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(11) | EP 1 693 433 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
| published in accordance with Art. 158(3) EPC |
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| (54) | ADDITIVE FOR HYDROCARBON FUELS |
| (57) The invention relates to petrochemistry, in particular to additive compositions for
hydrocarbon fuels, mainly to automobile gasoline which are added in order to reduce
fuel evaporation losses during storage and can be used for petroleum and fuel storage
depots. The inventive additive comprises a butanol-and-polyether mixture which is
based on ethylene and propylene oxides and whose molecular mass is equal to 402 conventional
units and in which a fluorine-containing chloride of a quaternary ammonium salt of
a formula C8F17CONCHC3H6N(C2H4OH)2Cl is dissolved. Said additive is also comprises an N-perfluoronanyl-β-aminosulfonic
acid sodium salt at the following component ratio: 6.0-12.0 mass % fluorine-containing
chloride of a quaternary ammonium salt of the formula C8F17CONCHC3H6N(C2H4OH)2Cl, 0.2-2.0 mass % N-perfluoronanyl-β-amino-sulfonic acid sodium salt, 30-55 mass
% ethylene and propylene oxide-based polyether with the molecular mass of 402 conventional
units and 35-60 mass % butanol. Said invention makes it possible to reduce the evaporation
of hydrocarbon fuel components during the tank storage thereof and to reuse said additive
by preventing additive precipitation on tank walls, in pipelines and filters of engine
fuel systems. |
Field of the Invention
[0001] The invention relates to petrochemistry, in particular to additive compositions for hydrocarbon fuels, mainly to automobile gasoline, which are added in order to reduce fuel evaporation losses during storage, and can be used at petroleum and fuel storage depots.
Description of the Prior Art
[0002] An additive is known, which comprises a fluorine-containing surfactant, a polyether with the molecular weight of 2500 which is based on ethylene oxide and propylene oxide, ethylene glycol, and an aliphatic alcohol taken as butanol-1 (see: V.V. Usin, A.V. Ulitko et al. The environment protection when using fuels and operating means of transportation, Ulianovsk, UTTsNTIP, 1993, p.25).
[0003] The said additive, however, comprises components in high concentrations and has low efficiency in reducing fuel evaporation losses during storage.
[0004] An additive is also known, which comprises a fluorine-containing surfactant, a polyether with the molecular weight of 3503 which is based on ethylene oxide and propylene oxide, ethylene glycol, and an aliphatic alcohol (see: V.V. Usin, A.V. Ulitko et al. The environment protection when using fuels and operating means of transportation, Ulianovsk, UTTsNTIP, 1993, p.34-35). The additive comprises, in % by weight: a fluorine-containing quaternary ammonium salt ― 4.5 to 5.5, a polyether with the molecular weight of 3503 which is based on ethylene oxide and propylene oxide ― 47.0 to 49.0, ethylene glycol ― 4.5 to 5.5, and butanol-1 the rest. The said additive is used for reducing evaporation losses and is added to a hydrocarbon fuel directly in the concentration of 0.2 % by weight. The experience of using the additive proves its insufficient efficiency in reducing evaporation fuel losses during storage.
[0005] The closest, as to its technical essence and achieved result, to the inventive additive is an additive to hydrocarbon fuels, which comprises a butanol-polyether mixture based on ethylene oxide and propylene oxide, in which a fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl is dissolved (see, RU 2208041 C10L 1/18, 2003). The said additive to hydrocarbon fuels also comprises decanol and a dioctyl ether of phthalic acid in the following component ratio, in % by weight:
| Fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl | 1.2 to 3.4 |
| Polyether with the molecular weight of 3503 which is based on ethylene oxide and propylene oxide | 3.5 to 7.5 |
| Dioctyl ether of phthalic acid | 3.5 to 7.5 |
| 1:1 mixture of decanol and butanol | the rest. |
[0006] The disadvantages of the known solution are its low efficiency in reducing evaporation fuel losses during storage (for A-76 gasoline the evaporation reduction is 30 %) as well as practically complete deposition of these additives on containment walls, pipelines and fuel system filters during fuel pumping and tank drying, which does not enable to use the said additives repeatedly when filling tanks. After fuel has been removed from a tank, it is practically impossible to separate the additive film from the tank surface by way of feeding a new batch of fuel.
Brief Description of the Invention
[0007] The objective of the invention is to develop and create an additive to hydrocarbon fuels, which would have improved performance and efficiency.
[0008] By achieving the said objective it is possible to obtain technical results comprising a reduction in evaporation of hydrocarbon fuel components when storing them in tanks, as well as in provision of repeated use of an additive by excluding its deposition on tank walls, pipelines and engine fuel system filters.
[0009] The said technical results may be achieved by using a polyether having the molecular weight of 402 as a polyether used in a hydrocarbon fuel additive comprising a butanol-polyether mixture based on ethylene oxide and propylene oxide, in which a fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl is dissolved, the said additive comprising, in addition, a sodium salt of the N-perfluorinenononail-β-aminosulfonic acid, with the following component ratio, in % by weight:
| Fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl | 6 to 12 |
| Sodium salt of the N-perfluorinenononail-β-aminosulfonic acid | 0.2 to 2.0 |
| Polyether with the molecular weight of 402, which is based on ethylene oxide and propylene oxide | 30 to 55 |
| Butanol | 35 to 60 |
[0010] The distinctive feature of the invention is that the said additive comprises, in addition, a sodium salt of the N-perfluorinenononail-β-aminosulfonic acid, and a polyether with the molecular weight of 402 is used as the polyether based on ethylene oxide and propylene oxide. In the result of a reaction of the said sodium salt of the N-perfluorinenononail-β-aminosulfonic acid with the said fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl and butanol fuel evaporation losses are reduced, and the polymeric film sticking to metallic surfaces of fuel tanks is precluded, which enables to use the said additive in tanks repeatedly.
[0011] The additive components content, which ensures obtaining of the above-said results, has been determined experimentally.
[0012] Further, it is advisable that the ratio of a polyether, which has the molecular weight of 402 and is based on ethylene oxide and propylene oxide, and butanol would be 49:40.
Description of the Preferred Embodiment
[0013] In order to prepare the additive, a fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl is dissolved in a mixture of butanol and a polyether with the molecular weight of 402, which is based on ethylene oxide and propylene oxide. A sodium salt of the N-perfluorinenononail-β-aminosulfonic acid is added to the obtained solution in the quantity from 0.2 to 2.0 % by weight.
[0014] The said fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl is a wax-like substance having a light-brown color, which is hygroscopically dissolved in alcohols. It has the density from 1560 to 1600 kg/m3, the melting point of 80°C, the chlorine content from 5.0 to 5.6 % by weight. Its technical designation is "CHAS 9". It is made according to the specification "TU 6-02-2-817-84".
[0015] The polyether having the molecular weight of 402, which is based on ethylene oxide and propylene oxide is a syrupy colorless liquid. The hydroxyl group content is 1.5 to 1.7 %, the acid number is < 0.1 mg KOH/g, the Heppler viscosity at 25°C is 450 to 600 MPa·s, the density is 1010 kg/m3, the molecular weight is 402. The technical designation is "Laprol-402". It is made according to the specification "TU 6-05-221-484-79".
[0016] Butanol is a colorless clear liquid. It has the density from 800 to 830 kg/m3, the boiling point is 108°C. It is produced in the industry according to GOST 6006. It is used as a solvent in the paint industry (see, Chemical Encyclopedia in 5 Volumes, V. 1, I.L. Knunyants et al., M., Soviet Encyclopedia Publishers, 1988, p.336-337).
[0017] The sodium salt of the N-perfluorinenononail-β-aminosulfonic acid is a colorless liquid produced by known methods.
[0018] The inventive additive is added to a hydrocarbon fuel after filling a tank with a fuel, e.g., automobile gasoline, in the quantity from 0.015 to 0.025 % by weight. The additive is added to a fuel by pulverizing it.
[0019] In order to establish the quantitative composition of the additive, some samples (see Table 1) have been prepared, which have been tested in a composition with A-76 automobile gasoline according to GOST 2084. Samples 1 - 5 differ in the percentage ratio of the components in the inventive additive.
[0020] The additive efficiency has been evaluated according to the quantity of evaporated fuel under storage in the static conditions for two days, as compared to the fuel without the additive and the fuel with the additive according to the closest analogous solution. The additive test results are given in Table 2.
[0021] The evaporation tests have been conducted in the static conditions in glasses with the evaporation area of 13.8 cm2 at the air temperature from 18°C to 20°C and the relative humidity from 85% to 95%. The error in determining evaporation is ±0.05 g/day/m2.
[0022] An analysis of the results given in Table 2 enables to draw a conclusion that the most preferred are Samples 1 and 2 of the additive, though all the tested compositions in the above-stated conditions reduce the quantity of gasoline evaporated from the surface.
[0023] The efficiency of the additives has been also evaluated according to a reduction in fuel evaporation when the repeatedly used compositions have been pulverized over the fuel surface ― when drying and subsequent filling of a tank with a fuel. As can be seen in Table 2, the efficiency of the inventive additive is practically not reduced because it is not deposited on the surfaces.
Table 1.
| Additive composition, in % by weight | SAMPLES | ||||
| 1 | 2 | 3 | 4 | 5 | |
| Fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl | 10 | 9 | 8 | 6 | 12 |
| Laprol-402 | 49 | 40 | 55 | 33.5 | 30 |
| Butanol | 40 | 49.5 | 35 | 60 | 57.8 |
| Sodium salt of the N-perfluorinenononail-β-aminosulfonic acid | 1 | 1.5 | 2 | 0.5 | 0.2 |
1. An additive for hydrocarbon fuels comprising a butanol-polyether mixture based on
ethylene oxide and propylene oxide, in which a fluorine-containing chloride of a quaternary
ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl is dissolved, wherein a polyether having the molecular weight of 402 is used as
the polyether in the said mixture, the said additive further comprising a sodium salt
of the N-perfluorinenononail-β-aminosulfonic acid and having the following component
ratio, in % by weight:
| Fluorine-containing chloride of a quaternary ammonium salt having the formula C8F17CONCHC3H6N(C2H4OH)CH3)2Cl | 6 to 12 |
| Sodium salt of the N-perfluorinenononail-β-aminosulfonic acid | 0.2 to 2.0 |
| Polyether with the molecular weight of 402, which is based on ethylene oxide and propylene oxide | 30 to 55 |
| Butanol | 35 to 60 |
2. The additive according to Claim 1, wherein the ratio of the polyether, which has the
molecular weight of 402 and is based on ethylene oxide and propylene oxide, and butanol
is 49:40.