KR20170010782A - Process for preparing a high purity fischer-tropsch gasoil fraction - Google Patents

Abstract

The present invention provides a process for the preparation of a feedstock comprising: a) providing a Fischer-Tropsch derived gas oil feedstock comprising at least one contaminant; b) feeding the Fischer-Tropsch-derived gas oil feedstock to a fractionation zone and separating the Fischer-Tropsch-derived gas oil feedstock into two or more Fischer-Tropsch gas oil fractions having different boiling ranges Wherein the at least one Fischer-Tropsch gas oil fraction is at least one contaminant enriched contaminant-rich Fischer-Tropsch gas oil fraction for the feedstock; c) providing a contaminant-rich Fischer-Tropsch gas oil fraction in an absorption zone comprising at least one absorbent material, contacting the contaminant-rich Fischer-Tropsch gas oil fraction with an absorbent material to absorb at least a portion of the contaminant step; And d) recovering the contaminant-reduced purified Fischer-Tropsch gas oil fraction from the absorption zone. The present invention also provides a further process for the preparation of high purity Fischer-Tropsch gas oil fractions and the use of purified Fischer-Tropsch gas oil fractions.

Description

TECHNICAL FIELD [0001] The present invention relates to a high-purity Fischer-Tropsch gas oil fraction,

The present invention relates to a process for the preparation of high purity Fischer-Tropsch gas fraction and its use as a solvent or functional fluid.

Over the last two decades interest in synthetic paraffinic hydrocarbon products has increased. Such synthetic paraffin products are produced, for example, by the so-called Fischer-Tropsch process, in which a synthesis gas, i. E. A mixture of mostly hydrogen and carbon monoxide, is converted to a higher hydrocarbon compound containing paraffins.

The synthetic paraffin product of particular interest is a Fischer-Tropsch-derived gas oil. Due to its synthetic origin, such Fischer-Tropsch-derived gas oils have very low levels of aromatics, naphthenes and impurities compared to their crude oil derived counterparts. In addition, the Fischer-Tropsch-derived gas oil has the property of providing advantages in solvent and functional fluid applications with low viscosity requirements.

US 2012/0048775 discloses a process for the preparation of intermediate fractions having an initial boiling point in the range of 150 ° C to 400 ° C and an end point in the range of 300 ° C to 450 ° C, Which is produced by the Fischer-Tropsch synthesis. US 2004/152793 describes a process for the preparation of olefin naphtha wherein the olefin naphtha stream is isolated from the Fischer-Tropsch hydrocarbon stream and purified over metal oxides at elevated temperatures. US 2004/152793 discloses that paraffins of the non-olefin component of the naphtha are mostly n-paraffin. US 5906727 discloses a Fischer-Tropsch derived solvent having a boiling range of about 160 to 370 ° C. According to US 5906727, the solvent is odorless and colorless (saybolt color number of +30). There is a need in the art for a Fischer-Tropsch derived solvent having a narrower boiling range than the solvent disclosed in US 5906727.

The present invention provides a process for preparing purified Fischer-Tropsch gas oil fractions. For example, if a Fischer-Tropsch-derived gas oil having a relatively broad boiling range within a range of about 150 to 450 DEG C is fractionated into two or more fractions having a narrower boiling range, one or more fractions may be increased Odor and / or discoloration. These adverse side effects encountered when separating virtually odorless and colorless Fischer-Tropsch-derived gas oils are not known until now. It has now been found that this problem can be solved by the method according to the invention.

Therefore,

a) providing a Fischer-Tropsch-derived gas oil feedstock comprising at least one contaminant, wherein the Fischer-Tropsch derived gas oil has an alkyl chain length ranging from 7 to 30 carbon atoms, Based on the total amount of Fischer-Tropsch derived paraffins, containing paraffins containing isoparaffins and normal paraffins and having 9 to 25 carbon atoms. ;

b) feeding the feedstock to a fractionation zone and separating the feedstock into at least two Fischer-Tropsch gas oil fractions having different boiling ranges, wherein at least one Fischer-Tropsch gas oil fraction is contaminated with feedstock contaminants Rich Fischer-Tropsch gas oil fraction;

c) providing a contaminant-rich Fischer-Tropsch gas oil fraction in an absorption zone comprising at least one water-absorbing material and contacting the contaminant-rich Fischer-Tropsch gas oil fraction with an absorbent material to form at least a portion ; And

d) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone as a high purity Fischer-Tropsch gas oil fraction, wherein the purified Fischer-Tropsch gas oil fraction is separated from the contaminant-rich Fischer-Tropsch gas oil fraction Lt; RTI ID = 0.0 > contaminant-reduced

And a first fraction of the purified Fischer-Tropsch gas oil fraction.

The process according to the invention comprises the preparation of a purified Fischer-Tropsch gas oil fraction having applicability as a solvent, diluent and functional fluid with a narrower boiling range than the Fischer-Tropsch-derived gas oil feedstock from which it is prepared .

The process according to the invention also contemplates the production of purified Fischer-Tropsch gas oil fractions having applicability as solvents, diluents and functional fluids with desired odor and / or color specifications.

The process according to the present invention also contemplates removing contaminants using relatively simple, inexpensive, and safe absorption methods, for example, in comparison with treatment with strong acids such as concentrated sulfuric acid or elaborate and expensive hydrotreating treatments.

In a further aspect,

i) providing a contaminant-containing Fischer-Tropsch gas oil fraction containing greater than 50 wt% of isoparaffin and having a final boiling point of less than or equal to 260 DEG C in an absorption zone comprising an absorbent material, Contacting the gas oil fraction with an absorbent material to absorb at least a portion of the contaminant; And

ii) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone as a high purity Fischer-Tropsch gas oil fraction, wherein the purified Fischer-Tropsch gas oil fraction is separated from the contaminant-containing Fischer-Tropsch gas oil fraction Lt; RTI ID = 0.0 > contaminant-reduced

And a second fraction of the purified Fischer-Tropsch gas oil fraction.

In a further aspect,

v) providing a contaminant-containing Fischer-Tropsch gas oil fraction having an initial boiling point above 260 ° C in an absorption zone comprising an absorbent material, contacting the contaminant-containing Fischer-Tropsch gas oil fraction with an absorbent material, Absorbing at least a portion thereof; And

vv) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone as a high purity Fischer-Tropsch gas oil fraction, wherein the purified Fischer-Tropsch gas oil fraction is separated from the contaminant-containing Fischer-Tropsch gas oil fraction Lt; RTI ID = 0.0 > contaminant-reduced

And a third step of producing a high-purity Fischer-Tropsch gas oil fraction.

In another aspect, the present invention provides the use of a purified Fischer-Tropsch gas oil fraction prepared by the process according to the present invention as a solvent, diluent or functional fluid.

The present invention provides a first process for preparing purified Fischer-Tropsch gas oil fractions. Such Fischer-Tropsch gas oil fractions are particularly suitable for use as solvents, diluents and functional fluids, particularly for the applications mentioned herein.

In the process according to the invention, the fractions are prepared by providing and fractionating Fischer-Tropsch-derived gas oil. The Fischer-Tropsch derived gas oil according to the present invention is a syngas oil derived from the Fischer-Tropsch process. Fischer-Tropsch-derived gas oil is known in the relevant 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. The syngas or syngas is a mixture of mostly hydrogen and carbon monoxide obtained by conversion of the hydrocarbon feedstock. Suitable feedstocks include natural gas, crude oil, heavy oil fractions, coal, biomass or lignocellulosic biomass and lignite. The Fischer-Tropsch-derived gas oil may also be referred to as GTL (Gas-to-Liquids) gas flow. The Fischer-Tropsch-derived gas oil can be a synthetic gas, or a mixture of mostly hydrogen and carbon monoxide, which is treated at elevated temperature by a Fischer-Tropsch catalyst, which is treated on a supported catalyst consisting of Group VIII metals or metals such as cobalt, ruthenium, Is a product of the process. In the hydrogenation cracking / hydrogenation isomerization conditions, a Fischer-Tropsch catalyst is preferably used on a catalyst containing a bifunctional catalyst or an acidic oxide support component which is active in producing both the metal or metals, the hydrogenation component and the hydrogenation cracking and the hydrogenation isomerization reaction At least a portion of the Loxian product is contacted with hydrogen. At least a portion of the resulting hydrogenated cracked / hydrogenated isomerized Fischer-Tropsch product may be provided as a Fischer-Tropsch-derived gas oil.

The Fischer-Tropsch-derived gas oil differs from the crude oil-derived gas oil. Despite having a similar boiling range, the specific molecular composition of the Fischer-Tropsch-derived gas oil is notably improved by the improved viscosity characteristics, improved pour point characteristics, improved density characteristics, and, in particular, A combination of features may be allowed. For example, a Fischer-Tropsch-derived gas oil can combine low volatility and high flash point, while the viscosity of such a Fischer-Tropsch-derived gas oil is similar to that of a crude oil-induced gas oil having a similar volatility and flash point It may be lower than the viscosity. Notwithstanding the foregoing, the Fischer-Tropsch derived gas oil is a complex mixture of molecules that should not be compared to pure paraffin molecules, such as, for example, pure n-dodecane.

The different characteristics of the Fischer-Tropsch-derived gas oil compared to the crude oil-derived gas oil generally include the weight ratio (i / n ratio) of the specific isoparaffin to its normal paraffin, the relative amount of mono-methyl branched isoparaffin And the molecular weight distribution of paraffins, as well as the absence of significant levels of aromatics and naphthenes.

A particular advantage of the Fischer-Tropsch-derived gas oil is that these gas oils show very little odor and are almost colorless. The color used herein is the Sabellot color measured by its Sabouraud number (ASTM D156: Standard Test Method for Sabotol Color of Petroleum Products). A high number of SeVolts, +30 represents a colorless fluid, while a low Se volt number, especially below zero, shows discoloration. The number of Sabbaths of less than 25 indicates that there is already visible discoloration. The Fischer-Tropsch-derived gas oil typically has a maximum number of cubic volts, i.e., +30. The high purity, low odor and minimal color features make the Fischer-Tropsch derived gas oil very suitable for solvent, diluent and functional fluid applications, together with the abovementioned improved viscosity, pour point, density and flash point characteristics.

These low odor and minimal color characteristics are due in part to the fact that the concentration of these contaminants in the Fischer-Tropsch-derived gas oil is relatively low, although contaminants are present in the Fischer-Tropsch-derived gas oil feedstock It is due to fact. This means that the feedstock for the Fischer-Tropsch process contains little or no sulfur, and the process produces a Fischer-Tropsch-derived < RTI ID = 0.0 > This is due to the characteristics of the Fischer-Tropsch process for the production of gas oil. It has now been found that the Fischer-Tropsch-derived gas oil can be separated into two or more fractions having different boiling ranges to meet the specific requirements of the specific use of the Fischer-Tropsch-derived gas oil. By fractionating the Fischer-Tropsch-derived gas oil, isoparaffins and normal paraffins are heterogeneously distributed over two or more fractions and have a different i / n ratio than the Fischer-Tropsch-derived gas oil feedstock Fischer-Tropsch gas oil fraction can be obtained. In addition, the relative amounts of mono-methyl branched isoparaffin and molecular weight distribution of paraffin may be different. As a result, the viscosity, pour point, density and flash point characteristics of the Fischer-Tropsch-derived gas oil fraction can be varied beyond predictable changes based on fractional solely based discrimination.

In the process according to the invention, the Fischer-Tropsch-derived gas oil feedstock is provided in the fractionation zone. Reference to fractionation zones herein is for one or more separation means for separating the Fischer-Tropsch derived gas oil feedstock into two or more fractions having different boiling ranges. Examples of suitable separation means include, but are not limited to, distillation units. Preferably, the Fischer-Tropsch-derived gas oil feedstock is fractionated by distillation. The Fischer-Tropsch derived gas oil feedstock can be fractionated in a single distillation column or in two or more distillation columns. It is preferred that the Fischer-Tropsch-derived gas oil feedstock be fractionated in one or more distillation columns.

In the fractionation zone, the Fischer-Tropsch-derived gas oil feedstock comprises two or more Fischer-Tropsch derived gas oil fractions, also referred to herein as Fischer-Tropsch gas oil fractions, each having a different boiling range . Preferably, the Fischer-Tropsch-derived gas oil feedstock is fractionated into three or more, more preferably four or more, Fischer-Tropsch gas oil fractions each having a different boiling range. Preferably, at least one, more preferably at least two, Fischer-Tropsch gas oil fractions have a final boiling point of at most 260 ° C, preferably at most 250 ° C, more preferably at most 215 ° C. The reference to the final boiling point herein refers to the upper limit of the boiling range of the Fischer-Tropsch gas oil fraction, which is defined as the range of initial boiling to final boiling measured under atmospheric conditions as determined according to ASTM D86.

Equally preferably, the at least one, more preferably at least two, Fischer-Tropsch gas oil fractions have an initial boiling point above 260 ° C, preferably above 300 ° C, more preferably above 310 ° C. The reference to the initial boiling point herein refers to the lower limit of the boiling range of the Fischer-Tropsch gas oil fraction, and this boiling range is defined as the range of initial boiling to final boiling measured under atmospheric conditions when measured according to ASTM D86.

When Fischer-Tropsch-derived gas oil is fractionated, the contaminants present in the Fischer-Tropsch-derived gas oil feedstock are not evenly distributed over two or more fractions, although their level is low. In particular, it has been observed that low molecular weight and / or more volatile contaminants may not be present in the high boiling fraction and may accumulate in the low boiling fraction. These contaminants are believed to cause unwanted odors and optionally discoloration of the fractions that were not observed in the Fischer-Tropsch-derived gas oil feedstock.

It has been observed that contaminants, especially high molecular weight and / or less volatile, can be accumulated in the high boiling fraction without being present in the low boiling fraction. Most of these contaminants are thought to cause unwanted discoloration of the fractions.

The contaminants herein are non-paraffinic, non-naphthenic compounds. The term contaminant herein refers to a compound selected from the group consisting of an oxygen-containing compound, an unsaturated hydrocarbon compound, a sulfur-containing compound and a nitrogen-containing compound.

The term unsaturated hydrocarbon compounds as used herein refers to compounds having at least one unsaturated bond, including aromatic.

As used herein, the term oxygen compound refers to an oxygen-containing hydrocarbon compound. Examples of oxygen-containing compounds include, but are not limited to, alcohols, ketones, aldehydes, ethers, epoxides, and acids.

As used herein, the term aromatic refers to a compound comprising at least one aromatic group, including an aromatic compound and a polycyclic aromatic.

More preferably, the term contaminants herein refers to compounds selected from the group consisting of oxygen-containing compounds and aromatics, which provide the greatest contribution to the odor and discoloration of the contaminant-rich Fischer-Tropsch gas oil fraction It is because it is thought.

The term contaminant concentrations herein are expressed in ppmw, unless otherwise explicitly indicated and refer to the respective total Fischer-Tropsch-derived gas oil, the contaminant-rich Fischer-Tropsch gas oil fraction or the purified Fischer-Tropsch gas And the contaminant concentrations calculated based on the total weight of the contaminants.

Thus, in the process according to the invention, the one or more Fischer-Tropsch gas oil fractions produced in step (b) are separated from the Fischer-Tropsch derived gas oil feedstock over the prepared Fischer-Tropsch gas oil fraction Due to the uneven distribution of contaminants, it is a contaminant-rich Fischer-Tropsch gas oil fraction. Reference herein to the contaminant-rich Fischer-Tropsch gas oil fraction is for a Fischer-Tropsch gas oil fraction containing a higher concentration of one or more contaminants than the Fischer-Tropsch-derived gas oil feedstock . In particular, the contaminant-rich Fischer-Tropsch gas oil fraction may comprise one or more contaminants selected from the group consisting of oxygenated compounds and aromatics.

The effect of the accumulation of contaminants in the contaminant-rich Fischer-Tropsch gas oil fraction is that the number of Sabot of the contaminant-rich Fischer-Tropsch gas oil fraction is lower than that of Fischer-Tropsch-derived gas oil feedstock That is, the coloration of the fraction is increased. This unwanted discoloration is observed especially in high boiling Fischer-Tropsch gas oil fractions. While not wishing to be bound by any particular theory, it is believed that more complex conjugated molecules, in particular, affect the emission and absorption of light. Such complex conjugated molecules are expected to have higher molecular weights. It has also been observed that discoloration of the lower fractions can occur, albeit to a lesser extent.

Another effect of the accumulation of contaminants in the contaminant-rich Fischer-Tropsch gas oil fraction may be an increase in the odor emitted by the Fischer-Tropsch gas oil fraction. This undesirable odor is especially observed in low boiling Fischer-Tropsch gas oil fractions. While not wishing to be bound by any particular theory, it is believed that low molecular weight molecules, especially more volatile, cause the presence of odor.

Fischer-Tropsch-derived gas oils and in particular Fischer-Tropsch-derived paraffins have an inherent odor. Thus, when referring to terms such as odorless, low odor or a little odor here, it refers to qualitatively the same or qualitatively similar odor as that of a Fischer-Tropsch-derived gas oil or paraffin. When referring to terms such as increased odor, strong odor and unwanted odor or similar terms herein, it refers to qualitatively different odors from those of Fischer-Tropsch-derived gas oils or paraffins. This difference in odor may optionally be characterized by comparing the odor of the contaminant-rich Fischer-Tropsch gas oil fraction and the Fischer-Tropsch-derived gas oil feedstock and classifying the difference, i.e. 1 is the Fischer- - qualitatively the same as that of the derived gas oil feedstock (good odor character), while 5 is very different in quality (poor odor character) from the Fischer-Tropsch derived gas oil feedstock.

Preferably, the Fischer-Tropsch-derived gas oil feedstock is fractionated into at least two Fischer-Tropsch gas oil fractions, at least one of the two or more Fischer-Tropsch gas oil fractions having a maximum of 260 < Rich Fischer-Tropsch gas oil fraction having a final boiling point of at most 250 ° C, more preferably at most 215 ° C. Equally preferably, the Fischer-Tropsch-derived gas oil feedstock is fractionated into at least two Fischer-Tropsch gas oil fractions, and at least one of the two or more Fischer- Rich Fischer-Tropsch gas oil fraction having an initial boiling point of at least 300 ° C, more preferably at least 310 ° C. Typically, the number of Sabbath-rich Fischer-Tropsch gas oil fraction having an initial boiling point of greater than 260 ° C is less than 30, in particular 2 or more, and optionally 5 or more, and the Fischer-Tropsch-derived gas oil feedstock It may be less than three.

When more than one contaminant-rich Fischer-Tropsch gas oil fraction is produced, the above-described characteristics of the contaminant-rich Fischer-Tropsch gas oil fraction can be applied to one or more contaminant-rich Fischer-Tropsch gas oil fractions However, it can be applied to other contaminant-rich Fischer-Tropsch gas oil fractions.

Both of the aforementioned discoloration and odor enhancement are undesirable properties and are not beneficial for use in Fischer-Tropsch gas oil fractions in solvents, diluents or functional fluid applications. For the production of a Fischer-Tropsch gas oil fraction suitable for a wide range of solvents, diluents or functional fluid applications, the contaminant-rich Fischer-Tropsch should be further treated to reduce odor and / or discoloration.

Thus, the process according to the present invention further comprises providing a contaminant-rich Fischer-Tropsch gas oil fraction in the absorption zone. The absorption zone includes one or more absorbent materials suitable for absorbing at least a portion of the contaminants. References herein to absorbent materials are directed to absorbent and absorbent materials. References to adsorption here are for adsorption and adsorption. The reference to absorption in this context is absorption and adsorption.

Preferably, the absorption zone comprises magnesium silicate, and 4A or 5A molecular sieve, zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, Zeolite beta, zeolite L, and molecular sieve materials including zeolite omega.

While not wishing to be bound by any particular theory, it is believed that absorbent materials, particularly those with large pore sizes, i.e., pore sizes greater than or equal to 0.5 nm (5 Angstroms), can absorb relatively large aromatic compounds in addition to oxygenated compounds and other contaminants . Absorbent materials with small pore sizes predominantly absorb non-aromatics, especially including oxygen-containing compounds.

Thus, the absorption zone should be greater than 0.5 nm (5 Angstroms), more preferably greater than 0.55 nm (5.5 Angstroms), even more preferably greater than 0.6 Angstroms (6 Angstroms), even more preferably greater than 0.65 nm (6.5 Angstroms) It is particularly preferred to include at least one absorbent material comprising pores having a pore size. Preferably, the absorption zone is selected from the group consisting of zeolite X, zeolite 13X, zeolite Y, dealuminated zeolite Y, superstable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite Omega, At least one water-absorbing material selected from the group consisting of zeolite 13X, zeolite Y, dealuminated zeolite Y, super stable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega, Even more preferably, the absorbent material is zeolite 13X, which is the sodium form of zeolite X. When the absorption zone comprises one or more molecular sieve absorbent materials, the one or more molecular sieve absorbent materials are preferably more than 0.5 nm (5 Angstroms), more preferably at least 0.55 nm (5.5 Angstroms) It is preferable to have a channel structure having a diameter of 0.6 nm (6 angstroms) or more, and even more preferably, 0.65 nm (6.5 angstroms) or more.

The absorption zone may comprise two or more kinds of water absorbent materials, preferably two or more kinds selected from the above-mentioned water absorbent materials. A preferred combination of absorbent material may comprise zeolite 13X and magnesium silicate. Another preferred combination of absorbent materials can include zeolite 13X and activated coal. The combination of sorbents can make it possible to absorb a wider range of contaminants, such as larger molecular sizes and smaller molecular size contaminants, such as oxygen-containing compounds and aromatic, or polar and non-polar contaminants, more efficiently.

The molecular sieve used as the absorbent material in the process of the present invention is based on an acidic molecular sieve having a constituent silica-to-alumina molar ratio of preferably less than 100, more preferably more than 10, for example 20 to 50. Low silica materials can be more effective than high silica molecular sieve materials since they have more sites for available adsorption sites.

The absorbent material used in the absorption zone of the method of the present invention may be provided in the form of particles, e.g. extrudates, spheres or pellets. The particles can improve the strength of the particles by including the absorbent material either alone or in combination with the binder material or filler material. The binder or filler material may be, for example, an amorphous metal oxide including alumina, silica, zirconia, and titania. Preferably, the binder or filler material is alumina.

Preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material at a temperature in the range of 0 to 150 DEG C in the absorption zone. The lower limit of the temperature range in which the contaminant-rich Fischer-Tropsch gas oil fraction is in contact with the water-absorbing material in the absorption zone is the diffusion with limited absorption, and a temperature below 0 ° C is the water- ≪ / RTI > will cause an undesirable reduction in the rate of diffusion of contaminants into the exhaust gas. When the contact temperature is increased, that is, when it is increased to more than 0 ° C, the diffusion rate may increase. By keeping the temperature below < RTI ID = 0.0 > 150 C, < / RTI > This is important because such by-products can have undesirable effects on the applicability of the Fischer-Tropsch gas oil fraction produced.

More preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material at a temperature in the absorption zone in the range of from 10 to 40 DEG C, most preferably in the range of from 10 to 30 DEG C.

Preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material at an absorption zone at a pressure in the range of 1 to 75 bar, preferably 1.1 to 50 bar.

The contaminant-rich Fischer-Tropsch gas oil fraction may be contacted with the absorbent material in a batch or continuous manner. It is preferred that the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with an absorbent material under turbulent conditions to stimulate fluid / solid material interactions. In the case of a continuous mode, the absorption zone may preferably comprise a fixed bed reactor comprising at least one fixed bed of absorbent material. Preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material under continuous or induced mixing, which is particularly preferred in the case of batch processing.

Preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material in the absorption zone for a time sufficient to absorb at least a portion of the contaminant. In the case of batch contact of the contaminant-rich Fischer-Tropsch gas oil fraction with the water absorbent material, the contaminant-rich Fischer-Tropsch gas oil fraction is allowed to react for 1 minute to 48 hours, preferably 30 minutes to 24 hours, And may be contacted with the absorbent material for any time in the range of 60 minutes to 24 hours.

Preferably, in batch contact, the contaminant-rich Fischer-Tropsch gas oil fraction is added to the contaminant-rich Fischer-Tropsch fraction for an absorbent material in the range of from 0.5 to 200, more preferably from 1 to 175, and even more preferably from 5 to 125 - The Tropsch gas oil fraction may be contacted with the absorbent material at a volume ratio.

In the case of continuous contact of the contaminant-rich Fischer-Tropsch gas oil fraction with the water-absorbing material, the contaminant-rich Fischer-Tropsch gas oil fraction is allowed to react for 1 minute to 48 hours, preferably 30 minutes to 24 hours, And may be contacted with the absorbent material for any time in the range of 60 minutes to 24 hours. Preferably, the contaminant-rich Fischer-Tropsch gas oil fraction is introduced into the absorption zone at an LHSV of from 0.0001 to 0.01 s ^-1 , more preferably from 0.0001 to 0.005 s ^-1 , even more preferably from 0.0001 to 0.003 s ^-1 Absorbent material.

The absorption zone may comprise one or more absorption zones. In one embodiment, the absorption zone may comprise two or more absorption zones in series. Optionally, the absorption zone may comprise two or more compartments each containing a separate absorbent. This has the advantage that different contaminants can be removed separately to the extent necessary. One example may be a first compartment containing Mg silicate or similar absorbent material and a second compartment containing zeolite 13X or similar large pore molecular sieve absorbent material. This combination has the advantage that Mg silicate or similar absorbent material absorbs a portion of the oxygenated compound so that a larger portion of the absorbent capacity of the zeolite 13X or similar large pore molecular sieve absorbent material can be used for the aromatic contaminant. Alternatively, the absorption zone may comprise a mixture of two or more absorbent materials.

In a further embodiment, the absorption zone may comprise two or more absorption compartments in parallel, preferably comprising the same absorbent material. An advantage of providing a parallel absorption zone is that it allows continuous operation of the absorption process (described in more detail herein below) in which the alternate absorbent layer is regenerated while the remaining zones are in normal working mode.

Other embodiments may include both the parallel as well as the absorption zones aligned in series.

In the process according to the invention, the purified Fischer-Tropsch gas oil fraction is recovered from the absorption zone as a high purity Fischer-Tropsch gas oil fraction. The purified Fischer-Tropsch gas oil fraction recovered from the absorption zone is a reduced pollutant, i.e. the purified Fischer-Tropsch gas oil fraction has a lower contaminant concentration than the contaminant concentration of the contaminant-rich Fischer-Tropsch gas oil fraction . Preferably, at least one of the aromatics and oxygen-oxygen compound concentrations of the purified Fischer-Tropsch gas oil fraction is lower than the corresponding concentration of the pollutant-rich Fischer-Tropsch gas oil fraction. More preferably, the aromatics and oxygen content of the purified Fischer-Tropsch gas oil fraction is lower than the corresponding concentration of the contaminant-rich Fischer-Tropsch gas oil fraction.

Preferably, the purified Fischer-Tropsch gas oil fraction according to the present invention comprises

0 to 500 ppmw, more preferably 0 to 200 ppmw, even more preferably 0 to 100 ppmw, even more preferably 0 to 50 ppmw, based on the weight of the refined Fischer-Tropsch gas oil fraction, Most preferably from 0 to 25 ppmw of aromatic;

An oxygen-containing compound in the range of 0 to 3 ppmw, more preferably 1 ppmw, calculated on the basis of the weight of the elemental oxygen and the purified Fischer-Tropsch gas oil fraction in the oxygen-containing compound;

Sulfur-containing hydrocarbon compounds of from 0 to 3 ppmw, more preferably 1 ppmw, even more preferably 0.2 ppmw, calculated on the basis of the weight of elemental sulfur and the weight of the purified Fischer-Tropsch gas oil fraction, Containing hydrocarbon compounds; And / or

- nitrogen-containing hydrocarbon compounds in the range of 0 to 1 ppmw, calculated on the basis of the weight of the elemental nitrogen and the purified Fischer-Tropsch gas oil fraction in the nitrogen-containing hydrocarbon compound.

More preferably, the purified Fischer-Tropsch gas oil fraction according to the present invention comprises

0 to 500 ppmw, more preferably 0 to 200 ppmw, even more preferably 0 to 100 ppmw, even more preferably 0 to 50 ppmw, based on the weight of the refined Fischer-Tropsch gas oil fraction, Most preferably from 0 to 25 ppmw of aromatic;

An oxygen-containing compound in the range of 0 to 3 ppmw, more preferably 1 ppmw, calculated on the basis of the weight of the elemental oxygen and the purified Fischer-Tropsch gas oil fraction in the oxygen-containing compound;

Sulfur-containing hydrocarbon compounds in the range of 0 to 3 ppmw, more preferably 1 ppmw, even more preferably 0.2 ppmw, calculated on the basis of the weight of the elemental sulfur and the purified Fischer-Tropsch gas oil fraction, Hydrocarbon compounds; And

- nitrogen-containing hydrocarbon compounds in the range of 0 to 1 ppmw, calculated on the basis of the weight of the elemental nitrogen and the purified Fischer-Tropsch gas oil fraction in the nitrogen-containing hydrocarbon compound. The concentration of the oxygen compound, the sulfur-containing hydrocarbon compound and the nitrogen-containing hydrocarbon compound in the present invention is not based on the weight of the complete molecule including oxygen, sulfur and nitrogen atoms, And elemental oxygen, elemental sulfur, and elemental nitrogen to indicate that they are determined based on the weight of the nitrogen atoms.

If more than one contaminant-rich Fischer-Tropsch gas oil fraction is present, each contaminant-rich Fischer-Tropsch gas oil fraction is preferably provided in a separate absorption zone having a separate absorbing substance (s) To produce more than one purified Fischer-Tropsch gas oil fraction. This is particularly appropriate when the fractionation and absorption process steps are operated in a continuous manner. Each of these individual more than one purified Fischer-Tropsch gas oil fraction may preferably have its own specific contaminant concentration within the above range.

In addition to the purified Fischer-Tropsch gas oil fraction, the contaminant-containing absorbent material can be recovered from the absorption zone. Contaminant-containing absorbent materials can be recycled, especially if they are recycled to the absorption zone or, in particular, when they reach the adsorption capacity of the absorbent material. The absorbent material may be regenerated in any suitable manner for desorbing or otherwise removing contaminants from the absorbent material. For example, the absorbent material may be stripped using a desorbent, such as steam or nitrogen, or by heating the absorbent material in the presence of, for example, oxygen, oxygen-enriched air, air or hydrogen- Can be regenerated by burning or otherwise decomposing contaminants. The absorbent material can be regenerated and then recycled to the absorption zone.

In addition to the contaminant-rich Fischer-Tropsch gas oil fraction, a Fischer-Tropsch gasoline fraction that is not also rich in contaminants may be prepared in step (b). The Fischer-Tropsch gasoline fraction that is not rich in these contaminants is a Fischer-Tropsch gasoline fraction that can be recovered directly from the process, that is, this fraction does not undergo absorption step (c) as an additional Fischer-Tropsch gasoline fraction.

The high purity Fischer-Tropsch gasoline fraction recovered as the purified Fischer-Tropsch gasoline fraction (step (d)) from the absorption zone may optionally be used after further treatment for the desired use.

In a further aspect, the present invention provides the use of a purified Fischer-Tropsch gas oil fraction as a solvent or diluent in a functional fluid formulation. The functional fluid formulations herein may preferably be preparations comprising a purified Fischer-Tropsch gas oil fraction, including those further containing an additive compound. Typically, solvents, functional fluid formulations and diluents are used in a wide variety of fields, such as oil and gas exploration and production, process oils, agricultural chemicals, process chemicals, construction, food and related industries, paper, It can be used for various household and consumer products. The type of additive used in the functional fluid formulation according to the invention also depends on the type of fluid formulation. Additives to the functional fluid formulations include, but are not limited to, corrosion and rheology control products, emulsifiers and wetting agents, borehole stabilizers, high pressure and abrasion resistant additives, defoamers and anti-foam agents, pour point depressants and antioxidants It is not.

Preferred solvent, diluent and / or functional fluid applications using the purified Fischer-Tropsch gas oil fraction obtained in the process according to the invention as diluent oil or base oil include drilling fluids, heating oils, kerosene, , Concrete de-molding, pesticide spraying oil, paint and coatings, personal hygiene and cosmetics, consumer goods, pharmaceuticals, industrial and institutional cleaning, adhesives, inks, fragrances, sealants, explosives, water treatment, cleaners, polishes, car wax remover, , Transformer oil, Process oil, Process chemicals, Silicone-based resin, Two-stroke motorcycle oil, Metal washing, Dry cleaning, Lubricants, Metalworking fluids, Aluminum roll oil, Explosives, Chlorinated paraffin, Timber processing, polymer processing oils, rust preventing oils, buffering agents, greenhouse fuels, cracking fluids and fuel additive formulations, But is not limited thereto.

Typical solvent, diluent 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, &Quot;, George Wypych, Willem Andrew publishing, 2001, ISBN 0-8155-1458-1).

An advantage of using the Fischer-Tropsch gas oil fraction purified as a solvent, diluent or in a functional fluid formulation is that the purified Fischer-Tropsch gas oil fraction has a low flash point, a low viscosity and a high flash point. This combination of physical characteristics of the refined Fischer-Tropsch gas oil fraction is highly desirable for its use in functional fluid formulations with low viscosity requirements.

For example, in drilling fluid applications, the temperature of the drilling fluid during use can decrease, which can lead to increased viscosity of the drilling fluid. High viscosity can be detrimental to the beneficial use of drilling fluids. Thus, a purified Fischer-Tropsch gas oil fraction having a low viscosity and a high flash point obtained from the process according to the invention is highly desirable for its use in drilling fluid applications.

The use of the refined Fischer-Tropsch gas oil fraction as a diluent may include use as a diluent oil or base oil for solvent and / or functional fluid applications.

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

The term base oil refers to an oil to which another oil, solvent or substance has been added to produce a solvent or functional fluid formulation.

Advantages of using purified Fisher-Tropsch gas oil fraction as a diluent oil or base oil for solvents and / or functional fluid formulations include the use of a functional fluid formulation comprising a purified Fischer-Tropsch gas oil fraction further containing an additive compound Lt; / RTI >

In a further aspect, the present invention provides the use of a purified Fischer-Tropsch gas oil fraction obtained by the process according to the invention for improving biodegradability and reducing toxicity in solvent and / or functional fluid applications .

As described above, the purified Fischer-Tropsch gas oil fraction preferably has very low levels of aromatic, sulfur, nitrogen compounds, preferably no polycyclic aromatic hydrocarbons. This low level can result in low aquatic bio-toxicity, low sediment organism toxicity, low human and animal toxicity, and low global ecotoxicity of the Fischer-Tropsch gas oil fraction, which is non-limitingly refined. The molecular structure of the refined Fischer-Tropsch gas oil fraction can lead to easy biodegradability of the Fischer-Tropsch-derived gas oil.

Any additional Fischer-Tropsch gas oil fractions obtained in step (b) of the process, which are not enriched with contaminants, may be separated in one or more ways as herein before described, similar to the purified Fischer-Tropsch gas oil fraction Can be used.

The specific use of a particular Fischer-Tropsch gas oil fraction may vary depending upon the exact composition and characteristics of a particular Fischer-Tropsch gas oil fraction. The Fischer-Tropsch-derived gas oil provided as feedstock in step (a) of the process according to the invention is derived from a feedstock other than crude oil, such as methane, coal or biomass, and is produced in a Fischer-Tropsch process It is synthetic gas oil. The preparation of the Fischer-Tropsch-derived gas oil is described, for example, in WO02 / 070628 and WO-A-9934917, especially in Example VII of WO-A-9934917 using the catalyst of Example III of WO- , All of which are incorporated herein by reference. As mentioned above, these Fischer-Tropsch-derived gas oils have different molecular compositions and have significantly different properties compared to crude oil-derived gas oil. Thus, the Fischer-Tropsch-derived gas oil can be clearly distinguished from the crude oil-derived gas oil. A number of preferred characteristics of a Fischer-Tropsch-derived gas oil are provided herein.

Preferably, the Fischer-Tropsch-derived gas oil comprises greater than 50 wt%, more preferably greater than 70 wt% isoparaffin, more preferably greater than 80 wt% isoparaffin. Preferably, the Fischer-Tropsch-derived gas oil is at least 2, more preferably at least 2.8, even more preferably at least 3.5, even more preferably at least 3.7, even more preferably at least 4 More preferably an i / n ratio of 4.5 or more.

Preferably, the Fischer-Tropsch-derived gas oil is present in the Fischer-Tropsch-derived gas oil in an amount of from 20 to 40 wt%, preferably from 21 to 37 wt%, based on the total weight of isoparaffin, Comprises from 23 to 37 wt% mono-methyl branched isoparaffins.

Preferably, the Fischer-Tropsch-derived gas oil has an initial boiling point of at least 150 캜 and a final boiling point of at most 450 캜 at atmospheric conditions. Suitably, the Fischer-Tropsch-derived gas oil has an initial boiling point of at least 175 캜 at atmospheric conditions as measured using ASTM D86. It will be appreciated that the initial boiling point, final boiling point, and boiling range provided herein when describing the present invention are the initial boiling point, final boiling point, and boiling range as measured by ASTM D86. Also, the initial boiling point, final boiling point, and boiling range, as measured by ASTM D86 for the Fischer-Tropsch-derived gas oil fraction, are determined by the respective ASTM D86-based initial boiling point of the Fischer-Tropsch- And does not exempt the presence of compounds or fractions with intrinsic boiling temperatures lower or higher than the D86-based final boiling point.

The Fischer-Tropsch-derived gas oil feedstock is preferably at a temperature of from 330 to 450 DEG C, more preferably from 331 to 370 DEG C, even more preferably from 332 to 365 DEG C, from 333 to 351 DEG C, Has a final boiling point of from 336 to 348 [deg.] C, even more preferably from 339 to 345 [deg.] C. The boiling point in an atmospheric condition means the boiling point measured by ASTM D86.

The Fischer-Tropsch-derived gas oil, also referred to as the Fischer-Tropsch full range gas flow, contains paraffins, including isoparaffins and normal paraffins, having alkyl chain lengths ranging from 7 to 30 carbon atoms , Preferably a paraffin having from 9 to 25 carbon atoms; The Fischer-Tropsch derived gas oil comprises a Fischer-Tropsch derived paraffin having 9 to 25 carbon atoms, preferably 7 to 30 carbon atoms, based on the total amount of Fischer-Tropsch derived paraffins More preferably at least 85 wt%, more preferably at least 90 wt%, more preferably at least 95 wt%, based on the amount of Fischer-Tropsch- And even more preferably at least 98 wt%.

In addition, the density of the Fischer-Tropsch derived gas oil at 15 DEG C according to ASTM D4052 is preferably in the range of 774 kg / m3 to 782 kg / m3, more preferably 775 kg / m3 to 780 kg / m3 And preferably 776 kg / m 3 to 779 kg / m 3.

Suitably, the kinematic viscosity at 40 캜 according to ASTM D445 of the Fischer-Tropsch derived gas oil is from 2.3 to 3.0 cSt, preferably from 2.5 cSt to 2.9 cSt.

In addition, the pour point of the Fischer-Tropsch-derived gas oil (according to ASTM D97) is preferably less than -10 ° C, more preferably less than -15 ° C, more preferably less than -17 ° C, 20 ° C, more preferably less than -22 ° C, even more preferably less than -27 ° C, preferably more than -40 ° C.

Suitably, the cloud point of the Fischer-Tropsch derived gas oil (according to ASTM D2500) is preferably less than -10 DEG C, more preferably less than -15 DEG C, more preferably less than -18 DEG C, Is less than -20 占 폚, more preferably less than -22 占 폚, most preferably less than -27 占 폚, preferably more than -40 占 폚.

Preferably, the flash point according to ASTM D93 of the Fischer-Tropsch-derived gas oil is at least 60 ° C, more preferably at least 70 ° C, even more preferably at least 80 ° C, even more preferably at least 85 ° C.

Fischer-Tropsch-derived gas oil The fume point according to ASTM D1322 is more than 50 mm.

Typically, the Fischer-Tropsch-derived gas oil provided as feedstock to the process according to the invention is

0 to 300 ppmw, more preferably 0 to 200 ppmw, even more preferably 0 to 100 ppmw, even more preferably 0 to 50 ppmw, based on the weight of the Fischer-Tropsch derived gas oil, Preferably 0 to 25 ppmw of aromatic;

Oxygen-oxygen compounds in the range of 0 to 3 ppmw, more preferably 0 to 1 ppmw, calculated on the basis of the weight of elemental oxygen in the oxygen-containing compound and the weight of the Fischer-Tropsch-derived gas oil;

0 to 3 ppmw, more preferably 0 to 1 ppmw, even more preferably 0 to 0.2 ppmw, calculated on the basis of the weight of the elemental sulfur in the sulfur-containing hydrocarbon compound and the weight of the Fischer-Tropsch- Of a sulfur-containing hydrocarbon compound;

Nitrogen-containing hydrocarbon compounds in the range of 0 to 1 ppmw, calculated on the basis of the weight of the elemental nitrogen in the nitrogen-containing hydrocarbon compound and the weight of the Fischer-Tropsch-derived gas oil; And / or

- from 0 to 2 wt% based on the weight of the Fischer-Tropsch derived gas oil,

Wherein at least one of the aromatic, oxygen-containing compound, sulfur-containing hydrocarbon compound and nitrogen-containing hydrocarbon compound is contained in the Fischer-Tropsch-derived gas oil feedstock, Is not. In particular, at least one of the aromatic and oxygen-containing compounds is contained in the Fischer-Tropsch-derived gas oil feedstock, that is, at least one of the aromatic and oxygen-containing compound concentrations is not zero.

Preferably, the Fischer-Tropsch-derived gas oil provided as feedstock in the process according to the invention is

0 to 300 ppmw, more preferably 0 to 200 ppmw, even more preferably 0 to 100 ppmw, even more preferably 0 to 50 ppmw, based on the weight of the Fischer-Tropsch derived gas oil, Preferably 0 to 25 ppmw of aromatic;

Oxygen-oxygen compounds in the range of 0 to 3 ppmw, more preferably 0 to 1 ppmw, calculated on the basis of the weight of elemental oxygen in the oxygen-containing compound and the weight of the Fischer-Tropsch-derived gas oil;

0 to 3 ppmw, more preferably 0 to 1 ppmw, even more preferably 0 to 0.2 ppmw, calculated on the basis of the weight of the elemental sulfur in the sulfur-containing hydrocarbon compound and the weight of the Fischer-Tropsch- Of a sulfur-containing hydrocarbon compound;

Nitrogen-containing hydrocarbon compounds in the range of 0 to 1 ppmw, calculated on the basis of the weight of the elemental nitrogen in the nitrogen-containing hydrocarbon compound and the weight of the Fischer-Tropsch-derived gas oil; And

-Fischer-Tropsch-derived gas oil, wherein at least one of the aromatic, oxygen-containing compound, sulfur-containing hydrocarbon compound and nitrogen-containing hydrocarbon compound is selected from the group consisting of Fischer- - Tropsch-derived gas oil feedstock, i. E. At least one of the concentrations is not zero. In particular, at least one of the aromatic and oxygen-containing compounds is contained in the Fischer-Tropsch-derived gas oil feedstock, that is, at least one of the aromatic and oxygen-containing compound concentrations is not zero. The concentration of the oxygen compound, the sulfur-containing hydrocarbon compound and the nitrogen-containing hydrocarbon compound in the present invention is not based on the weight of the complete molecule including oxygen, sulfur and nitrogen atoms, And elemental oxygen, elemental sulfur, and elemental nitrogen to indicate that they are determined based on the weight of the nitrogen atoms.

In addition, the Fischer-Tropsch derived gas oil preferably comprises less than 300 ppmw of polycyclic aromatic hydrocarbons, more preferably less than 25 ppmw of polycyclic aromatic hydrocarbons, more preferably less than 25 ppmw, based on the weight of the Fischer-Tropsch- Most preferably less than 1 ppmw of polycyclic aromatic hydrocarbons. In addition, the Fischer-Tropsch derived gas oil comprises n-paraffin and may comprise a cyclo-alkane.

In step (b) of the process according to the invention, the Fischer-Tropsch derived gas oil feedstock comprises at least two Fischer-Tropsch gas oil fractions, preferably at least three Fischer-Tropsch gas oil fractions, Preferably fractionated into at least four Fischer-Tropsch gas oil fractions. In particular, at least one of the Fischer-Tropsch gas oil fractions obtained in step (b), in particular the contaminant-rich Fischer-Tropsch gas oil fraction, may exhibit a stronger odor than the Fischer-Tropsch-derived gas oil feedstock .

Preferably, if step (b), or if the Fischer-Tropsch gas oil fraction is provided in step (c), ultimately at least one of the Fischer-Tropsch gas oil fractions obtained in step (d) Preferably at most 250 ° C, more preferably at most 215 ° C. Preferably, at least one of the Fischer-Tropsch gas oil fractions comprises (1) a Fischer-Tropsch gas oil fraction having a final boiling point of at most 180 DEG C, preferably at most 170 DEG C, (2) Tropsch gas fraction having an initial boiling point of at least 170 DEG C and a final boiling point of at most 200 DEG C, preferably at most 190 DEG C, (3) an initial boiling point of at least 180 DEG C, preferably at least 190 DEG C, (4) a final boiling point of 205 DEG C or higher, preferably 215 DEG C or higher and an initial boiling point of at most 260 DEG C, preferably at most 250 DEG C, and Fischer-Tropsch gas oil fraction, wherein the boiling point is measured at ambient conditions as measured using ASTM D86.

In particular, when step (b), or when the Fischer-Tropsch gas oil fraction is provided in step (c), ultimately at least one of the Fischer-Tropsch gas oil fractions obtained in step (d) (2) a final boiling point of 160 ° C or higher, preferably an initial boiling point of 170 ° C or higher and a maximum of 200 ° C, preferably of at most 190 ° C, at a final boiling point of at most 170 ° C And (3) a Fischer-Tropsch gas oil fraction having an initial boiling point of at least 180 ° C, preferably at least 190 ° C, and a final boiling point of at most 225 ° C, preferably at most 215 ° C Wherein the boiling point is measured at atmospheric conditions as determined using ASTM D86.

More particularly, if step (b), or if the Fischer-Tropsch gas oil fraction is provided in step (c), at least one of the Fischer-Tropsch gas oil fractions ultimately obtained in step (d) Tropsch gas oil fraction having an initial boiling point of at least 170 ° C, preferably at least 200 ° C and preferably at most 190 ° C, (3) an initial boiling point of at least 180 ° C, preferably at least 190 ° C, and A Fischer-Tropsch gas oil fraction having a final boiling point of at most 225 ° C, preferably at most 215 ° C, wherein the boiling point is determined by atmospheric conditions when measured using ASTM D 86 Lt; / RTI >

These Fischer-Tropsch gas oil fractions obtained in step (b), having a final boiling point of up to 260 ° C, preferably lower, are particularly prone to undesirable odor characteristics, and therefore, It has been found that it has the advantage of eliminating contaminants that cause unwanted odors.

Preferably, at least one of said fractions obtained in step (b) is provided as step (c) as a contaminant-rich Fischer-Tropsch gas oil fraction.

At least one of the Fischer-Tropsch gas oil fractions obtained in step (b), in particular the contaminant-rich Fischer-Tropsch gas oil fraction, has a lower number of Sabbaths than the number of Sabbaths of Fischer-Tropsch- Can be displayed.

The high purity Fischer-Tropsch gas oil fraction (s) recovered as the Fischer-Tropsch gas oil fraction (s) refined in step (d) may be recovered in step (d) will have the same boiling point range as the contaminant-rich Fischer-Tropsch gas oil fraction provided in step c).

Preferably, when step (b), or when the Fischer-Tropsch gas oil fraction is provided in step (c), ultimately at least one of the Fischer-Tropsch gas oil fractions obtained in step (d) Preferably 300 DEG C or higher, and more preferably 310 DEG C or higher. Preferably, at least one of the Fischer-Tropsch gas oil fractions comprises (1) a Fischer-Tropsch fraction having an initial boiling point of greater than 260 ° C, preferably greater than 270 ° C, and a final boiling point of at most 320 ° C, (2) a Fischer-Tropsch gas oil fraction selected from the group consisting of a Fischer-Tropsch gas oil fraction having an initial boiling point of at least 310 ° C, preferably at least 330 ° C, more preferably at least 360 ° C, Where the boiling point is measured at ambient conditions when measured using ASTM D86.

In particular, when step (b), or when the Fischer-Tropsch gas oil fraction is provided in step (c), ultimately at least one of the Fischer-Tropsch gas oil fractions obtained in step (d) May be a Fischer-Tropsch gas oil fraction having an initial boiling point of at least 330 ° C, more preferably at least 360 ° C, wherein the boiling point is measured at ambient conditions as measured using ASTM D86.

In particular, the Fischer-Tropsch gas oil fraction having an initial boiling point of more than 260 < 0 > C obtained in step (b) is subject to discoloration, that is to say, a lower number of Sabbaths than the Fischer- Of the number of seeds. More particularly, the contaminant-rich Fischer-Tropsch gas oil fraction having an initial boiling point of more than 330 ° C obtained in step (b), especially greater than 360 ° C obtained in step (b), is less than 28, In particular less than 25.

Preferably, at least one of said fractions obtained in step (b) is provided as step (c) as a contaminant-rich Fischer-Tropsch gas oil fraction.

The high purity Fischer-Tropsch gas oil fraction (s) recovered as the Fischer-Tropsch gas oil fraction (s) refined in step (d) is subjected to step (c) to produce the refined Fischer-Tropsch gas oil fraction Will have essentially the same boiling range as the contaminant-rich Fischer-Tropsch gas oil fraction provided in the < RTI ID = 0.0 >

Preferably, at least the purified Fischer-Tropsch gas oil fraction (s) recovered as the high purity Fischer-Tropsch gas oil fraction in step (b) or the Fischer-Tropsch gas oil fraction obtained in step (d) One has an i / n ratio ranging from 2 to 6. Preferably, most, or more than half, of the Fischer-Tropsch gas oil fraction obtained in step (b) or (d) has an i / n ratio in the range of 2 to 6. The high i / n ratio can in particular have an effect on the viscosity of the Fischer-Tropsch gas oil fraction. An increase in the relative concentration of isoparaffin may reduce the overall viscosity of the Fischer-Tropsch gas oil fraction. By fractionating the Fischer-Tropsch-derived gas oil feedstock, fractions with improved i / n ratios can be obtained depending on the particular intended use.

Preferably, at least one of the Fischer-Tropsch gas oil fractions obtained in step (b) or (d) is present in the Fischer-Tropsch gas oil fraction in an amount of from 30 to 75 wt%, more preferably By weight of mono-methyl branched isoparaffins in the range of 35 to 70 wt%, more preferably in the range of 35 to 60 wt%.

Preferably, the majority, or more than half, of the Fischer-Tropsch gas oil fraction obtained in step (b) or (d) is present in the Fischer-Tropsch gas oil fraction in an amount of from 30 to 75 wt%, based on the total weight of isoparaffin, ≪ / RTI > range of mono-methyl branched isoparaffins. Preferably, at least one of the Fischer-Tropsch gas oil fraction obtained in step (b) or (d) has a higher weight percent based on the total weight of isoparaffin than the Fischer-Tropsch- Of mono-methyl branched isoparaffins. More preferably, at least two, more preferably at least three, of the Fischer-Tropsch gas oil fractions obtained in step (b) or (d) are less than the Fischer-Tropsch derived gas oil feedstock Higher percent by weight mono-methyl branched isoparaffins based on the total weight of paraffins.

Mono-methyl branched isoparaffins exhibit favorable biodegradation characteristics over other isoparaffins. The relatively high concentration of mono-methyl isoparaffins on the other isoparaffins can in particular affect the biodegradation characteristics of the Fischer-Tropsch gas oil fraction in particular. Increasing the relative concentration of mono-methyl isoparaffin to other isoparaffins can improve the biodegradation characteristics of the Fischer-Tropsch gas oil fraction by overcoming the biodegradation characteristics of the Fischer-Tropsch-derived gas oil feedstock .

In a further aspect,

i) providing a contaminant-containing Fischer-Tropsch gas oil fraction having a final boiling point of less than or equal to 260 DEG C in an absorption zone comprising at least one water absorbent material and contacting the contaminant-containing Fischer-Tropsch gas oil fraction with the water absorbent material Absorbing at least a portion of the contaminant;

ii) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone as a high purity Fischer-Tropsch gas oil fraction, wherein the purified Fischer-Tropsch gas oil fraction is separated from the contaminant-containing Fischer-Tropsch gas oil fraction Lt; RTI ID = 0.0 > contaminant-reduced

And a second fraction of the purified Fischer-Tropsch gas oil fraction.

The limiting characteristics described above for the first method according to the invention herein apply only to a minor modification of the second method according to the invention. The limiting characteristics described above for the contaminant-rich Fischer-Tropsch gas oil fraction of the first process according to the invention herein are only a fraction of that required for the contaminant-containing Fischer-Tropsch gas oil fraction of the second process according to the invention And applied.

The limiting characteristics described above for each of steps (c) and (d) of the first method according to the present invention can be obtained by modifying only the necessary parts of steps (i) and (ii) of the second method according to the invention .

Preferably, in the second method according to the present invention, the contaminants are selected from the group consisting of oxygenated compounds and aromatics.

Preferably, in the second process according to the invention, the water absorbent material is selected from the group consisting of molecular sieve materials, preferably zeolite X, zeolite 13X, zeolite Y, dealuminated zeolite Y, superstable Y, ZSM-12, mordenite, Zeolite beta, zeolite L, zeolite omega, preferably zeolite 13X.

Preferably, in the second method according to the invention, the contaminant-containing Fischer-Tropsch-derived gas oil is contacted with the absorbent material at a temperature in the range of 0 to 150 ° C.

Preferably, in the second method according to the present invention, the contaminant-containing Fischer-Tropsch gas oil fraction is contacted with the absorbent material in a fixed bed reactor comprising at least one fixed bed of absorbent material.

The present invention also provides the use of the purified Fischer-Tropsch gas oil fraction obtained in the second process as a solvent, diluent or functional fluid.

In a further aspect,

v) providing a contaminant-containing Fischer-Tropsch gas oil fraction having an initial boiling point of greater than 260 DEG C, to an absorption zone comprising at least one water-absorbing material, contacting the contaminant-containing Fischer-Tropsch gas oil fraction with the water- Absorbing at least a portion of the contaminant;

vv) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone as a high purity Fischer-Tropsch gas oil fraction, wherein the purified Fischer-Tropsch gas oil fraction is separated from the contaminant-containing Fischer-Tropsch gas oil fraction Lt; RTI ID = 0.0 > contaminant-reduced

And a third fraction of the purified Fischer-Tropsch gas oil fraction.

The limiting characteristics described above for the first method according to the invention herein apply only to a minor modification of the third method according to the invention. The limiting characteristics described above for the contaminant-rich Fischer-Tropsch gas oil fraction of the first process according to the invention herein are only a fraction of that required for the contaminant-containing Fischer-Tropsch gas oil fraction of the third process according to the invention And applied.

The limiting characteristics described above for each of steps (c) and (d) of the first method according to the invention herein are only slightly modified as required for each of the steps (v), (vv) of the third method according to the invention .

Preferably, in the third method according to the present invention, the contaminants are selected from the group consisting of oxygenated compounds and aromatics.

Preferably, in the third method according to the present invention, the water absorbent material is a zeolite X, preferably zeolite X, zeolite 13X, zeolite Y, dealuminated zeolite Y, superstabil Y, ZSM-12, mordenite, Zeolite beta, zeolite L, zeolite omega, preferably zeolite 13X.

Preferably, in the third method according to the invention, the contaminant-containing Fischer-Tropsch-derived gas oil is contacted with the absorbent material at a temperature in the range of 0 to 150 ° C.

Preferably, in the third method according to the present invention, the contaminant-containing Fischer-Tropsch gas oil fraction is contacted with the absorbent material in a fixed bed reactor comprising at least one fixed bed of absorbent material.

The present invention also provides the use of the purified Fischer-Tropsch gas oil fraction obtained in the third process as a solvent, diluent or functional fluid.

Example

The invention is further illustrated by the following non-limiting examples.

Example 1.

The Fischer-Tropsch-derived gas oil having a boiling range of 185 to 350 DEG C as measured by ASTM D86 was fractionated by distillation into 7 fractions. The characteristics of the produced Fischer-Tropsch gas oil fraction are shown in Table 1. Aromatic content was determined by UV absorption spectrometry. The ratio of isoparaffin to normal paraffin and the concentration of mono-methyl branched isoparaffin were determined using gas chromatography.

Odor test procedure:

The fragrance of the Fischer-Tropsch-derived gas oil feed and resulting contaminant-rich and purified fractions was measured by a four member panel using the following procedure:

(1) Provide 30 mL of sample and store in a 60 mL glass bottle with screw cap;

(2) removing the cap and causing the panel member to be immediately exposed to the odor of the sample to record the odor characteristics of the sample;

(3) Immediately after exposing the panel member to the odor of the sample, the cap was reset.

During the odor test the following conditions were observed:

(a) All panel members were allowed to perform the test within 4 hours on the same day.

(b) Each panel member performed an odor test on the same sample, all in the same space at the same time, and evaluated.

Immediately after exposure to the individual samples, panel members were provided with the definition of odor, with 5 being a bad odor and 1 being a good odor. The reported odor quality was based on the number of votes provided by panel members.

<Table 1>

*% Of mono-methyl branched isoparaffin based on the total weight of isoparaffin in the sample.

The feedstock contains compounds that boil separately below the ASTM D86-based initial boiling point.

The feed gas oil had a relatively low odor and a relatively low aromatic content.

As can be seen in Table 1, aromatics have accumulated in the lightweight fraction during fractionation. In addition, the odor was the most pronounced in the low boiling fraction, strong and distinct from the feed.

Example 2.

Three Fischer-Tropsch gas oil fraction samples representing samples GS160, GS170 and GS190 from Example 1 were contacted with the absorbent material in the absorption zone. Each Fischer-Tropsch gas oil fraction was separately contacted with fresh absorbent material. The Fischer-Tropsch gas oil fraction sample was first contacted with the Mg silicate absorbent material and then contacted with the zeolite 13X absorbent material. The volume ratio of the Fischer-Tropsch gas oil fraction to the absorbent material was 82 for zeolite 13X and 210 for Mg silicate. The Fischer-Tropsch gas oil fraction was contacted with the absorbent material at ambient pressure and temperature. The properties of the purified Fischer-Tropsch gas oil fraction are shown in Table 2.

<Table 2>

As can be seen from Table 2, Mg silicate did not significantly remove the aromatics from the contaminant-rich Fischer-Tropsch gas oil fraction. However, improvement of odor was observed. This was due to the absorption of other contaminants, especially oxygen-containing compounds. Zeolite 13X absorbed a significant portion of the aromatics and further improved odor was observed.

Example 3.

A Fischer-Tropsch gas oil fraction sample showing sample GS270 from Example 1 was contacted with the zeolite 13X absorbent material in the absorption zone. The properties of the refined Fischer-Tropsch gas oil fraction are shown in Table 3. As can be seen in Table 3, both the color and odor characteristics of the Fischer-Tropsch gas oil fraction samples were significantly improved after contacting the contaminant-rich fraction with the water absorbent material in accordance with the present invention.

<Table 3>

Claims (15)

a) providing a Fischer-Tropsch-derived gas oil feedstock comprising at least one contaminant, wherein the Fischer-Tropsch-derived gas oil has a composition of from 7 to 30 carbon atoms Tropsch derived paraffins having an alkyl chain length of from 9 to 25 carbon atoms and comprising a paraffin comprising isoparaffin and normal paraffin in an amount based on the total amount of the Fischer-Tropsch derived paraffins 70 wt% or more;
b) feeding the Fischer-Tropsch-derived gas oil feedstock to a fractionation zone and separating the Fischer-Tropsch-derived gas oil feedstock into two or more Fischer-Tropsch gas oil fractions having different boiling ranges Wherein the at least one Fischer-Tropsch gas oil fraction is at least one contaminant enriched contaminant-rich Fischer-Tropsch gas oil fraction for the feedstock;
c) providing a contaminant-rich Fischer-Tropsch gas oil fraction in an absorption zone comprising at least one absorbent material, contacting the contaminant-rich Fischer-Tropsch gas oil fraction with an absorbent material to absorb at least a portion of the contaminant step; And
d) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone, wherein the purified Fischer-Tropsch gas oil fraction is contaminant-reduced for the contaminant-rich Fischer-Tropsch gas oil fraction
/ RTI &gt; wherein the crude Fischer-Tropsch gaseous fraction is purified. The method of claim 1, wherein the at least one contaminant is selected from the group consisting of oxygenated compounds and aromatics. 3. The process according to claim 1 or 2, wherein the one or more water absorbent materials are selected from the group consisting of molecular sieve materials, preferably zeolite X, zeolite 13X, zeolite Y, dealuminated zeolite Y, superstabil Y, ZSM- Zeolite beta, zeolite L, zeolite omega, preferably zeolite 13X. 4. The process according to any one of claims 1 to 3, wherein the absorption zone comprises two or more absorbent materials, preferably at least zeolite 13X and magnesium silicate. 5. The process according to any one of claims 1 to 4, wherein the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with the absorbent material at a temperature in the range of 0 to 150 &lt; 0 &gt; C. 6. A method according to any one of claims 1 to 5, wherein the contaminant-rich Fischer-Tropsch gas oil fraction is contacted with an absorbent material in a fixed bed reactor comprising at least one fixed bed of an absorbent material. 7. A process according to any one of claims 1 to 6, wherein the contaminant-rich Fischer-Tropsch gas oil fraction has a final boiling point of less than or equal to 260 &lt; 0 &gt; C. 7. The process according to any one of claims 1 to 6, wherein the contaminant-rich Fischer-Tropsch gas oil fraction has an initial boiling point of greater than 260 &lt; 0 &gt; C. 9. The process according to any one of claims 1 to 8, wherein the contaminant-rich Fischer-Tropsch gas oil fraction has a Saybolt number of less than 30. 10. The process according to any one of claims 1 to 9, wherein the Fischer-Tropsch-derived gas oil has a final boiling point of 450 DEG C or less. Use of the purified Fischer-Tropsch gas oil fraction obtained in the process of any one of claims 1 to 10 as a solvent, diluent or functional fluid. i) providing a contaminant-containing Fischer-Tropsch gas oil fraction containing greater than 50 wt% of isoparaffin and having a final boiling point below 260 DEG C in an absorption zone comprising at least one water absorbent material, Contacting the Tropsch gas oil fraction with an absorbent material to absorb at least a portion of the contaminant; And
ii) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone, wherein the purified Fischer-Tropsch gas oil fraction is contaminant-reduced for the contaminant-containing Fischer-Tropsch gas oil fraction;
/ RTI &gt; wherein the crude Fischer-Tropsch gaseous fraction is purified. Use of the purified Fischer-Tropsch gas oil fraction obtained in the process of claim 12 as a solvent, diluent or functional fluid. v) providing a contaminant-containing Fischer-Tropsch gas oil fraction having an initial boiling point greater than 260 DEG C in an absorption zone comprising at least one water-absorbing material, contacting the contaminant-containing Fischer-Tropsch gas oil fraction with the water- Absorbing at least a portion of the contaminant; And
vv) recovering the purified Fischer-Tropsch gas oil fraction from the absorption zone, wherein the purified Fischer-Tropsch gas oil fraction is contaminant-reduced for the contaminant-containing Fischer-Tropsch gas oil fraction
/ RTI &gt; wherein the crude Fischer-Tropsch gaseous fraction is purified. Use of the purified Fischer-Tropsch gas oil fraction obtained in the process of claim 14 as a solvent, diluent or functional fluid.