gas-emissions were measured for four samples of each fuel.

(49) The additive of Example 1 is used, in accordance with a ratio additive/crude oil of 1/800 (v/v).

(50) Gas-emissions in the flue gas were measured using methods of the US Environmental Protection Agency (USEPA) as indicated below, for the following gas: sulphur dioxide (SO.sub.2), method USEPA 6C:2015/SOP WL-IP-086, nitrogen oxids (NO.sub.x), method USEPA 7E:2015/SOP WL-IP-086, nitrogen monoxide (NO), method USEPA 7E:2015/SOP WL-IP-086, nitrogen dioxide (NO.sub.2), method USEPA 7E:2015/SOP WL-IP-086, and carbon monoxide (CO), method USEPA 10:2015/SOP WL-IP-046.

(51) The measurements were done in the following conditions:

(52) at a temperature of 27.6° C., a flue gas temperature of 377.4° C., % oxygen flue gas 16.88 and % carbon dioxide in flue gas 3.68, for the tests with diesel (without additive) and

(53) at a temperature of 28.2° C., a flue gas temperature of 408.44° C., % oxygen flue gas 10.86 and % carbon dioxide in flue gas 7.86, for the tests with diesel with additive.

(54) The results are reported in table 4 below.

(55) TABLE-US-00004 TABLE 4 Emitted gas SO.sub.2 NO.sub.x NO NO.sub.2 CO Trial mg/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 Diesel 1 236.0 433.2 426.0 6.2 456.0 fuel 2 256.0 438.6 430.0 6.6 454.0 3 258.0 446.0 438.0 6.7 460.0 4 250.0 439.2 431.3 6.5 456.6 Diesel 5 48.2 126.1 122.6 1.8 176.9 fuel + 6 51.2 129.2 127.1 2.2 182.1 additive 7 56.2 136.1 132.6 2.3 178.2 8 51.8 130.9 127.4 2.1 179.1

(56) These results evidence the exceptional ability of an additive of the disclosure to reduce the gas emission of an engine powered with a fuel comprising an additive of the disclosure.