KR20160065936A - Fischer-tropsch derived gas oil fraction - Google Patents

Abstract

The present invention provides a Fischer-Tropsch derived gas oil fraction having an initial boiling point of 215 캜 or higher and a final boiling point of 250 캜 or lower. In another aspect, the present invention provides a functional fluid formulation comprising a Fischer-Tropsch derived gas fraction having an initial boiling point of 215 캜 or higher and a final boiling point of 250 캜 or lower.

Description

FISCHER-TROPSCH DERIVED GAS OIL FRACTION}

The present invention relates to a fractionated Fischer-Tropsch derived gas oil and a functional fluid formulation comprising the same.

The Fischer-Tropsch derived gas oil fraction can be obtained by various processes. The Fischer-Tropsch derived gas oil is obtained using the so-called Fischer-Tropsch process. An example of such a process is disclosed in WO 02/070628.

It has now surprisingly been found that certain Fischer-Tropsch derived gas oil fractions can be advantageously used in solvent and functional fluid applications.

To this end, the present invention provides a Fischer-Tropsch gas oil fraction having an initial boiling point of 215 캜 or higher and a final boiling point of 250 캜 or lower.

The advantage of the present invention is that the combination of these properties is advantageous in that the Fischer-Tropsch derived gas oil fraction has a surprisingly low viscosity, low pour point, while having a high flash point, It provides an advantage in application.

Typically, the Fischer-Tropsch derived gas oil fraction according to the present invention has very low levels of aromatic, naphthenic and impurities.

Thus, the use of Fischer-Tropsch derived gas oil fractions improves biodegradability and provides lower toxicity in solvent and / or functional fluid applications.

The Fischer-Tropsch derived gas oil according to the present invention is derived from the Fischer-Tropsch process. Fischer-Tropsch derived gas oil is known in the art. The term "Fischer-Tropsch derived" means that the gas oil is the synthetic product of the Fischer-Tropsch process or is derived therefrom. In the Fischer-Tropsch process, the synthesis gas is converted to the synthesis product. Syngas or syngas is a mixture of hydrogen and carbon monoxide obtained by conversion of the hydrocarbonaceous feedstock. Suitable feedstocks include natural gas, crude oil, heavy oil fraction, coal, biomass and lignite. The Fischer-Tropsch derived gas oil can also be referred to as a gas-to-liquid (GTL) gas flow.

Fischer-Tropsch derived gas oil is mainly iso-paraffin. Preferably, the Fischer-Tropsch derived gas oil comprises greater than 70 wt%, preferably greater than 75 wt% iso-paraffin.

The Fischer Tropsch gas fraction is a narrow boiling range distillation cut of Fisher Tropsch gas and can also be seen as a GTL-derived solvent distilled from the Fischer-Tropsch gas channel.

According to the present invention, the Fischer-Tropsch derived gas oil fraction has an initial boiling point of 215 캜 or higher and a final boiling point of 250 캜 or lower at atmospheric conditions. Suitably, the Fischer-Tropsch derived gas oil has an initial boiling point of at least 219 캜 at atmospheric conditions. In addition, the Fischer-Tropsch derived gas oil fraction preferably has an initial boiling point of at least 217 ° C.

The Fischer-Tropsch derived gas oil fraction preferably has a final boiling point of at most 248 캜 at atmospheric conditions. In addition, the Fischer-Tropsch derived gas oil fraction preferably has a final boiling point of at most 246 ° C at atmospheric conditions.

The boiling point in the atmospheric condition means the atmospheric boiling point, and the boiling point is determined according to ASTM D86.

Preferably, the Fischer-Tropsch derived gas oil fraction has a T10 volume% boiling point of 211 to 229 占 폚, more preferably 214 to 226 占 폚, most preferably 217 to 223 占 폚, and a T90 volume% boiling point of 227 to 245 Deg.] C, preferably 230 to 242 [deg.] C, and more preferably 233 to 239 [deg.] C.

T10 vol.% Is the temperature corresponding to the atmospheric boiling point at which 10 vol% of the cumulative amount of product is recovered. Likewise, T90 vol% is the temperature corresponding to the atmospheric boiling point at which 90 vol% of the cumulative amount of product is recovered. Atmospheric distillation method ASTM D86 can be used to determine the recovery level, or alternatively, gas chromatographic methods such as ASTM D2887 (calibrated for similar result delivery) can be used.

The Fischer-Tropsch derived gas oil fraction preferably comprises paraffins having 12 to 15 carbon atoms; Based on the total amount of Fischer-Tropsch derived paraffins, based on the amount of Fischer-Tropsch derived paraffins preferably having 9 to 17 carbon atoms, the Fischer-Tropsch derived paraffin gas oil fraction is preferably at least 70 By weight, more preferably at least 85% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, most preferably at least 98% Includes Lop-derived paraffin.

In addition, the Fischer-Tropsch derived gas oil fraction is preferably 762 kg / m ³ to 768 kg / m ³ , more preferably 763 kg / m ³ to 767 kg / m ³ , most preferably 764 kg / m ³ to 766 kg / m ³ at 15 ° C according to ASTM D4052.

Suitably, the kinematic viscosity at 25 캜 according to ASTM D445 is 1.9 to 2.5 cSt, preferably 2.0 cSt to 2.4 cSt, more preferably 2.1 cSt to 2.3 cSt.

Preferably, the Fischer-Tropsch derived gas oil fraction has a flash point according to ASTM D93 of 80 to 95 占 폚, more preferably 82 to 93 占 폚, and most preferably 84 to 91 占 폚.

The Fischer-Tropsch derived gas oil fraction has a fume point in accordance with ASTM D1322 of greater than 50 mm.

Typically, the Fischer-Tropsch gas oil fraction according to the present invention comprises less than 500 ppm aromatics, preferably less than 200 ppm aromatics, less than 3 ppm sulfur, preferably less than 1 ppm sulfur, more preferably less than 0.2 less than ppm sulfur, less than 1 ppm nitrogen, and less than 5 wt% naphthenic, preferably less than 4 wt% naphthenic, and more preferably less than 3 wt% naphthenic.

In addition, the Fischer-Tropsch derived gas fraction preferably contains less than 0.1% by weight of polycyclic aromatic hydrocarbons, more preferably less than 25 ppm of polycyclic aromatic hydrocarbons, most preferably less than 1 ppm of polycyclic aromatic hydrocarbons .

The amount of isoparaffin is suitably more than 75% by weight, preferably more than 80% by weight, based on the total amount of paraffins having 10 to 15 carbon atoms.

In addition, the Fischer-Tropsch derived gas oil fraction may comprise n-paraffins and cyclo-alkanes.

The production of Fischer-Tropsch derived gas oil having an initial boiling point of 215 DEG C or higher and a final boiling point of 250 DEG C or lower is described, for example, in WO02 / 070628.

In a further aspect, the present invention provides a functional fluid formulation comprising a Fischer-Tropsch derived gas oil fraction according to the present invention, further comprising an additive compound. Typically, functional fluid formulations can be used in many areas, such as oil and gas exploration and production, construction, food-related industries, paper, textiles and leather, and various household and consumer goods. In addition, the type of additive used in the functional fluid formulation according to the present invention depends on the type of fluid formulation. Additives for functional fluid formulations include, but are not limited to, corrosion and rheology control products, emulsifiers and wetting agents, borehole stabilizers, high pressure and antiwear additives, defoamers and anti-foaming agents, pour point depressants, Do not.

The advantage of using the Fischer-Tropsch derived gas oil fraction in the functional fluid formulation is that the Fischer-Tropsch derived gas oil fraction has a low viscosity, a low pour point, but a high flash point. Preferably, the above combination of physical properties of the Fischer-Tropsch derived gas oil fraction is highly desirable for its use in functional fluid formulations with low viscosity requirements.

For example, in drilling fluid applications, in use, the temperature of the drilling fluid can be reduced, which can lead to an increase in the viscosity of the drilling fluid. The high viscosity may be detrimental to the beneficial use of the drilling fluid. Thus, the Fischer-Tropsch derived gas oil fraction according to the present invention with low viscosity and high flash point is highly desired for its use in drilling fluid applications.

In another aspect, the present invention provides the use of a Fischer-Tropsch derived gas oil fraction according to the present invention as a dilute or base oil for solvent and / or functional fluid applications.

The term diluent oil refers to oils used to reduce viscosity and / or to improve other properties of solvents and functional fluid formulations.

The term base oil refers to oils in which other oils, solvents or materials are added to produce a solvent or functional fluid formulation.

The advantage of using a Fischer-Tropsch derived gas oil fraction as a diluent oil or base oil for a solvent and / or a functional fluid formulation is that it comprises a Fischer-Tropsch derived gas oil fraction according to the invention, Is as described above in functional fluid formulations.

Preferred solvent and / or functional fluid applications using the Fischer-Tropsch gas oil fraction according to the present invention as a dilute oil or base oil include, but are not limited to, drilling fluids, fracturing fluids, heating fuels, lamp oils, barbecue lighters, Molding damping oil, water treatment, cleaning agent, polish, car dewaxer, discharge processing, transformer oil, silicone mastic, two-stroke motorcycle oil, metal cleaning, dry cleaning, lubricant , Metalworking fluids, aluminum roll oil, molding oils, explosives, printing inks, cosmetics and personal care, rust preventive oils, wood processing, polymer processing oils, and fuel additive formulations, paints and coatings, adhesives, sealants and air fresheners However, it is not limited thereto.

Exemplary solvent and functional fluid applications are described in, for example, " The Index of Solvents ", Michael Ash, Irene Ash, Gower publishing Ltd, 1996, ISBN 0-566-07884-8 and Handbook of Solvents, George Wypych , Willem Andrew publishing, 2001, ISBN 0-8155-1458-1. In a further aspect, the present invention provides the use of a Fischer-Tropsch derived gas oil fraction according to the present invention for improved biodegradability and lower toxicity in solvent and / or functional fluid applications.

As described above, the Fischer-Tropsch derived gas oil fraction preferably has very low levels of aromatic, sulfur, nitrogen compounds, preferably no polycyclic aromatic hydrocarbons. These low levels can, but are not limited to, lead to low aquatic toxicity, low sediment bioaccumulation and low biocidal toxicity of Fischer-Tropsch derived gas oil. The molecular structure of the Fischer-Tropsch derived gas oil fraction according to the present invention can lead to easy biodegradability of the Fischer-Tropsch derived gas oil.

The invention is described below with reference to the following examples, which are not intended to limit the scope of the invention in any way.

Example

Example 1

Production of Fischer-Tropsch derived gas oil fraction having an initial boiling point of 215 ° C or higher and a final boiling point of 250 ° C or lower

The Fischer-Tropsch product was prepared using a catalyst of Example III of WO-A-9934917 in a process analogous to the process described in Example VII of WO-A-9934917. The C ₅ + fraction of the thus obtained product (liquid at ambient conditions) was continuously fed to the hydrocracking step (step (a)). The C ₅ + fraction contained about 60 wt% C ₃₀ + product. The ratio C ₆₀ + / C ₃₀ + was about 0.55. In the hydrocracking step, the fraction was contacted with the hydrocracking catalyst of Example 1 of EP-A-532118. The effluent of step (a) was successively distilled under vacuum to obtain a hard product, fuel and residue "R" (boiling above 370 ° C). The conversion of the boiling product above 370 占 폚 to the boiling product below 370 占 폚 was 45-55 wt%. The residue "R " was recycled to step (a). The conditions of the hydrocracking step (a) were: fresh feed weight hourly space velocity (WHSV) 0.8 kg / lh, recycle feed WHSV 0.4 kg / lh, hydrogen gas velocity = 1000 Nl / kg, total pressure = The reactor temperature ranges from 330 ° C to 340 ° C.

The resulting fuel fraction (C5 ⁺ -370 占 폚) was successively distilled under the conditions shown in Table 1 to obtain a gas oil fraction as a bottom product.

Physical properties are shown in Tables 1 and 2.

Example 2

Use of Fischer-Tropsch derived gas oil as a dilute oil / base oil for solvent and / or functional fluid applications .

The characteristics of the Fischer-Tropsch derived gas oil as shown in Tables 1 and 2 can be used in various applications such as drilling fluids, crushing fluids, heating fuels, lamp oils, barbecue lighters, concrete demoulding, pesticide spraying oils, Heat-stable printing ink, heat-resistant printing ink, heat-resistant printing ink, heat-seal printing ink, Is an important characteristic in the beneficial use of wood-treated, polymer-processed oils, and Fischer-Tropsch derived gas oils in fuel additive formulations, paints and coatings, adhesives, sealants, and air fresheners.

Example 3

In Table 4, the characteristics of the Fischer-Tropsch derived gas oil according to the present invention were compared with those of Isopar ™ M.

Argument

The results of Tables 1 to 3 indicate that a gas-oil fraction derived from Fischer-Tropsch having low viscosity and high flash point was obtained.

The results in Table 4 show that the Fischer-Tropsch derived gas oil has a kinematic viscosity lower than that of Isopar ™ M at initial boiling points and flash points similar.

This indicates that the Fischer-Tropsch derived gas oil fraction is more desirable when compared to the use of Isopar ™ M in the same formulation for use in solvents and functional fluid formulations with low viscosity requirements.

Claims (11)

A Fischer-Tropsch derived gas oil fraction having an initial boiling point of 215 캜 or higher and a final boiling point of 250 캜 or lower. The Fischer-Tropsch derived gas fraction according to claim 1 having an initial boiling point of at least 219 ° C. The Fischer-Tropsch derived gas fraction according to any of the preceding claims, having a final boiling point of at least 246 ° C and not more than 248 ° C. 4. The process according to any one of claims 1 to 3, wherein the T10 volume% boiling point is from 211 to 229 deg. C, preferably from 214 to 226 deg. C, more preferably from 217 to 223 deg. Deg.] C, preferably 230 to 242 [deg.] C, more preferably 233 to 239 [deg.] C. Any one of claims 1 to 4, according to any one of items, to a density of from 15 ℃ according to ^{ASTM D4052 762 768 kg / m 3} , preferably 763 to 767 kg / m ^3, more preferably from 764 to 766 kg / m < ³ >. 6. The composition according to any one of claims 1 to 5, characterized in that the kinematic viscosity at 25 DEG C according to ASTM D445 is 1.9 to 2.5 cSt, preferably 2.0 to 2.4 cSt, more preferably 2.1 to 2.3 cSt Fischer-Tropsch derived gas oil fraction. 7. The process according to any one of claims 1 to 6, wherein the flash point according to ASTM D93 is 80 to 95 占 폚, preferably 82 to 93 占 폚, more preferably 84 to 91 占 폚, . 8. The Fischer-Tropsch derived gas fraction according to any one of claims 1 to 7, wherein the fume point according to ASTM D1322 is greater than 50 mm. A functional fluid formulation comprising a Fischer-Tropsch derived gas oil fraction according to any one of claims 1 to 8, further comprising an additive compound. The use of a Fischer-Tropsch derived gas fraction as defined in any one of claims 1 to 9 as a diluent oil or base oil for solvent and / or functional fluid formulations. Use of a Fischer-Tropsch derived gas fraction as defined in any one of claims 1 to 10 for improved biodegradability and lower toxicity in solvent and / or functional fluid applications.